JPH06136281A - Dye water-based liquid composition - Google Patents
Dye water-based liquid compositionInfo
- Publication number
- JPH06136281A JPH06136281A JP31077492A JP31077492A JPH06136281A JP H06136281 A JPH06136281 A JP H06136281A JP 31077492 A JP31077492 A JP 31077492A JP 31077492 A JP31077492 A JP 31077492A JP H06136281 A JPH06136281 A JP H06136281A
- Authority
- JP
- Japan
- Prior art keywords
- liquid composition
- dye
- parts
- formula
- reaction
- 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
Classifications
-
- 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
- C09B67/0072—Preparations with anionic dyes or reactive dyes
- C09B67/0073—Preparations of acid or reactive dyes in liquid form
-
- 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
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/08—Azo dyes
- C09B62/085—Monoazo dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は黄色染料の水性液状組成
物に関する。更に詳しくは反応染料の貯蔵安定性に優れ
る濃厚水性液状組成物に関する。FIELD OF THE INVENTION The present invention relates to an aqueous liquid composition of a yellow dye. More specifically, it relates to a concentrated aqueous liquid composition having excellent storage stability of a reactive dye.
【0002】[0002]
【従来の技術】従来より、染料の製品形態として粉末状
のものが多用されているが、近年粉塵汚染防止等作業環
境改善、計量、及び溶解等に於ける取扱いの容易さ、自
動計量への対応等から、液状品が広く用いられる様にな
って来ている。2. Description of the Related Art Conventionally, powdered products have been widely used as product forms of dyes, but in recent years, improvement of work environment such as prevention of dust pollution, easy handling in weighing and dissolving, and automatic weighing As a result, liquid products have come to be widely used.
【0003】その液状品として、保管に於て分解、結晶
析出等を起こさない貯蔵安定性が大きな要件であり、又
運搬、保管、使用の便宜上から可及的高濃度化が課題で
ある。As the liquid product, storage stability which does not cause decomposition, crystal precipitation, etc. during storage is a major requirement, and the highest possible concentration is a problem from the viewpoint of transportation, storage and use.
【0004】安定性向上のため、液状品中の脱塩処理及
び各種の溶解助剤の添加が実施されているが、染料のス
ルホン酸基の型として、遊離酸、ナトリウム塩或はカリ
ウム塩は、多くの場合溶解度が十分でなく、結晶析出等
問題ある事からその安定性向上には高度の脱塩処理、各
種の溶解助剤の組合せ及び多量添加等の煩雑な操作を要
しており、更に低温時の安定性、染料高濃度化に自ずと
限界を有している。後記の式(1)の遊離酸、ナトリウ
ム塩或はカリウム塩(Mが水素、Na或はKの場合)の
染料液状品も例外ではなく、低温乃至室温での長期間貯
蔵安定性、特に染料高濃度に於て問題を有している。In order to improve stability, desalting treatment in liquid products and addition of various solubilizing agents have been carried out. Free acid, sodium salt or potassium salt is used as a type of sulfonic acid group of dye. , In many cases, the solubility is not sufficient and there is a problem such as crystal precipitation, so that the stability is improved by a complicated desalting treatment, a combination of various dissolution aids, and a complicated operation such as large addition, Furthermore, there are naturally limits to stability at low temperatures and higher dye concentrations. Liquid dyes of the free acid, sodium salt or potassium salt of formula (1) (M is hydrogen, Na or K) described below are not exceptions, and long-term storage stability at low temperature to room temperature, especially dyes It has problems at high concentrations.
【0005】[0005]
【発明が解決しようとする課題】後記の式(1)の反応
染料について、低温乃至室温(−10℃〜40℃)に於
て長期間貯蔵安定な濃厚水性液状組成物が要望されてい
る。With respect to the reactive dye of the formula (1) described below, there is a demand for a concentrated aqueous liquid composition which is stable in storage at low temperature to room temperature (-10 ° C to 40 ° C) for a long period of time.
【0006】[0006]
【課題を解決するための手段】本発明者らは、前記の課
題を解決すべく鋭意検討の結果、本発明を完成するに至
ったものである。The present inventors have completed the present invention as a result of intensive studies to solve the above-mentioned problems.
