JP2549583B2 - Method for preventing fading of unfixed dye in reactive dyeing of cellulose fiber - Google Patents
Method for preventing fading of unfixed dye in reactive dyeing of cellulose fiberInfo
- Publication number
- JP2549583B2 JP2549583B2 JP3135446A JP13544691A JP2549583B2 JP 2549583 B2 JP2549583 B2 JP 2549583B2 JP 3135446 A JP3135446 A JP 3135446A JP 13544691 A JP13544691 A JP 13544691A JP 2549583 B2 JP2549583 B2 JP 2549583B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- dyeing
- discoloration
- dye
- fading
- 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
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、セルロース繊維の反応
染色における未固着の染料が、ＳＯ2 、ＮＯ、ＮＯ2 等
の燃焼廃ガスと接触した際に退色するのを防止するため
の方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing unfixed dyes in reactive dyeing of cellulose fibers from fading when they come into contact with combustion exhaust gas such as SO 2 , NO and NO 2. It is a thing.
【０００２】[0002]
【従来の技術】これまでに、繊維の染色に使用される染
料が、ある種のガスと接触することによって変退色を起
こすことが知られており、又、このような変退色は、染
料が固着される繊維の種類によって、かなり挙動が異な
ることも知られている。2. Description of the Related Art Up to now, it has been known that a dye used for dyeing a fiber causes a discoloration or fading when it comes into contact with a certain gas. It is also known that the behavior varies considerably depending on the type of the fibers to be fixed.
【０００３】例えば、ジアセテート繊維やトリアセテー
ト繊維の染色において分散染料を使用した場合には、燃
焼廃ガスと接触した際、著しい退色が起こるが、ポリエ
ステル繊維の場合では、このような退色はほとんど起こ
らない。又、セルロース繊維の場合では、一般には燃焼
廃ガスとの接触による変退色は生じにくいが、条件によ
っては問題を生ずる場合がある。この場合において、変
退色の大きな要因となるのは、光、熱、湿度、染料の種
類、染色濃度、染料の繊維への固着状態等である。For example, when disperse dyes are used for dyeing diacetate fibers or triacetate fibers, remarkable discoloration occurs when contacting with combustion exhaust gas, but in the case of polyester fibers, such discoloration hardly occurs. Absent. Further, in the case of cellulose fibers, generally, discoloration and fading due to contact with combustion waste gas is unlikely to occur, but problems may occur depending on conditions. In this case, the major factors that cause discoloration and fading are light, heat, humidity, the type of dye, the dyeing density, the fixing state of the dye on the fiber, and the like.
【０００４】セルロース繊維の染色において、これまで
に広く使用されてきた染料はビニルスルフォン型染料で
あり、このタイプの染料には、色相が鮮明であること、
一般に溶解性が良好であること、連続染色にも十分適し
ていること等の長所があるが、中色以下、特に１〜２重
量％以下の低い染色濃度で変退色を起こし易く、又、湿
度が高い場合にも変退色を起こし易いことが知られてい
る。A dye which has been widely used until now in dyeing cellulose fibers is a vinyl sulfone type dye, and this type of dye has a clear hue.
In general, it has advantages such as good solubility and good suitability for continuous dyeing, but it tends to cause discoloration and fading at low dyeing concentrations of medium or less, especially 1 to 2% by weight or less, and humidity. It is known that discoloration and fading easily occur even when the value is high.
【０００５】更に、セルロース繊維の反応染色にあって
は、変退色に大きな影響を及ぼす要因として、染色後の
染料の固着状態が挙げられ、染料が未固着の状態である
場合には、燃焼廃ガスとの接触による変退色が生じ易
い。一般に、セルロース繊維用染料に対して変退色をも
たらすことが知られているガスとしては、Ｃｌ2 、Ｂｒ
2 、ＳＯ2 、ＮＯ、ＮＯ2 等があり、この中で最も大き
な原因群であると考えられているのは、燃焼廃ガス中に
含まれるＳＯ2 、ＮＯ、ＮＯ2 である。Further, in the reactive dyeing of cellulose fibers, a factor that greatly affects discoloration and fading is a fixed state of the dye after dyeing. When the dye is not fixed, combustion waste is generated. Discoloration and fading easily occur due to contact with gas. In general, gases known to cause discoloration and fading of dyes for cellulose fibers include Cl 2 and Br.
There are 2, SO 2, NO, NO 2 , etc., what is believed to be the most significant source group in this, SO 2, NO contained in the combustion exhaust gas, a NO 2.
