JPH04333676A - Method for preventing unfixed dye from fading in reaction dyeing of cellulosic fiber - Google Patents
Method for preventing unfixed dye from fading in reaction dyeing of cellulosic fiberInfo
- Publication number
- JPH04333676A JPH04333676A JP3135446A JP13544691A JPH04333676A JP H04333676 A JPH04333676 A JP H04333676A JP 3135446 A JP3135446 A JP 3135446A JP 13544691 A JP13544691 A JP 13544691A JP H04333676 A JPH04333676 A JP H04333676A
- Authority
- JP
- Japan
- Prior art keywords
- fading
- dye
- dyeing
- parts
- formula
- 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.)
- Granted
Links
- 238000005562 fading Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004043 dyeing Methods 0.000 title claims abstract description 25
- 239000000835 fiber Substances 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 229920003043 Cellulose fiber Polymers 0.000 claims description 18
- 238000004045 reactive dyeing Methods 0.000 claims description 12
- 239000000975 dye Substances 0.000 abstract description 40
- 238000002485 combustion reaction Methods 0.000 abstract description 17
- 239000002912 waste gas Substances 0.000 abstract description 15
- -1 polyoxyethylene dimethacrylate Polymers 0.000 abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000985 reactive dye Substances 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract 1
- 230000006866 deterioration Effects 0.000 abstract 1
- 238000009980 pad dyeing Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 25
- 238000002845 discoloration Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000000126 substance Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 7
- 239000004202 carbamide Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 235000010413 sodium alginate Nutrition 0.000 description 5
- 239000000661 sodium alginate Substances 0.000 description 5
- 229940005550 sodium alginate Drugs 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 229940001482 sodium sulfite Drugs 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- HFIYIRIMGZMCPC-YOLJWEMLSA-J remazole black-GR Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=C(\N=N\C=3C=CC(=CC=3)S(=O)(=O)CCOS([O-])(=O)=O)C(O)=C2C(N)=C1\N=N\C1=CC=C(S(=O)(=O)CCOS([O-])(=O)=O)C=C1 HFIYIRIMGZMCPC-YOLJWEMLSA-J 0.000 description 2
- 239000012192 staining solution Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010014 continuous dyeing Methods 0.000 description 1
- 238000009990 desizing Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229920006239 diacetate fiber Polymers 0.000 description 1
- OVFWQJVENRZWTG-UHFFFAOYSA-L disodium 5-hydroxy-6-[[3-(2-sulfonatooxyethylsulfonyl)phenyl]diazenyl]naphthalene-1-sulfonate Chemical compound [Na+].[Na+].Oc1c(ccc2c(cccc12)S([O-])(=O)=O)N=Nc1cccc(c1)S(=O)(=O)CCOS([O-])(=O)=O OVFWQJVENRZWTG-UHFFFAOYSA-L 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- DHHGSXPASZBLGC-VPMNAVQSSA-L remazole orange-3R Chemical compound [Na+].[Na+].OC=1C2=CC(NC(=O)C)=CC=C2C=C(S([O-])(=O)=O)C=1\N=N\C1=CC=C(S(=O)(=O)CCOS([O-])(=O)=O)C=C1 DHHGSXPASZBLGC-VPMNAVQSSA-L 0.000 description 1
- DFJPOQQGSZVLDZ-UHFFFAOYSA-M sodium phosphoric acid nitrite Chemical compound [Na+].[O-]N=O.OP(O)(O)=O DFJPOQQGSZVLDZ-UHFFFAOYSA-M 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920006304 triacetate fiber Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Coloring (AREA)
Abstract
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。[Industrial Application Field] The present invention provides that unfixed dyes in reactive dyeing of cellulose fibers are
The present invention relates to a method for preventing color fading when coming into contact with combustion waste gas such as.