【0007】即ち本発明は、式(1)That is, the present invention uses the formula (1)
【0008】[0008]
【化2】 [Chemical 2]
【0009】(式中、RはC1 〜C4 のアルキル基又は
アルコキシアルキル基を表しXは水素又は−SO3 M基
を表し、Mは各々独立に水素、Li、Na又はKを表
す。但しMの内、少なくとも1個のMは、Liを表
す。)で表される反応染料の水性液状組成物に関し、効
率的、工業的有利な方法に依り、低温乃至室温に於て長
期間貯蔵安定な濃厚水性液状組成物を提供するものであ
る。(In the formula, R represents a C 1 -C 4 alkyl group or an alkoxyalkyl group, X represents hydrogen or a —SO 3 M group, and each M independently represents hydrogen, Li, Na or K. However, regarding the aqueous liquid composition of the reactive dye represented by the formula (1), at least one of M represents Li), which is stored at low temperature to room temperature for a long time by an efficient and industrially advantageous method. The present invention provides a stable concentrated aqueous liquid composition.
【0010】本発明を詳細に説明する。式(1)に於
て、Mが水素、Na、Kで表される反応染料は、それ自
体特公昭57−14779に依り公知であり、例えば以
下の様にして製造される。遊離酸として式(2)The present invention will be described in detail. The reactive dye represented by the formula (1) in which M is hydrogen, Na or K is known per se from Japanese Patent Publication No. 57-14779, and is produced, for example, as follows. Formula (2) as free acid
【0011】[0011]
【化3】 [Chemical 3]
【0012】(式中、Xは水素又は−SO3 H基を表
す。)で表される化合物と塩化シアヌルとを縮合させ、
次いでその生成物をジアゾ化し次いで、遊離酸として式
(3)A compound represented by the formula (wherein X represents hydrogen or a --SO 3 H group) and cyanuric chloride are condensed,
The product is then diazotized and then used as the free acid of formula (3)
【0013】[0013]
【化4】 [Chemical 4]
【0014】(式中、RはC1 〜C4 のアルキル基又は
アルコキシアルキル基を表す)で表される化合物とカッ
プリングさせ、次いで、遊離酸として4−又は、3−ア
ミノベンゼンスルホン酸と反応せしめる事に依り得られ
る。(Wherein R represents a C 1 -C 4 alkyl group or an alkoxyalkyl group), and then, as a free acid, 4- or 3-aminobenzenesulfonic acid. It can be obtained by reacting.
【0015】式(2)で表される化合物の具体例として
は、2,4−ジアミノベンゼンスルホン酸、2,4−ジ
アミノ−1,5−ベンゼンジスルホン酸等が挙げられ
る。Specific examples of the compound represented by the formula (2) include 2,4-diaminobenzenesulfonic acid and 2,4-diamino-1,5-benzenedisulfonic acid.
【0016】更に、式(3)で表される化合物の具体例
としては、3−スルホメチル−1,4−ジメチル−6−
ヒドロキシ−2−ピリドン、1−エチル−3−スルホメ
チル−4−メチル−6−ヒドロキシ−2−ピリドン、1
−プロピル−3−スルホメチル−4−メチル−6−ヒド
ロキシ−2−ピリドン、1−ブチル−3−スルホメチル
−4−メチル−6−ヒドロキシ−2−ピリドン、1−メ
トキシプロピル−3−スルホメチル−4−メチル−6−
ヒドロキシ−2−ピリドン等が挙げられる。又、式
(3)に於て、5位に−CONH2基の化合物は、カッ
プリング時、それ自身が離脱するため、各々相当する化
合物も反応に使用出来る。Further, specific examples of the compound represented by the formula (3) include 3-sulfomethyl-1,4-dimethyl-6-.
Hydroxy-2-pyridone, 1-ethyl-3-sulfomethyl-4-methyl-6-hydroxy-2-pyridone, 1
-Propyl-3-sulfomethyl-4-methyl-6-hydroxy-2-pyridone, 1-butyl-3-sulfomethyl-4-methyl-6-hydroxy-2-pyridone, 1-methoxypropyl-3-sulfomethyl-4- Methyl-6-
Hydroxy-2-pyridone and the like can be mentioned. Further, in the formula (3), the compound having a —CONH2 group at the 5-position itself leaves during coupling, so that corresponding compounds can also be used in the reaction.