【０００６】そして、このようなＳＯ2 、ＮＯ、ＮＯ2
等の燃焼廃ガスとの接触により、セルロース繊維の反応
染色における未固着染料が変退色を起こした場合には、
色彩の劣化により染色製品の品質及び価値が著しく低下
することになるため、未固着染料が燃焼廃ガスと接した
場合にも退色を起こさないようにするための変退色防止
法を開発することは極めて重要な課題である。しかしな
がら、今日までに、効果的に未固着染料の変退色を防止
でき、しかも染色作業が安全かつ簡単であるような方法
は提案されていない。And, such SO 2 , NO, NO 2
When unfixed dye in reactive dyeing of cellulose fiber causes discoloration due to contact with combustion waste gas such as
Since the quality and value of dyed products will be significantly reduced due to color deterioration, it is not possible to develop a discoloration and fading prevention method to prevent discoloration even when unfixed dye comes into contact with combustion exhaust gas. This is a very important issue. However, to date, no method has been proposed that can effectively prevent discoloration and fading of unfixed dyes and that the dyeing work is safe and easy.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、上記の欠点
を改良し、燃焼廃ガスとの接触によって変退色を起こし
易い未固着染料を効果的に保護して、安全かつ簡単に染
色作業を行うことができる、セルロース繊維の反応染色
における未固着染料の退色防止法を提供することを課題
とする。DISCLOSURE OF THE INVENTION The present invention improves the above-mentioned drawbacks and effectively protects unfixed dyes, which are liable to undergo discoloration or fading due to contact with combustion exhaust gas, for safe and easy dyeing work. An object of the present invention is to provide a method of preventing fading of unfixed dye in reactive dyeing of cellulose fiber, which can be performed.
【０００８】本発明者らは、セルロース繊維用染料が変
退色を起こす際に最も大きな原因であると考えられてい
るＳＯ2 、ＮＯ及びＮＯ2 ガスをテストガスとして使用
し、ＪＩＳ Ｌ０６５５−６７及び、ＡＡＴＣＯ試験法
２３−１９６２に準ずる方法を用いて退色防止効果を研
究した。The present inventors have used SO 2 , NO and NO 2 gas, which are considered to be the most important cause when the dye for cellulose fiber causes discoloration and fading, as JIS G0655-67 and JIS L0655-67. , AATCO Test Method 23-1962 was used to study the effect of preventing fading.
【０００９】その結果、特定の化学構造を有する化合物
を、染色液又は捺染糊中に添加することにより、燃焼廃
ガスと接触した際の未固着染料の退色が防止できること
を見い出し、本発明を完成させた。尚、本発明の方法に
よって未固着染料の退色が防止できることを確認する
際、ＪＩＳ Ｌ０６５５−６７に準ずる方法では、単独
ガスとして燐酸−亜硝酸ソーダによるＮＯ、ＮＯ2 ガス
を使用し、ＡＡＴＣＯ試験法２３−１９６２に準ずる方
法では、混合ガスとして都市ガス燃焼廃ガスを使用し
た。As a result, it was found that by adding a compound having a specific chemical structure to a dyeing solution or a printing paste, fading of an unfixed dye upon contact with combustion waste gas can be prevented, and the present invention was completed. Let In addition, when confirming that the unfixed dye can be prevented from fading by the method of the present invention, in the method according to JIS L0655-67, NO and NO 2 gas by phosphoric acid-sodium nitrite are used as the sole gas, and the AATCO test method is used. In the method according to 23-1962, city gas combustion waste gas was used as a mixed gas.
【００１０】[0010]
【課題を解決するための手段】本発明の、未固着染料の
退色防止法は、セルロース繊維の反応染色を行う際、染
色液又は捺染糊中に、下記の化合物〜The method for preventing discoloration of unfixed dyes according to the present invention comprises the following compounds in a dyeing solution or printing paste when reactive dyeing of cellulose fibers:
【００１１】[0011]
【化１】[Chemical 1]
【００１２】[0012]
【化２】Embedded image
【００１３】[0013]
【化３】Embedded image
【００１４】[0014]
【化４】[Chemical 4]
【００１５】[0015]
【化５】Embedded image
【００１６】より選ばれた少なくとも１種を添加するこ
とを特徴とする。まず初めに、本発明の退色防止法にお
いて使用される上記の５種類の化合物について説明す
る。It is characterized in that at least one selected from the above is added. First, the above-mentioned five types of compounds used in the anti-fading method of the present invention will be described.
【００１７】上記の構造式で示される５種類の化合物
〜は、セルロース繊維用染料の退色の原因となるＳＯ
2 、ＮＯ、ＮＯ2 等の燃焼廃ガスから、染料を効果的に
保護する作用を有するものであって、これらの化合物
は、それぞれ単独でセルロース繊維用染色液又は捺染糊
中に添加しても良いし、あるいはこれらの化合物を２種
類以上組み合わせて添加しても良い。The five kinds of compounds represented by the above structural formulas are SO which cause discoloration of the dye for cellulose fiber.
