KR960005657B1 - Process for producing reactive liquid dye - Google Patents
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- KR960005657B1 KR960005657B1 KR1019930003338A KR930003338A KR960005657B1 KR 960005657 B1 KR960005657 B1 KR 960005657B1 KR 1019930003338 A KR1019930003338 A KR 1019930003338A KR 930003338 A KR930003338 A KR 930003338A KR 960005657 B1 KR960005657 B1 KR 960005657B1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/22—Dyes with unsubstituted amino groups
- C09B1/24—Dyes with unsubstituted amino groups sulfonated
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0083—Solutions of dyes
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Abstract
Description
본 발명은 안트라퀴논계 화합물을 주성분으로 하고 있어 셀룰로스 섬유에 밝은 청색으로 나염되며 유리산의 형태로 다음 구조식(I)의 반응성 액체염료의 제조방법에 관한 것이다.The present invention relates to a method for preparing a reactive liquid dye of the following structural formula (I) having an anthraquinone-based compound as a main component, which is printed in light blue on cellulose fibers and in the form of a free acid.
본 발명에 따른 구조식(I)의 화합물은 유리산 상태에서 분말상태나 액체상태로 존재할 수 있다.The compound of formula (I) according to the present invention may exist in powder or liquid state in the free acid state.
본 발명의 액체염료는 수용성 음이온 염료로서 장기 보관하거나 광범위한 온도범위(-10℃~30℃)에서도 침전되지 않고 안정성이 우수하고 장기보관이 가능한 액체염료이다.Liquid dye of the present invention is a water-soluble anionic dye is a liquid dye that is excellent in stability and long-term storage without long-term storage or precipitation in a wide temperature range (-10 ℃ ~ 30 ℃).
종래 셀룰로스 섬유 나염에는 분말염료를 용액상태로 만들어 사용하여 왔으나 염색 및 나염공정의 자동화 설비에 맞추어 주는데는 액체상태의 염료가 적합하므로 최근에는 고농도의 액체염료가 요구되고 있는 실정이다.Conventional cellulose fiber printing has been used in the form of a powder dye in a solution state, but the liquid dye is suitable for the dyeing and dyeing automation equipment to meet the situation in recent years, a high concentration of liquid dye is required.
그러나 고농도의 액체염료는 온도변화나 장기 보관시에 염료의 침전이 일어나기 쉽고 침전이 일어나게 되면 자동화 설비에 사용이 불가능하게 되므로 저농도 제품으로 밖에 사용할 수 없었다.However, high concentration liquid dyes could be used only as low-concentration products because it would be easy to precipitate dyes during temperature changes or long-term storage, and it would be impossible to use them in automated facilities.
본 발명은 상기의 결점을 보완함으로서 하기 구조식으로 표시되는 시.아이 리액티브 블루우 49(C.I. Reactive Blue 49)에 비해 균염성 및 축적성(build up)이 진전된 특성을 갖는 염료의 제조방법에 관한 것이다.The present invention is directed to a method for preparing a dye having the properties of improved leveling and build up compared to CI Reactive Blue 49 represented by the following structural formula by supplementing the above drawbacks. It is about.
특히 기존 제품에 비해 용해성이 우수해서 침전방지를 위해 다른 첨가물을 부과하지 않아도 장기 보관이 가능하다. 또한 용해도를 증진시키고 불순물 등을 완전히 제거하기 위하여 역삼투압법을 이용하여 막(Membrane)을 거쳐서 순수한 염료를 만들므로서 습윤, 세탁견뢰도, 마찰, 땀, 일광견뢰도 등을 증진시킬 수 있고, 염착력이 뛰어나 잔염이 별로 남지 않으며, 폐수처리에도 용이한 특징을 갖고 있다.In particular, it has excellent solubility compared to existing products, so long-term storage is possible without imposing other additives to prevent precipitation. In addition, by improving the solubility and completely removing impurities, we can improve the wetness, washing fastness, friction, sweat, daylight fastness by making reverse dye through membrane (Membrane) by using reverse osmosis method. It has excellent features, so there is not much residual salt, and it is easy to treat wastewater.
본 발명의 목적은 장기간 보관하거나 해외에 수출시 기후변화(온도변화)에 안정성이 있어 침전이 생기지 않으며, 자동화설비(자동염색설비)에 안정하게 사용할 수 있는 고농도의 액체염료의 제법에 관한 것이다.An object of the present invention relates to a method of producing a high concentration of liquid dyes that can be used stably in an automated facility (auto dyeing facility) because it is stable to climate change (temperature change) when stored for a long time or exported abroad.
본 발명에서 제조된 고농도 액체염료는 셀룰로스를 포함하여 종이, 피혁의 염색 또는 나염에 사용할 수 있다.The high concentration liquid dye prepared in the present invention can be used for dyeing or printing of paper, leather, including cellulose.