【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。[Prior Art] It has been known that dyes used for dyeing fibers change color and fade when they come into contact with certain types of gases. It is also known that the behavior varies considerably depending on the type of fiber 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。[0003] For example, when disperse dyes are used to dye diacetate fibers or triacetate fibers, significant discoloration occurs when they come into contact with combustion exhaust gas, but in the case of polyester fibers, such discoloration hardly occurs. do not have. Furthermore, in the case of cellulose fibers, discoloration and fading due to contact with combustion waste gas is generally less likely to occur, but problems may occur depending on the conditions. In this case, the major factors causing discoloration and fading are light, heat, humidity, type of dye, dyeing density, state of fixation of dye to fibers, etc.
【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。[0004] The dyes that have been widely used in the dyeing of cellulose fibers are vinyl sulfone type dyes, and this type of dye has the following characteristics:
It generally has good solubility and is well suited for continuous dyeing, but it tends to discolor and fade at low dyeing concentrations below medium color, especially below 1-2% by weight, and due to high It is known that discoloration and fading are likely to occur even when the temperature 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。Furthermore, in the case of reactive dyeing of cellulose fibers, one of the factors that has a major influence on discoloration and fading is the fixation state of the dye after dyeing, and if the dye is in an unfixed state, combustion waste Discoloration and fading are likely to occur due to contact with gas. In general, gases known to cause discoloration and fading of dyes for cellulose fibers include Cl2 and Br.
2, SO2, NO, NO2, etc. Among these, SO2, NO, and NO2 contained in combustion waste gas are considered to be the largest group of causes.
【０００６】そして、このようなＳＯ２ 、ＮＯ、ＮＯ
２ 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。[0006] And, such SO2, NO, NO
If unfixed dyes in reactive dyeing of cellulose fibers change color and fade due to contact with combustion waste gases such as It is extremely important to develop a method to prevent color change and fading so that fixed dyes do not fade even when they come into contact with combustion waste gas. However, to date, no method has been proposed that can effectively prevent discoloration and fading of unfixed dyes and also allows for safe and easy dyeing operations.
【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。[Problems to be Solved by the Invention] The present invention improves the above-mentioned drawbacks, effectively protects unfixed dyes that tend to discolor and fade due to contact with combustion waste gas, and allows dyeing operations to be carried out safely and easily. An object of the present invention is to provide a method for preventing fading of unfixed dye in reactive dyeing of cellulose fibers.
【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。[0008] The present inventors used SO2, NO, and NO2 gases, which are considered to be the most important causes of discoloration and fading in dyes for cellulose fibers, as test gases, and tested JIS L0655-67 and AATCO.
The anti-fading effect was studied using a method similar to Test Method 23-1962.
【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 discovered that by adding a compound having a specific chemical structure to the dyeing solution or printing paste, fading of unfixed dye when it comes into contact with combustion waste gas can be prevented, and the present invention was completed. I let it happen. In addition, when confirming that fading of unfixed dye can be prevented by the method of the present invention, in a method according to JIS L0655-67, NO, NO2 gas from phosphoric acid-sodium nitrite is used as the sole gas, and AATCO test method 23 is used. -1962, city gas combustion waste gas was used as the 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■〜■[Means for Solving the Problems] The method for preventing fading of unfixed dyes of the present invention involves adding the following compounds (■ to ■) to the dyeing solution or printing paste when performing reactive dyeing of cellulose fibers.
【００１１】[0011]
【化１】[Chemical formula 1]
【００１２】0012
【化２】[Case 2]
【００１３】[0013]
【化３】[Chemical formula 3]
【００１４】[0014]
【化４】[C4]
【００１５】[0015]
【化５】[C5]
【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 following is added. First, the above-mentioned five types of compounds used in the method for preventing discoloration of the present invention will be explained.
【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。Five types of compounds represented by the above structural formula ■
～■ is SO, which causes discoloration of dyes for cellulose fibers.
2. It has the effect of effectively protecting dyes from combustion waste gases such as NO, NO2, etc., and each of these compounds may be added alone to the cellulose fiber dyeing solution or printing paste. or these compounds
A combination of more than one type may be 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。[0018] In the structural formulas of the five compounds (1) to (4) used in the present invention, s is an integer of 5 to 20, and p is an integer of 0 to 1.
This 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, even when a solubility-improving aid such as urea or methyl alcohol is used together.