It has an effect of effectively protecting the dye from combustion waste gas such as 2 , NO, NO 2 and the like. Even if these compounds are individually added to the dyeing solution for cellulose fiber or the printing paste, Alternatively, two or more kinds of these compounds may be combined and added.
【００１８】尚、本発明に使用される上記５種類の化合
物〜の構造式中、ｓは５〜２０の整数、ｐは０〜１
０の整数に限定されるが、これは以下の理由による。即
ち、ｓが４以下の整数、又はｐが１１以上の整数である
化合物は、水に対して不溶であって、尿素、メチルアル
コール等の溶解性向上助剤を併用した場合においても、
水に分散したり可溶化せず、染色液又は捺染糊中に均一
に混和することができないので、上述の燃焼廃ガスとの
接触による退色防止効果が十分に発揮できない。In the structural formulas of the above-mentioned 5 kinds of compounds used in the present invention, s is an integer of 5 to 20, and p is 0 to 1.
It is limited to an integer of 0 for the following reason. That is, a compound in which s is an integer of 4 or less, or p is an integer of 11 or more is insoluble in water, and even when a solubility improving aid such as urea or methyl alcohol is used in combination,
Since it does not disperse or solubilize in water and cannot be uniformly mixed in the dyeing liquid or the printing paste, the effect of preventing discoloration due to contact with the combustion waste gas cannot be sufficiently exerted.
【００１９】又、上記５種類の化合物〜の構造式に
おいて、ｓ＋ｐが３１以上の整数である化合物の場合に
は、末端ビニル基の活性度合が弱くなり、空気中に存在
するＳＯ2 、ＮＯ、ＮＯ2 ガス等との結合力が弱まっ
て、その結果、未固着染料を、このようなガスから保護
する働きが著しく低下する。Further, in the structural formulas of the above-mentioned 5 kinds of compounds to, in the case of a compound in which s + p is an integer of 31 or more, the activity degree of the terminal vinyl group becomes weak, and SO 2 and NO existing in the air, The binding force with NO 2 gas or the like is weakened, and as a result, the function of protecting the unfixed dye from such gas is significantly reduced.
【００２０】次に、本発明の、未固着染料の退色防止法
を用いて、セルロース繊維の反応染色を行う際の工程に
ついて説明する。本発明では、未固着染料の退色防止を
図る際、通常の組成比率にて調製された染色液又は捺染
糊中に、上述の化合物を適宜選択して添加するだけで良
く、このようにして得た染色液又は捺染糊を、セルロー
ス繊維に塗布して、その後、固着処理を行う。Next, the steps for reactive dyeing of cellulose fibers using the method for preventing fading of unfixed dye of the present invention will be described. In the present invention, in order to prevent discoloration of the unfixed dye, it suffices to appropriately select and add the above-mentioned compound to the dyeing solution or printing paste prepared in a usual composition ratio, and thus obtain The dyeing solution or printing paste is applied to the cellulose fibers, and then a fixing process is performed.
【００２１】本発明の退色防止法は、染料の吸収と固着
が別々に行われる反応染色にすべて適用可能であるが、
最も効果的かつ実用性のある加工法としては、パッド−
スチーム及びパッド−キュアーによるパッド法、プリン
ト・アルカリパッドによる捺染法が挙げられる。これら
の方法を実施する際には、染色液又は捺染糊中に、前述
の化合物〜を０．１〜１０重量％、好ましくは０．
５〜５重量％の割合で添加することが好ましい。The anti-fading method of the present invention can be applied to all reactive dyeing in which absorption and fixation of dye are carried out separately.
The most effective and practical processing method is pad-
The pad method by steam and pad-cure, and the printing method by a print / alkali pad are mentioned. When these methods are carried out, 0.1 to 10% by weight, preferably 0.1 to 10% by weight of the above-mentioned compounds are added to the dyeing solution or the printing paste.
It is preferable to add 5 to 5% by weight.
【００２２】又、本発明の方法では、特定の構造式で表
される化合物〜を、染色液又は捺染糊中に添加する
だけで未固着染料の退色防止を図ることができるので、
染色作業が、安全かつ円滑に実施できるという利点があ
る。しかも、本発明の方法によって処理された染色布
は、染色作業中において染料の変退色を起こし難いだけ
でなく、処理を行った後、退色の原因となる燃焼廃ガス
中に保存した場合であっても、染料の変退色を起こし難
い。Further, in the method of the present invention, it is possible to prevent discoloration of the unfixed dye by simply adding the compounds represented by the specific structural formulas to the dyeing solution or the printing paste.