본 발명의 구조식(I)의 새로운 반응성 액체 나염염료의 제조방법을 상세히 설명하면 다음과 같다.Hereinafter, a method for preparing a novel reactive liquid printing dye of formula (I) of the present invention will be described in detail.
하기 구조식(II)의 1-아미노-4-브로모안트라퀴논-2-술폰산(1-Amino-4-Bromoantraquinone-2-sulfonic acid)와 구조식(II)의 1.3-디아미노-2.4.6-트리메틸벤젠-5-술폰산(1.3-Diamino-2.4.6-trimethylbenzene-5-sulfonic acid)을 수용액 중에서 촉매 염화제일구리(CuCl)를 사용하여 65℃~70℃에서 12~15시간 축합반응시킨 후 염산이나 농황산으로 산석시키고 여과하여 구조식(IV)의 축합반응을 얻는다.1-Amino-4-bromoanthraquinone-2-sulfonic acid of formula (II) and 1.3-diamino-2.4.6-trimethyl of formula (II) Condensation reaction of benzene-5-sulfonic acid (1.3-Diamino-2.4.6-trimethylbenzene-5-sulfonic acid) in aqueous solution using catalytic cupric chloride (CuCl) at 65 ℃ ~ 70 ℃ for 12-15 hours The precipitate is concentrated with concentrated sulfuric acid and filtered to obtain a condensation reaction of Structural Formula (IV).
여기에서 얻은 구조식(IV)의 축합반응물을 중성 수용액으로 조정하고 구조식(V)의 염화시아눌을 첨가하여 0℃~5℃의 온도에서 pH를 5.0~6.0으로 조절하여 1차 축합시켜 구조식(VI)의 축합반응물을 얻을 수 있으며 여기에 계속해서 일반식(VII)의 설포안트라아니릭산(Sulfoanthranilic acid)을 첨가하여 pH 5.0~6.0으로 조절하면서 20℃~40℃의 온도를 유지하여 반응을 완료시키면 구조식(I)의 반응성 청색염료를 얻을 수 있다.The condensation reaction product of the structural formula (IV) obtained here was adjusted to a neutral aqueous solution, and cyanuric chloride of the structural formula (V) was added to adjust the pH to 5.0 to 6.0 at a temperature of 0 ° C. to 5 ° C. to condense the first condensation. ) Condensation reaction product is added to the mixture. Subsequently, sulfoanthranilic acid of general formula (VII) is added to adjust the pH to 5.0 to 6.0, and the temperature is maintained at 20 ° C to 40 ° C to complete the reaction. The reactive blue dye of structural formula (I) can be obtained.
최종염료는 유리산의 형태나 염의 형태일 수 있다.The final dye may be in the form of a free acid or in the form of a salt.
본 발명 반응성 액체염료의 제조방법을 실시예에 의해 설명하면 다음과 같다.When explaining the method for producing a reactive liquid dye of the present invention by the following examples.
[실시예 1]Example 1
19.1중량부의 1-아미노-4-브로모안트라퀴논-2-술폰산(II)을 150중량부의 중성 수용액으로 조정하고 16.1중량부의 1,3-디아미노-2,4,6-트리메틸벤젠-5-술폰산(III)을 수용액으로 첨가하고 20.16중량부의 중탄산나트륨을 첨가하고 염화제일구리 1.05중량부를 가하여 65℃~70℃에서 12~15시간 반응시켜서 반응이 완료되면 여과하고 농염산으로 산식시킨 후 염석시켜서 일반식(IV)의 축합반응 화합물을 얻었다.19.1 parts by weight of 1-amino-4-bromoanthraquinone-2-sulfonic acid (II) was adjusted to 150 parts by weight of a neutral aqueous solution and 16.1 parts by weight of 1,3-diamino-2,4,6-trimethylbenzene-5- Sulfonic acid (III) was added as an aqueous solution, 20.16 parts by weight of sodium bicarbonate was added, 1.05 parts by weight of cuprous chloride was added and reacted at 65 ° C. to 70 ° C. for 12 to 15 hours. The reaction was completed, filtered, concentrated with hydrochloric acid and salted out. The condensation reaction compound of general formula (IV) was obtained.
상기 구조식(IV)의 화합물 12.98중량부를 150부의 중성용액으로 만든 후 4.2중량부의 염화시아놀(V)을 첨가하고 0℃~5℃로 축합시켜서 pH를 5.5~6.5으로 조정하여 2시간 동안 축합반응시켰다.12.98 parts by weight of the compound of formula (IV) was made into 150 parts of neutral solution, and then 4.2 parts by weight of cyano chloride (V) was added and condensed at 0 ° C. to 5 ° C. to adjust the pH to 5.5 to 6.5 for 2 hours. I was.