Since it is not dispersed or solubilized in water and cannot be mixed uniformly into a dyeing solution or printing paste, it cannot sufficiently exhibit the effect of preventing discoloration due to contact with combustion waste gas.
【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。In addition, in the structural formulas of the five types of compounds ① to ②, in the case of compounds in which s+p is an integer of 31 or more, the activity of the terminal vinyl group becomes weaker, and SO2 and NO present in the air , NO2 gas, etc., and as a result, the ability to protect the unfixed dye from such gases 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 of preventing fading of unfixed dye according to the present invention will be explained. In the present invention, in order to prevent fading of unfixed dyes, it is sufficient to simply select and add the above-mentioned compounds to the dyeing liquid or printing paste prepared at a normal composition ratio, and the obtained compound can be obtained in this way. The dyeing liquid or printing paste is applied to the cellulose fibers, and then a fixing treatment 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 fading prevention method of the present invention is applicable to all reactive dyeings in which dye absorption and fixation are carried out separately.
The most effective and practical processing method is pad-
Examples include a pad method using steam and pad-cure, and a printing method using a print alkaline pad. When carrying out these methods, 0.1 to 10% by weight, preferably 0.1 to 10% by weight, preferably 0.1 to 10% by weight of the above-mentioned compounds (1) to (2) are added to the dyeing solution or printing paste.
It is preferable to add it in a proportion of 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
。Furthermore, in the method of the present invention, fading of unfixed dye can be prevented by simply adding compounds (1) to (2) represented by specific structural formulas to the dyeing solution or printing paste.
There is an advantage that the dyeing work can be carried out safely and smoothly. Moreover, the dyed fabric treated by the method of the present invention is not only resistant to discoloration and fading of the dye during the dyeing process, but also resistant to combustion waste gases that cause discoloration after the treatment. However, the dye is less likely to change color or fade.
【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 reactive dyeing of cellulose fibers is carried out without adding the above-mentioned compounds 1 to 2, changes occur even during the drying process due to contact with gases present in the air. Discoloration may occur, and significant discoloration and fading may occur even during the transition to the next step without fixation. Since such discoloration and fading are irreversible changes, their effects remain even after the fixing treatment is performed.
【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, compounds with particularly low solubility, such as polyoxyethylene dimethacrylate (a compound in which R is a methyl group, s=5, and p=0 in the chemical formula (1)), polyoxyethylene trimethylolpropane triacrylate (In the chemical formula (■), R is hydrogen, s=5,
A compound in which p = 0), polyoxyethylene polyoxypropylene dipentaerythritol hexaacrylate (a compound in which R is hydrogen, s = 5, and p = 10 in the chemical formula (2)), etc. are added to the dyeing solution or printing paste. In order to prevent unfixed dye from fading, a solubility-improving aid such as urea or methyl alcohol may be used in combination in any proportion. Examples of the method for preventing fading of unfixed dyes in reactive dyeing of cellulose fibers of the present invention are shown below.
It is not limited to this. In each example, "parts" indicate "parts 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 (in the chemical formula (1), R is a methyl group, s=14, p=0 compound)
【
００２６】[
0026
【化６】[C6]
【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 C. I. Add water to 800 parts of a solution containing 2 parts of Reactive Orange 16 (Remazol Orange 3R), 1 part of sodium alginate, 5 parts of sodium metanitrobenzenesulfonate, 20 parts of sodium bicarbonate, and 80 parts of urea, and add water to the mixture. A staining 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。[0028] Then, the desizing and refined No. 60 broad cloth was immersed in the above dyeing liquid (squeezing ratio 70%), and then 1
The sample was dried at 00° C. for 3 minutes to obtain a test sample (sample treated with the fading prevention method of the present invention). At the same time, a sample to which the above-mentioned compound was not added (an additive-free sample) was also prepared for reference using 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 3 units were treated in nitrogen oxide gas according to S L0855-67, they were heat treated and fixed at 140°C for 2 minutes. Thereafter, it was washed with water, treated with 2% acetic acid, further washed with water, and air-dried. As a result of measuring the fastness using gray scale as a scale, the additive-free sample showed discoloration and fading corresponding to No. 3 on the gray scale, while the test sample showed fastness corresponding to No. 5 on the gray scale.