There is an advantage that the dyeing work can be carried out safely and smoothly. Moreover, the dyed cloth treated by the method of the present invention is not only difficult to cause discoloration and discoloration of the dye during the dyeing operation, but also when it is stored in the combustion exhaust gas that causes discoloration after the processing. However, it is difficult to cause discoloration of the dye.
【００２３】これに対し、前述の化合物〜を添加し
ないでセルロース繊維の反応染色を行った場合には、染
色工程中にも、空気中に存在するガスとの接触によって
ドライ上りで既に変退色を起こすことがあり、又、未固
着にて次の工程に移行する間にも、著しい変退色を起こ
すことがある。このような変退色は、不可逆な変化であ
るため、固着処理を行った後においてもその影響が残留
する。On the other hand, when the reactive dyeing of the cellulose fiber is carried out without adding the above-mentioned compounds (1) to (3), even during the dyeing process, discoloration or fading has already occurred due to the contact with the gas existing in the air during the dry process. In some cases, the discoloration may occur during the transfer to the next step due to non-fixation. Since such discoloration and fading is an irreversible change, the effect remains even after the fixing process.
【００２４】尚、本発明では、溶解度の特に低い化合
物、例えばポリオキシエチレンジメタクリレート（前記
化学式においてＲがメチル基、ｓ＝５、ｐ＝０の化合
物）、ポリオキシエチレントリメチロールプロパントリ
アクリレート（前記化学式においてＲが水素、ｓ＝
５、ｐ＝０の化合物）、ポリオキシエチレンポリオキシ
プロピレンジペンタエリスリトールヘキサアクリレート
（前記化学式においてＲが水素、ｓ＝５、ｐ＝１０の
化合物）等を、染色液又は捺染糊中に添加して未固着染
料の退色防止を図る際、尿素、メチルアルコール等の溶
解向上助剤を任意の割合に併用して使用しても良い。以
下に、本発明の、セルロース繊維の反応染色における未
固着染料の退色防止法における実施例を示すが、本発明
は、これに限定されるものではない。尚、各実施例中、
「部」は「重量部」を示す。In the present invention, a compound having a particularly low solubility, such as polyoxyethylene dimethacrylate (a compound in which R is a methyl group, s = 5 and p = 0 in the above chemical formula), polyoxyethylene trimethylolpropane triacrylate ( In the above chemical formula, R is hydrogen, s =
5, a compound of p = 0), polyoxyethylene polyoxypropylene dipentaerythritol hexaacrylate (a compound of the above chemical formula, wherein R is hydrogen, s = 5, p = 10) and the like are added to the dyeing solution or the printing paste. In order to prevent discoloration of the unfixed dye, a dissolution improving aid such as urea or methyl alcohol may be used in combination at an arbitrary ratio. Examples of the method for preventing discoloration of unfixed dye in reactive dyeing of cellulose fibers of the present invention will be shown below, but the present invention is not limited thereto. Incidentally, in each example,
"Part" indicates "part by weight".
【００２５】[0025]
実施例１ ポリオキシエチレンジメタクリレート（前記化学式に
おいて、Ｒがメチル基、ｓ＝１４、ｐ＝０の化合物）Example 1 Polyoxyethylene dimethacrylate (a compound in which R is a methyl group, s = 14 and p = 0 in the above chemical formula)
【００２６】[0026]
【化６】 [Chemical 6]
【００２７】の１０部を熱湯９０部に溶解し、このよう
にして調製した溶液を、Ｃ．Ｉ．リアクティブ オレン
ジ１６（レマゾール オレンジ３Ｒ）の２部、アルギン
酸ソーダの１部、メタニトロベンゼンスルフォン酸ソー
ダの５部、重炭酸ソーダの２０部及び尿素の８０部を含
む溶液８００部に加えて補水し、全体を１０００部とし
た染色液を得た。10 parts of was dissolved in 90 parts of hot water, and the solution prepared in this manner was used as C.I. I. Add 800 parts of a solution containing 2 parts of Reactive Orange 16 (Remazol Orange 3R), 1 part of sodium alginate, 5 parts of sodium metanitrobenzene sulfonate, 20 parts of sodium bicarbonate and 80 parts of urea, and rehydrate the whole. A dye solution of 1000 parts was obtained.