【0017】本発明の水性液状組成物に於いては、式
(1)で表される反応染料の3又は、4個のスルホン酸
基の内、少なくとも1個が−SO3 Li基を形成してい
るが、この塩を形成せしめる方法としては、特に限定さ
れないが、例えば反応染料を製造するに際し、溶解剤、
中和剤として通常用いる炭酸ナトリウム、重炭酸ナトリ
ウム、水酸化ナトリウム、水酸化カリウム等の代わりに
その一部又は、全部を水酸化リチウム、炭酸リチウム等
を使用する事に依り、−SO3 Li基に変換出来る。こ
の際、使用量としては、反応染料1モルに対し1〜10
モル、より好適には2〜5モルであり、反応の各段階で
適宜使用する事が出来る。In the aqueous liquid composition of the present invention, at least one of the three or four sulfonic acid groups of the reactive dye represented by the formula (1) forms a —SO 3 Li group. However, the method for forming this salt is not particularly limited, for example, in the case of producing a reactive dye, a solubilizer,
Usually sodium carbonate used as a neutralizing agent, sodium bicarbonate, sodium hydroxide, a part in place, such as potassium hydroxide or, all lithium hydroxide, depending on the use of lithium carbonate, -SO 3 Li groups Can be converted to. At this time, the amount used is 1 to 10 with respect to 1 mol of the reactive dye.
The amount is more preferably 2 to 5 mol and can be appropriately used in each step of the reaction.
【0018】又、通常の方法にて反応染料を製造し、濾
過分離し得られた結晶を水酸化リチウム又は炭酸リチウ
ムを用いて再溶解し、−SO3 Li基に変換する事も出
来る。又、通常の方法による反応液を、塩化リチウム溶
液にての透析法に依り、カチオン交換し−SO3 Li基
を形成する事も出来る。It is also possible to produce a reactive dye by an ordinary method, filter and separate the obtained crystal, and redissolve it with lithium hydroxide or lithium carbonate to convert it into a --SO 3 Li group. Further, the reaction solution obtained by a usual method can be cation exchanged by a dialysis method using a lithium chloride solution to form a —SO 3 Li group.
【0019】本発明に於いて、得られた反応液を所望の
染料濃度の水性液状組成物と成すためには、蒸発濃縮す
るか又は、より好適には逆浸透法に依り脱塩濃縮する。
逆浸透法に於いては、濾過膜として、ポリベンツイミダ
ゾロン、セルロースアセテート、ポリアミド系等を用い
て、通常10〜30Kgの圧力下で実施する。In the present invention, in order to form the reaction solution obtained into an aqueous liquid composition having a desired dye concentration, it is concentrated by evaporation or, more preferably, desalted and concentrated by a reverse osmosis method.
The reverse osmosis method is usually carried out under a pressure of 10 to 30 kg using polybenzimidazolone, cellulose acetate, polyamide or the like as a filtration membrane.
【0020】安定な濃厚液状組成物とするためには、液
中のNaCl、Na2 SO4 、KCl等の無機塩の可及
的低減化が望ましく、煩雑な脱塩処理操作が実施される
が、本発明の液状組成物の場合、溶解度、安定性が極め
て高く、高度又は高次の脱塩処理を必要としない。In order to obtain a stable concentrated liquid composition, it is desirable to reduce inorganic salts such as NaCl, Na 2 SO 4 and KCl in the liquid as much as possible, and a complicated desalting treatment operation is carried out. In the case of the liquid composition of the present invention, the solubility and stability are extremely high, and no advanced or high-order desalting treatment is required.
【0021】脱塩程度としては、液中濃度概ね1%程度
で充分その目的は達成され、この点、実施上操作の簡略
化、効率化、工業的有利性が特記される。Regarding the degree of desalting, a concentration of about 1% in the liquid is sufficient to achieve the purpose, and in this respect, the simplification of the operation in practice, efficiency improvement, and industrial advantage are noted.
【0022】本発明の水性液状組成物は、通常20〜4
0重量%の染料分を含有するが、必要に応じ水を加え所
望の濃度に調整される。尚、該液状組成物に通常用いら
れる添加剤、例えばε−カプロラクトン、尿素、エチレ
ングリコール類、ポリアクリル酸ナトリウム、縮合燐酸
塩類等の溶解助剤、金属イオン封鎖剤、pH調整剤、防
菌防カビ剤等を必要に応じ通常0.5〜50重量%添加
する事又、液状組成物のpHを6.0〜8.0程度に調
整する事等は、経時安定性のより向上に有効である。The aqueous liquid composition of the present invention is usually 20 to 4
It contains 0% by weight of dye, but is adjusted to the desired concentration by adding water if necessary. Additives that are usually used in the liquid composition, for example, ε-caprolactone, urea, ethylene glycols, sodium polyacrylate, dissolution aids such as condensed phosphates, sequestering agents, pH adjusting agents, antibacterial agents, etc. It is effective to add 0.5 to 50% by weight of a fungicide, etc., if necessary, and to adjust the pH of the liquid composition to about 6.0 to 8.0 to improve the stability with time. is there.