【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 chemical formula (2), R is hydrogen, s=9,
compound with p=0)
【００３１】[0031]
【化７】[C7]
【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. I. 20 parts of Reactive Blue 28 (Remazol Blue 3R), 25 parts of sodium alginate
50 parts of urea and 5 parts of sodium metanitrobenzenesulfonate were added to 800 parts of a paste and replenished with water to obtain a printing paste with a total volume of 1000 parts.
【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。[0033] The above-mentioned printing paste was printed on No. 60 broad cloth which had been desized and refined, and then dried at 100°C for 5 minutes to obtain a test sample. At the same time, an additive-free sample to which the above-mentioned compound was not added was also prepared as a reference using 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 SO2 gas for the test sample and the additive-free sample, JIS
According to L0855-67, instead of sodium sulfite,
An equimolar amount of anhydrous sodium sulfite was added to generate SO2 gas, and both samples were suspended in the SO2 gas atmosphere and treated for 30 minutes. After the above treatment, both samples were immersed in a 15% solution of sodium orthosilicate at 90 to 95°C for 20 seconds to fix the dye, washed under running water, and further soaked in 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。[0035] As a result of measuring fastness using gray scale as a scale, the additive-free sample showed discoloration and fading corresponding to No. 3 or 4, while the test sample showed 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 Polyoxyethylenepolyoxypropylenetrimethylolpropane triacrylate (in the chemical formula (1) above,
Compounds in which R is hydrogen, s=9, p=5)
【００３７】[0037]
【化８】[Chemical formula 8]
【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。Add 3 parts of polyoxyethylene cetyl ether (30 moles of E.O added) to 10 parts of [0038], make a homogeneous liquid with 20 parts of methanol, and then add 70 parts of hot water at 60 to 70°C to disperse. A liquid was prepared. Then, the dispersion prepared in this way was mixed with C.I. I. Add water to 800 parts of a solution containing 2 parts of Reactive Red 22 (Remazol Red B), 1 part of sodium alginate, 5 parts of sodium metanitrobenzenesulfonate, 20 parts of sodium bicarbonate, and 80 parts of urea, and then A staining solution of 1000 parts was obtained.
【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 broadcloth, which had been desized and refined in the same manner as in Example 1, was immersed in the above dyeing liquid and then dried to obtain a test sample. At the same time, an additive-free sample to which the above-mentioned compound was not added was also prepared as a reference using 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ＡＡＴ
ＣＣ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, the test sample and the additive-free sample were subjected to AAT to measure their fastness to urban combustion gas.
In a gas chamber according to CC test method 23-1962,
Both samples were suspended in an urban combustion gas atmosphere and treated at 60° C. for 1 hour. After performing the above gas treatment, both samples were taken out, steamed at 100° C. for 15 minutes, washed with water for neutralization, washed with water again, and air-dried. As a result of measuring fastness using gray scale as a scale, the additive-free sample showed discoloration and fading equivalent to No. 3, while the test sample showed fastness equivalent 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 chemical formula
Compounds in which R is hydrogen, s=14, p=4)
【００４２】[0042]
【化９】[Chemical formula 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２
５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. I. 20 parts of Reactive Yellow 23 (Remazol Yellow GNL), 2 parts of sodium alginate
5 parts of urea, and 5 parts of sodium metanitrobenzenesulfonate were added to 800 parts of a paste and supplemented with water to obtain a printing paste with a total volume of 1000 parts.