【００２８】そして、糊抜き精錬した６０番ブロード布
を、上記の染色液に浸漬（絞率７０％）し、その後、１
００℃で３分間乾燥してテスト試料（本発明の退色防止
法を施した試料）を得た。これと同時に、同様の方法に
て、参照用として上記の化合物が添加されていない試料
（無添加試料）も作製した。Then, the desizing-refined No. 60 broad cloth is immersed in the above dyeing solution (squeeze ratio 70%), and then 1
It was dried at 00 ° C. for 3 minutes to obtain a test sample (sample subjected to the anti-fading method of the present invention). At the same time, a sample to which the above compound was not added (non-added sample) was also prepared as a reference by the same method.
【００２９】次に、テスト試料及び無添加試料を、ＪＩ
Ｓ Ｌ０８５５−６７に準じて酸化窒素ガス中３ユニッ
トの処理を行った後、１４０℃で２分間熱処理固着し
た。その後、水洗し、２％酢酸処理、更に水洗後、風乾
した。グレースケールを尺度として堅牢度を測定した結
果、無添加試料がグレースケールの３号に相当する変退
色を示したのに対して、テスト試料は５号に相当する堅
牢度を示した。Next, the test sample and the additive-free sample were subjected to JI
After treating 3 units in nitric oxide gas according to S L0855-67, heat treatment and fixation were performed at 140 ° C. for 2 minutes. Then, it was washed with water, treated with 2% acetic acid, further washed with water, and then air dried. As a result of measuring the fastness using the gray scale as a scale, the additive-free sample showed discoloration and fading corresponding to gray scale No. 3, while the test sample showed fastness corresponding to No. 5.
【００３０】実施例２ ポリオキシエチレンジペンタエリスリトールヘキサアク
リレート（前記化学式において、Ｒが水素、ｓ＝９、
ｐ＝０の化合物）Example 2 Polyoxyethylene dipentaerythritol hexaacrylate (in the above chemical formula, R is hydrogen, s = 9,
compound with p = 0)
【００３１】[0031]
【化７】 [Chemical 7]
【００３２】の２０部を、メタノールの４０部にて湿ら
せ熱湯１００部を加えて溶解し、このようにして調製し
た溶液を、Ｃ．Ｉ．リアクティブ ブルー２８（レマゾ
ールブルー３Ｒ）の２０部、アルギン酸ソーダの２５
部、尿素の５０部及びメタニトロベンゼンスルフォン酸
ソーダの５部を溶解したペースト８００部に加えて補水
し、全体を１０００部とした捺染糊を得た。20 parts of C. are moistened with 40 parts of methanol and 100 parts of hot water is added to dissolve them, and the solution thus prepared is used as C.I. I. 20 parts of Reactive Blue 28 (Remazol Blue 3R), 25 parts of sodium alginate
Parts, 50 parts of urea and 5 parts of sodium metanitrobenzene sulfonate were dissolved in 800 parts of the paste, and water was added to obtain 1000 parts of the printing paste.
【００３３】そして、上記の捺染糊を、糊抜き精錬した
６０番ブロード布に印捺した後、１００℃で５分間乾燥
してテスト試料を得た。これと同時に、同様の方法に
て、参照用として上記の化合物が添加されていない無添
加試料も作製した。Then, the above printing paste was printed on a desizing-refined No. 60 broad cloth and dried at 100 ° C. for 5 minutes to obtain a test sample. At the same time, a non-added sample to which the above compound was not added was also prepared as a reference by the same method.
【００３４】次に、テスト試料及び無添加試料につい
て、ＳＯ2 ガスに対する堅牢度を測定するためにＪＩＳ
Ｌ０８５５−６７に準じ、亜硫酸ソーダに代えて、等
モルの無水亜硫酸ソーダを加えてＳＯ2 ガスを発生さ
せ、両試料をＳＯ2 ガス雰囲気中に懸吊し、３０分間処
理した。上記の処理を行った後、両試料を、正硅酸ソー
ダの１５％溶液に９０〜９５℃で２０秒間浸漬して染料
を固着させ、流水中で試料を洗い、更に２％酢酸にて中
和した後、水洗乾燥した。Next, in order to measure the fastness to SO 2 gas of the test sample and the additive-free sample, JIS was used.
According to L0855-67, instead of sodium sulfite, equimolar anhydrous sodium sulfite was added to generate SO 2 gas, and both samples were suspended in an SO 2 gas atmosphere and treated for 30 minutes. After the above treatment, both samples were immersed in a 15% solution of sodium orthosilicate for 20 seconds at 90 to 95 ° C. to fix the dye, and the samples were washed in running water, and then with 2% acetic acid. After soaking, it was washed with water and dried.
【００３５】グレースケールを尺度として堅牢度を測定
した結果、無添加試料が３〜４号に相当する変退色を示
したのに対して、テスト試料は５号に相当する堅牢度を
示した。As a result of measuring the fastness using a gray scale as a scale, the additive-free sample showed discoloration corresponding to Nos. 3 to 4, while the test sample showed the fastness corresponding to No. 5.