【0023】本発明の反応染料の水性液状組成物は、低
温乃至室温(−10℃〜40℃)の長期保管に於いても
分解、結晶析出等の問題無く安定性に優れるものであ
り、特に、適度な脱塩処理に於いて、染料高濃度化が可
能な事で意義付けられる。The aqueous liquid composition of the reactive dye of the present invention is excellent in stability without problems such as decomposition and crystal precipitation even during long-term storage at low temperature to room temperature (-10 ° C to 40 ° C). , It is significant that the dye concentration can be increased in the moderate desalting process.
【0024】該液状組成物は、セルロース繊維及びセル
ロース含有繊維の染色に適用される。木綿、レーヨン、
麻及びこれ等の混紡、交織品更に、木綿/ポリエステル
混紡品等のセルロース/合成繊維混紡、交織品を対象と
して、通常の染色法にて行う。The liquid composition is applied for dyeing cellulose fibers and fibers containing cellulose. Cotton, rayon,
The usual dyeing method is applied to hemp and blended fabrics of these and mixed woven products, and further to cellulose / synthetic fiber blended fabrics and mixed woven products such as cotton / polyester blended products.
【0025】[0025]
【実施例】以下、実施例により本発明を更に詳細に説明
する。尚、実施例中、部は重量部、%は重量%である。EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, parts are parts by weight and% is% by weight.
【0026】実施例1 2,4−ジアミノベンゼンスルホン酸18.8部を水酸
化ナトリウムを加え、水300部に溶解した。その溶液
に塩化シアヌル19部を加え、0〜5℃、pH6〜7に
て一次縮合を行った。反応中、炭酸ナトリウムを添加し
反応を完結させた。次いで、その生成物を塩酸及び亜硝
酸ナトリウムを用い常法にてジアゾ化した。次いで、1
−エチル−5−カルバモイル−3−スルホメチル−4−
メチル−6−ヒドロキシ−2−ピリドン29部を水20
0部に溶解し加え、10℃、pH6〜7にてカップリン
グを行った。反応中、水酸化リチウム4.8部を添加し
反応を完結させた。次いで4−アミノベンゼンスルホン
酸18部を水150部に溶解し加え、50℃、pH7〜
8にて二次縮合を行った。反応中、水酸化リチウム4.
8部を添加し反応を完結させた。反応液を逆浸透装置に
依り脱塩濃縮処理し、水性液状組成物210部を得た。
尚、逆浸透装置についてはポリアミド系膜(帝人エンジ
ニアリング社製)を用いて、15Kg/cm2 の圧力で
実施した。得られた液状組成物中の染料構造を分析した
結果、式(4)で表される染料に於いて3個のMの内、
2個はLi、1個はNaであった。染料濃度は32.9
%で、NaCl0.9%、Na2 SO4 0.2%を含有
していた。Example 1 14.8 parts of 2,4-diaminobenzenesulfonic acid was added to sodium hydroxide and dissolved in 300 parts of water. 19 parts of cyanuric chloride was added to the solution, and primary condensation was performed at 0 to 5 ° C and pH 6 to 7. During the reaction, sodium carbonate was added to complete the reaction. Then, the product was diazotized with hydrochloric acid and sodium nitrite by a conventional method. Then 1
-Ethyl-5-carbamoyl-3-sulfomethyl-4-
Methyl-6-hydroxy-2-pyridone 29 parts water 20
It was dissolved in 0 part and added, and coupling was performed at 10 ° C. and pH 6 to 7. During the reaction, 4.8 parts of lithium hydroxide was added to complete the reaction. Then, 18 parts of 4-aminobenzenesulfonic acid is dissolved in 150 parts of water and added, and the mixture is added at 50 ° C. and pH 7 to 7.
Secondary condensation was carried out at 8. During the reaction, lithium hydroxide 4.