다음 구조식(VII)의 5-술포안트라니릭에시드(5-Sulfoanthranilic acid) 5.01중량부를 80중량부의 중성용액으로 만들어 상기 반응액에 가하여 20℃~40℃의 온도에서 수시간 반응시켜서 pH를 5.0~6.0으로 조절하여 반응을 완결시켰다.5.01 parts by weight of 5-Sulfoanthranilic acid (5-Sulfoanthranilic acid) of the following formula (VII) was made into 80 parts by weight of a neutral solution, and added to the reaction solution and reacted at a temperature of 20 ° C.-40 ° C. for several hours. Controlled to complete the reaction.
여기에서 얻은 반응액을 역삼투압장치인 막을 통과시킴으로서 무기염을 제거하여 구조식(I)의 고농도의 액체염료를 얻었다. 이 액체염료의 염료함량은 32중량부였고 수율은 74.5%이었다.The reaction solution obtained was passed through a membrane, which is a reverse osmosis system, to remove inorganic salts, thereby obtaining a liquid dye having a high concentration of structural formula (I). The dye content of this liquid dye was 32 parts by weight and the yield was 74.5%.
이 염료는 셀룰로스 섬유에 나염하면 선명한 청색염색물을 얻을 수가 있으며, 용해도가 우수하여 높은 축적성(build up 효과)으로 잔액이 적으며, 습윤, 세탁견뢰도, 마찰견뢰도, 땀, 일광견뢰도가 우수한 염색물을 얻을 수 있었다.This dye has a clear blue dye when printed on cellulose fibers. It has excellent solubility, low build-up due to high build-up effect, and excellent wet, wash fastness, friction fastness, sweat, and light fastness. Could get water
실시예 1의 방법으로 제조된 염료의 특성을 다음 표 1에 기재하였다.The properties of the dyes prepared by the method of Example 1 are set forth in Table 1 below.
[표 1]TABLE 1
염료의 특성Dye Properties
[실시예 2]Example 2
실시예 1과 동일한 조건하에서, 실시예 1에서 얻은 구조식(IV)의 축합반응 화합물 13중량부를 150중량부의 중성 수용액으로 만들고, 4.2중량부의 염화시아눌을 첨가시켜서 0℃~5℃로 축합시켜 pH를 5.5~6.5로 조절하여 2~3시간 교반시킨 다음 구조식(VII)의 4-설포안트라니릭에시드(4-sulfoanthranilic acid)를 5.01중량부를 80중량부의 중성용액으로 만들어 상기 반응액에 가하여 20℃~40℃의 온도로 반응시키면 실시예 1에서 얻은 것과 동등한 색상 및 제반견뢰도가 우수한 밝은 청색염료 화합물을 얻을 수 있고, 이 반응액을 역삼투압장치인 막을 통과시켜서 구조식(I)의 염료를 얻는다.Under the same conditions as in Example 1, 13 parts by weight of the condensation reaction compound of Structural Formula (IV) obtained in Example 1 were made into 150 parts by weight of a neutral aqueous solution, 4.2 parts by weight of cyanuric chloride was added and condensed at 0 ° C. to 5 ° C. to pH To 5.5 to 6.5, and stirred for 2 to 3 hours. Then, 5.01 parts by weight of 4-sulfoanthranilic acid (4-sulfoanthranilic acid) of the formula (VII) was made into 80 parts by weight of a neutral solution, and added to the reaction solution. When the reaction is carried out at a temperature of 40 ° C., a light blue dye compound having excellent color and overall fastness equivalent to that obtained in Example 1 can be obtained. The reaction solution is passed through a membrane, which is a reverse osmosis apparatus, to obtain a dye of formula (I).
실시예 2에서도 염료의 수율은 74.5%이었다.In Example 2, the yield of the dye was 74.5%.
종래의 시.아이 리엑티브 블루우 49의 제조방법에서는 상기 구조식(IV)의 화합물에 메타아니릭산(metanilic acid)와 설파아니릭산(Sulfanilic acid)를 반응시켜 제조되는데 비하여 본 발명에서는 상기 구조식(IV)의 화합물에 술포안트라니릭산(Sulfoanthranilic acid)를 반응시켜 제조된다. 종래 시.아이. 리엑티브 블루우 49가 분말상태의 것인데 비하여 본 발명의 제품은 유리산 상태에서 액체상태나 분말상태로 존재할 수 있다.In the conventional method for preparing S.I. reactive blue cow 49, the compound of formula (IV) is prepared by reacting metaanilic acid (metanilic acid) with sulfanilic acid (Sulfanilic acid). Prepared by reacting sulfoanthranilic acid with a compound of Conventional S.I. Whereas reactive blue cow 49 is in powder form, the product of the present invention may exist in liquid or powder form in the free acid state.
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