【００３６】実施例３ ポリオキシエチレンポリオキシプロピレントリメチロー
ルプロパントリアクリレート（前記化学式において、
Ｒが水素、ｓ＝９、ｐ＝５の化合物）Example 3 Polyoxyethylene polyoxypropylene trimethylolpropane triacrylate (in the above chemical formula,
R is hydrogen, s = 9, p = 5)
【００３７】[0037]
【化８】 Embedded image
【００３８】の１０部に、ポリオキシエチレンセチルエ
ーテル（Ｅ．Ｏ添加３０モル）の３部を加え、メタノー
ルの２０部をもって均一液とした後、６０〜７０℃の湯
７０部を加えて分散液を調製した。そして、このように
して調製した分散液を、Ｃ．Ｉ．リアクティブ レッド
２２（レマゾール レッドＢ）の２部、アルギン酸ソー
ダの１部、メタニトロベンゼンスルフォン酸ソーダの５
部、重炭酸ソーダの２０部及び尿素の８０部を含む溶液
８００部に加えて補水し、全体を１０００部とした染色
液を得た。After adding 3 parts of polyoxyethylene cetyl ether (30 mol of EO added) to 10 parts of the mixture and making 20 parts of methanol into a uniform solution, 70 parts of hot water at 60 to 70 ° C. was added to disperse. A liquid was prepared. Then, the dispersion liquid thus prepared was used as C.I. I. 2 parts of Reactive Red 22 (Remazol Red B), 1 part of sodium alginate, 5 parts of sodium metanitrobenzene sulfonate
Parts, 20 parts of sodium bicarbonate, and 800 parts of a solution containing 80 parts of urea were added and replenished with water to obtain 1000 parts of the whole dyeing solution.
【００３９】実施例１と同様に糊抜き精錬した６０番ブ
ロード布を、上記の染色液に浸漬した後、乾燥させ、テ
スト試料を得た。これと同時に、同様の方法にて、参照
用として上記の化合物が添加されていない無添加試料も
作製した。A No. 60 broad cloth which had been desizing and refined in the same manner as in Example 1 was dipped in the above dyeing solution and then dried to obtain a test sample. At the same time, a non-added sample to which the above compound was not added was also prepared as a reference by the same method.
【００４０】次に、テスト試料及び無添加試料につい
て、都市燃焼ガスに対する堅牢度を測定するためにＡＡ
ＴＣＣ試験法２３−１９６２に準ずるガスチェンバー
中、両試料を都市燃焼ガス雰囲気中に懸吊し、６０℃で
１時間処理した。上記のガス処理を行った後、両試料を
取り出し、１００℃で１５分間蒸熱し、水洗中和後、再
び水洗して風乾した。グレースケールを尺度として堅牢
度を測定した結果、無添加試料が３号に相当する変退色
を示したのに対し、テスト試料は５号に相当する堅牢度
を示した。Next, for the test sample and the additive-free sample, AA was used to measure the fastness to city combustion gas.
In a gas chamber according to TCC Test Method 23-1962, both samples were suspended in a city combustion gas atmosphere and treated at 60 ° C for 1 hour. After the above gas treatment, both samples were taken out, steamed at 100 ° C. for 15 minutes, washed with water to neutralize, washed again with water and air dried. As a result of measuring the fastness using a gray scale as a scale, the additive-free sample showed discoloration and fading corresponding to No. 3, while the test sample showed fastness corresponding to No. 5.
【００４１】実施例４ ポリオキシエチレンポリオキシプロピレンペンタエリス
リトールテトラアクリレート（前記化学式において、
Ｒが水素、ｓ＝１４、ｐ＝４の化合物）Example 4 Polyoxyethylene polyoxypropylene pentaerythritol tetraacrylate (in the above chemical formula,
R is hydrogen, s = 14, p = 4)
【００４２】[0042]
【化９】 [Chemical 9]
【００４３】の２０部を、メタノールの４０部にて湿ら
せ熱湯１００部を加えて溶解し、このようにして調製し
た溶液を、Ｃ．Ｉ．リアクティブ エロー２３（レマゾ
ールエローＧＮＬ）の２０部、アルギン酸ソーダの２５
部、尿素の５０部及びメタニトロベンゼンスルフォン酸
ソーダの５部を溶解したペースト８００部に加えて補水
し、全体を１０００部とした捺染糊を得た。20 parts of C. are moistened with 40 parts of methanol and 100 parts of hot water is added to dissolve them, and the solution thus prepared is used as C.I. I. 20 parts of Reactive Yellow 23 (Remazol Yellow GNL), 25 parts of sodium alginate
Parts, 50 parts of urea and 5 parts of sodium metanitrobenzene sulfonate were dissolved in 800 parts of the paste, and water was added to obtain 1000 parts of the printing paste.