8 parts were added to complete the reaction. The reaction solution was desalted and concentrated by a reverse osmosis apparatus to obtain 210 parts of an aqueous liquid composition.
A polyamide membrane (manufactured by Teijin Engineering Co., Ltd.) was used as the reverse osmosis device at a pressure of 15 kg / cm 2 . As a result of analyzing the dye structure in the obtained liquid composition, among the three M's in the dye represented by the formula (4),
Two were Li and one was Na. Dye density is 32.9
%, NaCl 0.9%, Na 2 SO 4 0.2%.
【0027】[0027]
【化5】 [Chemical 5]
【0028】実施例2 実施例1に準じて染料製造を行ったが、二次縮合に於い
て、4−アミノベンゼンスルホン酸及び反応中和剤の水
酸化リチウムの代わりに、各々3−アミノベンゼンスル
ホン酸18部及び水酸化ナトリウム8部を使用して実施
した。反応液を同様に逆浸透法に依り脱塩濃縮処理し、
液状組成物220部を得た。得られた液状組成物中の染
料構造は、式(5)で表される染料に於いて3個のMの
内、1個はLi、2個はNaであった。染料濃度は3
2.3%で、NaCl1.1%、Na2 SO4 0.2%
を含有していた。Example 2 A dye was prepared according to Example 1, except that in the secondary condensation, 4-aminobenzenesulfonic acid and lithium hydroxide as a reaction neutralizing agent were used instead of 3-aminobenzene, respectively. It was carried out using 18 parts of sulfonic acid and 8 parts of sodium hydroxide. Similarly, the reaction solution is desalted and concentrated by the reverse osmosis method,
220 parts of liquid composition was obtained. Regarding the dye structure in the obtained liquid composition, in the dye represented by the formula (5), among 3 M, 1 was Li and 2 was Na. Dye density is 3
2.3%, NaCl 1.1%, Na 2 SO 4 0.2%
Was included.
【0029】[0029]
【化6】 [Chemical 6]
【0030】実施例3 実施例1に準じて染料製造を行ったが、一次縮合に於け
る反応中和剤の炭酸ナトリウムの代わりに、炭酸リチウ
ム7.4部を用い、カップリング及び二次縮合に於ける
水酸化リチウムの代わりに、水酸化ナトリウムを使用し
て実施した。反応液を同様に逆浸透法に依り脱塩濃縮処
理し、液状組成物220部を得た。得られた液状組成物
中の染料構造は、式(4)で表される染料に於いて3個
のMの内、1個はLi、2個はNaであった。染料濃度
は32.5%で、NaCl1.0%、Na2 SO4 0.
2%を含有していた。Example 3 A dye was prepared according to Example 1, except that 7.4 parts of lithium carbonate was used instead of sodium carbonate as a reaction neutralizing agent in the primary condensation, and coupling and secondary condensation were carried out. Sodium hydroxide was used instead of lithium hydroxide in. The reaction solution was similarly desalted and concentrated by the reverse osmosis method to obtain 220 parts of a liquid composition. Regarding the dye structure in the obtained liquid composition, in the dye represented by the formula (4), among 3 M, 1 was Li and 2 was Na. The dye concentration is 32.5%, NaCl 1.0%, Na 2 SO 4 0.
It contained 2%.
【0031】実施例4 実施例1に準じて染料製造を行ったが、二次縮合に於け
る反応中和剤の水酸化リチウムの代わりに、水酸化カリ
ウムを使用して実施した。反応液を同様に逆浸透法に依
り脱塩濃縮処理し、液状組成物210部を得た。得られ
た液状組成物中の染料構造は、式(4)で表される染料
に於いて3個のMの内、1個はLi、2個はKであっ
た。 染料濃度は33.0%で、NaCl0.3%、K
Cl0.7%、Na2 SO4 0.1%、K2 SO4 0.
1%を含有していた。Example 4 A dye was prepared according to Example 1, except that potassium hydroxide was used instead of lithium hydroxide as a reaction neutralizing agent in the secondary condensation. The reaction solution was similarly desalted and concentrated by the reverse osmosis method to obtain 210 parts of a liquid composition. Regarding the dye structure in the obtained liquid composition, in the dye represented by the formula (4), among 3 M, 1 was Li and 2 was K. Dye concentration is 33.0%, NaCl 0.3%, K
Cl 0.7%, Na 2 SO 4 0.1%, K 2 SO 4 0.