【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。[0044] The above printing paste was printed on a size-refined No. 60 broadcloth, and then dried at 100°C for 5 minutes to obtain a test sample. At the same time, an additive-free sample to which the above-mentioned compound was not added was also prepared as a reference using 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 SO2 gas for the test sample and the additive-free sample, JIS
According to L0855-67, instead of sodium sulfite,
An equimolar amount of anhydrous sodium sulfite was added to generate SO2 gas, and both samples were suspended in the SO2 gas atmosphere and treated for 30 minutes. After the above treatment, both samples were immersed in a 15% solution of sodium orthosilicate at 90 to 95°C for 20 seconds to fix the dye, washed under running water, and further soaked in 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 gray scale as a scale, the additive-free sample showed discoloration and fading corresponding to No. 3 or 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 chemical formula (2), R is hydrogen, s=4, p
=0 compound)
【００４８】[0048]
【化１０】[Chemical formula 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 C. I. 20 parts of Reactive Black 5 (Remazol Black B), 25 parts of sodium alginate
50 parts of urea and 5 parts of sodium metanitrobenzenesulfonate were added to 800 parts of a paste and replenished with water to obtain a printing paste with a total volume of 1000 parts.
【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。[0050] The above printing paste was printed on a size-refined No. 60 broadcloth, and then dried at 100°C for 5 minutes to obtain a test sample. At the same time, an additive-free sample to which the above-mentioned compound was not added was also prepared as a reference using 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 SO2 gas for the test sample and the additive-free sample, JIS
According to L0855-67, instead of sodium sulfite,
An equimolar amount of anhydrous sodium sulfite was added to generate SO2 gas, and both samples were suspended in the SO2 gas atmosphere and treated for 30 minutes. After the above treatment, both samples were immersed in a 15% solution of sodium orthosilicate at 90 to 95°C for 20 seconds to fix the dye, washed under running water, and further soaked in 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
。[0052] As a result of measuring fastness using gray scale as a scale, the additive-free sample showed discoloration and fading equivalent to No. 3, while the test sample showed fastness equivalent 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。[Effects of the Invention] By using the method of preventing fading of unfixed dye in reactive dyeing of cellulose fibers of the present invention,
It can effectively protect unfixed reactive dyes from combustion waste gases such as SO2, NO, and NO2, which cause discoloration and fading, and prevent the color of dyed products from deteriorating due to contact with the above combustion waste gases. can be prevented. Furthermore, when the method of the present invention is used, it is sufficient to simply add compounds (1) to (4) having a specific chemical structure to the dyeing solution or printing paste, so there is an advantage that the dyeing operation can be carried out safely and easily.
Claims (1)
染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】[Claim 1] When performing reactive dyeing of cellulose fibers,
A method for preventing fading of unfixed dye in reactive dyeing of cellulose fibers, which comprises adding at least one selected from the following compounds (1) to (2) to a dyeing solution or printing paste. [Formula 1] [Formula 2] [Formula 3] [Formula 4] [Formula 5]
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 true JPH04333676A (en) | 1992-11-20 |
| JP2549583B2 JP2549583B2 (en) | 1996-10-30 |
Family
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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 (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8450302B2 (en) | 2002-08-02 | 2013-05-28 | Ab Science | 2-(3-aminoaryl) amino-4-aryl-thiazoles and their use as c-kit inhibitors |
| US8835435B2 (en) | 2002-08-02 | 2014-09-16 | 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 |
| CN105019274A (en) * | 2015-08-18 | 2015-11-04 | 青岛大学 | Method for improving reactive dye ground color white resist printing effect of pure cotton fabric |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4668687B2 (en) | 2005-05-27 | 2011-04-13 | 矢崎総業株式会社 | Piercing terminal, connection structure between flat circuit body and piercing terminal, and connection method between flat circuit body and piercing terminal |
-
1991
- 1991-05-10 JP JP3135446A patent/JP2549583B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8450302B2 (en) | 2002-08-02 | 2013-05-28 | Ab Science | 2-(3-aminoaryl) amino-4-aryl-thiazoles and their use as c-kit inhibitors |
| US8835435B2 (en) | 2002-08-02 | 2014-09-16 | Ab Science | 2-(3-aminoaryl) amino-4-aryl-thiazoles and their use as c-kit inhibitors |
| US8993573B2 (en) | 2002-08-02 | 2015-03-31 | 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 |
| CN105019274A (en) * | 2015-08-18 | 2015-11-04 | 青岛大学 | Method for improving reactive dye ground color white resist printing effect of pure cotton fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2549583B2 (en) | 1996-10-30 |
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