【００４４】そして、上記の捺染糊を、糊抜き精錬した
６０番ブロード布に印捺した後、１００℃で５分間乾燥
してテスト試料を得た。これと同時に、同様の方法に
て、参照用として上記の化合物が添加されていない無添
加試料も作製した。Then, the above printing paste was printed on a desizing-refined No. 60 broad cloth and dried at 100 ° C. for 5 minutes to obtain a test sample. At the same time, a non-added sample to which the above compound was not added was also prepared as a reference by the same method.
【００４５】次に、テスト試料及び無添加試料につい
て、ＳＯ2 ガスに対する堅牢度を測定するためにＪＩＳ
Ｌ０８５５−６７に準じ、亜硫酸ソーダに代えて、等
モルの無水亜硫酸ソーダを加えてＳＯ2 ガスを発生さ
せ、両試料をＳＯ2 ガス雰囲気中に懸吊し、３０分間処
理した。上記の処理を行った後、両試料を、正硅酸ソー
ダの１５％溶液に９０〜９５℃で２０秒間浸漬して染料
を固着させ、流水中で試料を洗い、更に２％酢酸にて中
和した後、水洗乾燥した。Next, in order to measure the fastness to SO 2 gas of the test sample and the additive-free sample, JIS was used.
According to L0855-67, instead of sodium sulfite, equimolar anhydrous sodium sulfite was added to generate SO 2 gas, and both samples were suspended in an SO 2 gas atmosphere and treated for 30 minutes. After the above treatment, both samples were immersed in a 15% solution of sodium orthosilicate for 20 seconds at 90 to 95 ° C. to fix the dye, and the samples were washed in running water, and then with 2% acetic acid. After soaking, it was washed with water and dried.
【００４６】グレースケールを尺度として堅牢度を測定
した結果、無添加試料が３〜４号に相当する変退色を示
したのに対して、テスト試料は５号に相当する堅牢度を
示した。As a result of measuring the fastness using a gray scale as a scale, the additive-free sample showed discoloration and fading corresponding to Nos. 3 to 4, while the test sample showed fastness corresponding to No. 5.
【００４７】実施例５ ポリオキシエチレンジグリシジルエーテルのアクリル酸
付加物（前記化学式において、Ｒが水素、ｓ＝４、ｐ
＝０の化合物）Example 5 Acrylic acid adduct of polyoxyethylene diglycidyl ether (in the above chemical formula, R is hydrogen, s = 4, p
= 0 compound)
【００４８】[0048]
【化１０】 [Chemical 10]
【００４９】の３０部を、メタノールの６０部にて湿ら
せ熱湯１００部を加えて溶解し、このようにして調製し
た溶液を、Ｃ．Ｉ．リアクティブ ブラック５（レマゾ
ールブラックＢ）の２０部、アルギン酸ソーダの２５
部、尿素の５０部及びメタニトロベンゼンスルフォン酸
ソーダの５部を溶解したペースト８００部に加えて補水
し、全体を１０００部とした捺染糊を得た。30 parts of was moistened with 60 parts of methanol and 100 parts of hot water was added to dissolve, and the solution prepared in this manner was added to C.I. I. 20 parts of Reactive Black 5 (Remazol Black B), 25 parts of sodium alginate
Parts, 50 parts of urea and 5 parts of sodium metanitrobenzene sulfonate were dissolved in 800 parts of the paste, and water was added to obtain 1000 parts of the printing paste.
【００５０】そして、上記の捺染糊を、糊抜き精錬した
６０番ブロード布に印捺した後、１００℃で５分間乾燥
してテスト試料を得た。これと同時に、同様の方法に
て、参照用として上記の化合物が添加されていない無添
加試料も作製した。Then, the above printing paste was printed on No. 60 broad cloth which had been desizing and refined, and then dried at 100 ° C. for 5 minutes to obtain a test sample. At the same time, a non-added sample to which the above compound was not added was also prepared as a reference by the same method.
【００５１】次に、テスト試料及び無添加試料につい
て、ＳＯ2 ガスに対する堅牢度を測定するためにＪＩＳ
Ｌ０８５５−６７に準じ、亜硫酸ソーダに代えて、等
モルの無水亜硫酸ソーダを加えてＳＯ2 ガスを発生さ
せ、両試料をＳＯ2 ガス雰囲気中に懸吊し、３０分間処
理した。上記の処理を行った後、両試料を、正硅酸ソー
ダの１５％溶液に９０〜９５℃で２０秒間浸漬して染料
を固着させ、流水中で試料を洗い、更に２％酢酸にて中
和した後、水洗乾燥した。Next, in order to measure the fastness to SO 2 gas for the test sample and the additive-free sample, JIS was used.