It contained 1%.
【0032】実施例5 2,4−ジアミノ−1,5−ベンゼンジスルホン酸2
6.8部を水酸化ナトリウムを加え、水250部に溶解
した。その溶液に塩化シアヌル19部を加え、0〜5
℃、pH6〜7にて一次縮合を行った。反応中、炭酸リ
チウム4部を添加し反応完結させた。次いで、生成物を
塩酸及び亜硝酸ナトリウムを用いてジアゾ化した。次い
で、1−ブチル−5−カルバモイル−3−スルホメチル
−4−メチル−6−ヒドロキシ−2−ピリドン31.8
部を水250部に溶解し加え、10℃、pH6〜7にて
カップリングを行った。反応中、水酸化リチウム4.8
部を添加し反応を完結させた。次いで、4−アミノベン
ゼンスルホン酸18部を水150部に溶解し加え、50
℃、pH7〜8にて二次縮合を行った。反応中、水酸化
リチウム4.8部を添加し反応完結させた。反応液を同
様に逆浸透法に依り脱塩濃縮処理し、液状組成物230
部を得た。得られた液状組成物中の染料構造は、式
(6)で表される染料に於いて4個のMの内、3個はL
i、1個はNaであった。染料濃度は33.3%で、N
aCl1.1%、Na2 SO4 0.1%を含有してい
た。Example 5 2,4-Diamino-1,5-benzenedisulfonic acid 2
Sodium hydroxide was added to 6.8 parts and dissolved in 250 parts of water. Add 19 parts of cyanuric chloride to the solution, and add 0-5
Primary condensation was performed at a temperature of 6 to 7. During the reaction, 4 parts of lithium carbonate was added to complete the reaction. The product was then diazotized with hydrochloric acid and sodium nitrite. Then 1-butyl-5-carbamoyl-3-sulfomethyl-4-methyl-6-hydroxy-2-pyridone 31.8
Part was dissolved in 250 parts of water and added, and coupling was performed at 10 ° C. and pH 6 to 7. During the reaction, lithium hydroxide 4.8
Parts were added to complete the reaction. Then, 18 parts of 4-aminobenzenesulfonic acid is dissolved in 150 parts of water and added,
Secondary condensation was performed at a temperature of 7 to 8 ° C. During the reaction, 4.8 parts of lithium hydroxide was added to complete the reaction. Similarly, the reaction solution was desalted and concentrated by the reverse osmosis method to give a liquid composition 230
I got a part. The dye structure in the obtained liquid composition is as follows. Of the four M's in the dye represented by the formula (6), three are L's.
i, one was Na. Dye concentration is 33.3%, N
It contained aCl 1.1% and Na 2 SO 4 0.1%.
【0033】[0033]
【化7】 [Chemical 7]
【0034】実施例6〜12 式(7)に於いて、以下の表の構造の染料について、得
られた結果を示す。Examples 6 to 12 In the formula (7), the results obtained for the dyes having the structures shown in the following table are shown.
【0035】[0035]
【化8】 [Chemical 8]
【0036】[0036]
【表1】 [Table 1]
【0037】比較例 本発明の水性液状組成物の、特に低温貯蔵安定性を測定
するため、それ等の組成物を水で希釈し染料濃度30%
とし、以下の表1の安定性試験を行った。比較の対象と
しては、下記の式(8)、(9)、(10)、(11)
及び、(12)の構造の染料とし、同様に逆浸透法に依
り脱塩濃縮処理し、染料濃度30%の濃厚液とした。
尚、液状組成物中の無機塩含有量は0.8〜1.2%の
範囲に、又組成物のpHは6.5〜7.5の範囲に調整
した。Comparative Example In order to measure the low temperature storage stability of the aqueous liquid compositions of the present invention, these compositions were diluted with water to obtain a dye concentration of 30%.
The stability test shown in Table 1 below was performed. The objects of comparison are the following equations (8), (9), (10), (11)
Further, the dye having the structure of (12) was also desalted and concentrated by the reverse osmosis method to obtain a concentrated liquid having a dye concentration of 30%.
The content of the inorganic salt in the liquid composition was adjusted to 0.8 to 1.2%, and the pH of the composition was adjusted to 6.5 to 7.5.