According to L0855-67, instead of sodium sulfite, equimolar anhydrous sodium sulfite was added to generate SO 2 gas, and both samples were suspended in an SO 2 gas atmosphere and treated for 30 minutes. After the above treatment, both samples were immersed in a 15% solution of sodium orthosilicate for 20 seconds at 90 to 95 ° C. to fix the dye, and the samples were washed in running water, and then with 2% acetic acid. After soaking, it was washed with water and dried.
【００５２】グレースケールを尺度として堅牢度を測定
した結果、無添加試料が３号に相当する変退色を示した
のに対し、テスト試料は５号に相当する堅牢度を示し
た。As a result of measuring the fastness using a gray scale as a scale, the additive-free sample showed discoloration and fading corresponding to No. 3, while the test sample showed fastness corresponding to No. 5.
【００５３】[0053]
【発明の効果】本発明の、セルロース繊維の反応染色に
おける未固着染料の退色防止法を用いることによって、
変退色の原因となるＳＯ2 、ＮＯ、ＮＯ2 等の燃焼廃ガ
スから、未固着の反応染料を効果的に保護することがで
き、上記の燃焼廃ガスとの接触によって染色製品の色彩
が劣化するのを防止できる。しかも、本発明の方法を用
いた場合では、染色液又は捺染糊中に特定の化学構造を
有する化合物〜を添加するだけで良いので、染色作
業が安全かつ簡単に行えるという利点もある。By using the method for preventing fading of unfixed dye in reactive dyeing of cellulose fiber of the present invention,
SO 2 which causes discoloration, NO, from combustion exhaust gases, such as NO 2, it is possible to protect the reactive dyes unfixed effectively, deterioration colors of dye product by contact with the combustion exhaust gas Can be prevented. Moreover, when the method of the present invention is used, since it is only necessary to add the compound having a specific chemical structure to the dyeing solution or the printing paste, there is an advantage that the dyeing work can be performed safely and easily.
Claims (1)
色液又は捺染糊中に、下記の化合物〜より選ばれた
少なくとも１種を添加することを特徴とする、セルロー
ス繊維の反応染色における未固着染料の退色防止法。 【化１】 【化２】 【化３】 【化４】 【化５】 1. Non-fixation in reactive dyeing of cellulose fibers, characterized in that, when reactive dyeing of cellulose fibers is performed, at least one selected from the following compounds is added to a dyeing solution or a printing paste. Dye fading prevention method. Embedded image Embedded image Embedded image Embedded image Embedded image
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3135446A JP2549583B2 (en) | 1991-05-10 | 1991-05-10 | Method for preventing fading of unfixed dye in reactive dyeing of cellulose fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3135446A JP2549583B2 (en) | 1991-05-10 | 1991-05-10 | Method for preventing fading of unfixed dye in reactive dyeing of cellulose fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04333676A JPH04333676A (en) | 1992-11-20 |
| JP2549583B2 true JP2549583B2 (en) | 1996-10-30 |
Family
ID=15151913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3135446A Expired - Fee Related JP2549583B2 (en) | 1991-05-10 | 1991-05-10 | Method for preventing fading of unfixed dye in reactive dyeing of cellulose fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2549583B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7338310B2 (en) | 2005-05-27 | 2008-03-04 | Yazaki Corporation | Piercing terminal and connector using same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0313165B8 (en) | 2002-08-02 | 2021-05-25 | Ab Science | 2-(3-aminoaryl)amino-4-aryl-thiazoles and their use as c-kit inhibitors |
| US8450302B2 (en) | 2002-08-02 | 2013-05-28 | Ab Science | 2-(3-aminoaryl) amino-4-aryl-thiazoles and their use as c-kit inhibitors |
| CN104389197A (en) * | 2014-12-15 | 2015-03-04 | 常熟市启弘纺织实业有限公司 | Fabric printing and dyeing method |
| CN105019274B (en) * | 2015-08-18 | 2017-03-08 | 青岛大学 | A kind of method improving pure cotton fabric reactive dye ground colour white resist printing effect |
-
1991
- 1991-05-10 JP JP3135446A patent/JP2549583B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7338310B2 (en) | 2005-05-27 | 2008-03-04 | Yazaki Corporation | Piercing terminal and connector using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04333676A (en) | 1992-11-20 |
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