【0038】[0038]
【化9】 [Chemical 9]
【0039】[0039]
【化10】 [Chemical 10]
【0040】[0040]
【化11】 [Chemical 11]
【0041】[0041]
【化12】 [Chemical 12]
【0042】[0042]
【化13】 [Chemical 13]
【0043】低温貯蔵安定性試験結果(−5℃保管)Results of low temperature storage stability test (-5 ° C. storage)
【表2】 表中、○は完溶状態、△は僅かに結晶析出の状態、×は
全体に結晶析出の状態を示す。[Table 2] In the table, ◯ indicates a completely dissolved state, Δ indicates a slightly crystallized state, and x indicates a crystallized state as a whole.
【0044】尚、別途、実施例2の液状組成物を調製す
る際、ε−カプロラクトンを5%添加した組成物は、9
0日後迄完溶状態であった。又、実施例3の液状組成物
に同様に、ε−カプロラクトンを5%添加した組成物
は、90日後迄完溶状態であった。又、実施例9の液状
組成物に同様に、ε−カプロラクトンを10%添加した
組成物は、60日後迄完溶状態であった。Separately, when the liquid composition of Example 2 was prepared, the composition containing 5% of ε-caprolactone was 9%.
It was in a completely dissolved state until 0 days later. Further, similarly to the liquid composition of Example 3, the composition containing 5% of ε-caprolactone was in a completely dissolved state until 90 days later. Also, similarly to the liquid composition of Example 9, the composition containing 10% of ε-caprolactone was in a completely dissolved state until 60 days later.
【0045】染色例 実施例1で得た液状組成物を水で希釈し染料濃度30%
とした液状組成物を用いて、下記組成の捺染糊を調製し
た。その色糊を木綿布に印捺し、80℃にて中間乾燥し
た後、102℃、10分間のスチーミングを行った。次
いで、ソーピング、水洗、乾燥し、鮮明な緑味黄色の捺
染染色物を得た。 捺染糊の組成 実施例1の液状組成物(染料濃度30%) 7部 5%アルギン酸ナトリウム水溶液 50″ 重炭酸ナトリウム 3″ 尿素 10″ 水 30″ 計 100部Dyeing Example The liquid composition obtained in Example 1 was diluted with water to give a dye concentration of 30%.
A printing paste having the following composition was prepared using the liquid composition described above. The color paste was printed on a cotton cloth, intermediately dried at 80 ° C., and then steamed at 102 ° C. for 10 minutes. Then, soaping, washing with water and drying were carried out to obtain a vivid green-yellow print dyeing product. Composition of printing paste Liquid composition of Example 1 (dye concentration 30%) 7 parts 5% sodium alginate aqueous solution 50 ″ sodium bicarbonate 3 ″ urea 10 ″ water 30 ″ 100 copies
【0046】[0046]
【発明の効果】長期の保管、特に低温貯蔵に於いても安
定な反応染料の濃厚水性液状組成物が得られた。Industrial Applicability A concentrated aqueous liquid composition of a reactive dye is obtained which is stable even during long-term storage, particularly at low temperature storage.
Claims (1)
ルキル基を表し、Xは水素又は−SO3 M基を表し、M
は各々独立に水素、Li、Na又はKを表す。但しMの
内、少なくとも1個のMは、Liを表す。)で表される
反応染料の水性液状組成物。1. A general formula: (In the formula, R represents a C 1 to C 4 alkyl group or an alkoxyalkyl group, X represents hydrogen or a —SO 3 M group, and M
Each independently represent hydrogen, Li, Na or K. However, among M, at least one M represents Li. ) An aqueous liquid composition of a reactive dye represented by:
Priority Applications (1)
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JP4310774A JP3068351B2 (en) | 1992-10-27 | 1992-10-27 | Dye aqueous liquid composition |
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JP4310774A JP3068351B2 (en) | 1992-10-27 | 1992-10-27 | Dye aqueous liquid composition |
Publications (2)
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JPH06136281A true JPH06136281A (en) | 1994-05-17 |
JP3068351B2 JP3068351B2 (en) | 2000-07-24 |
Family
ID=18009313
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JP4310774A Expired - Fee Related JP3068351B2 (en) | 1992-10-27 | 1992-10-27 | Dye aqueous liquid composition |
Country Status (1)
Country | Link |
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JP (1) | JP3068351B2 (en) |
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1992
- 1992-10-27 JP JP4310774A patent/JP3068351B2/en not_active Expired - Fee Related
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