JP2016034989A - Trisazo compound for black color, dye composition containing the same, and usage for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellent azo dye compound for a black color which can be produced without using dianisidine of a first category of a specified chemical substance, has adequate dyeing properties and light resistance and is used for paper and pulp.SOLUTION: There is provided a trisazo compound represented by a formula (1) or a salt thereof. The trisazo compound is obtained by azocoupling a monoazo compound synthesized from 1-amino-8-(4-methylphenylsulfonyloxy)naphthalene-3,6-disulfonic acid with a monoazo compound synthesized from 4-amino-5-hydroxynaphthalene-1,7-disulfonic acid. In the formula (1), A represents 7-sulfoxynaphthaleneazo-1-yl or 4-carboxybenzeneazenyl substituent.SELECTED DRAWING: None

Description

本発明は黒色用トリスアゾ化合物又はその塩、それを含有する染料組成物、それを使用する染色方法及びその染色物に関する。   The present invention relates to a black trisazo compound or a salt thereof, a dye composition containing the same, a dyeing method using the same, and a dyed product thereof.

セルロース繊維材料、特に紙・パルプ用の染料としては染着性がよい直接染料が多く用いられている。中でも黒色用染料としてＣ．Ｉ．ダイレクトブラック１９やＣ．Ｉ．ダイレクトブラック１６８等がよく使用されている。しかしながら、これらの染料は耐光性が低く、更にその製造にはジアニシジンを使用し、Ｃ．Ｉ．ダイレクトブラック１９は変異原性試験として知られるエームズ（Ａｍｅｓ）試験が陽性である。エームズ試験が陽性であれば、その使用による人体や環境への悪影響が知られており、その使用及び製造は極めて厳重な防護設備の下で作業する必要がある等、安全衛生管理面及び生産効率の面等から多くの問題を抱えている。   As a dye for cellulosic fiber materials, particularly paper and pulp, direct dyes having good dyeing properties are often used. Among them, C.I. I. Direct Black 19 and C.I. I. Direct black 168 or the like is often used. However, these dyes have low light resistance, and dianisidine is used for the production thereof. I. Direct Black 19 is positive for the Ames test, known as the mutagenicity test. If the Ames test is positive, the adverse effects on the human body and the environment due to its use are known, and its use and production must be carried out under extremely strict protective equipment. Have many problems in terms of

近年、工場の安全操業や環境保護の観点からエームズ試験陰性染料の開発が進められているが、染着性、耐光性を備えた染料が少ない等の未だ克服すべき課題も多い。エームズ試験陰性染料の使用分野を拡大する為に、エームズ試験陰性染料組成物やその染色物に耐光性の向上が求められているが、現状では満足出来る染料、染料組成物は見出されていない。   In recent years, Ames test negative dyes have been developed from the viewpoint of safe operation of plants and environmental protection, but there are still many problems to be overcome such as few dyes with dyeing and light fastness. In order to expand the field of use of Ames test negative dyes, Ames test negative dye compositions and dyed products are required to have improved light resistance, but no satisfactory dyes or dye compositions have been found at present. .

特開平９−２３０１４２号公報JP-A-9-230142 特開平８−１４６５５０号公報JP-A-8-146550 特開２００６−１９３７２２公報JP 2006-193722 A 特開２０１３−２４９３５８公報JP2013-249358A

細田 豊著「染料化学：理論製造」技報堂出版（１９６３）Hosoda Yutaka "Dye Chemistry: Theoretical Manufacturing" Gihodo Publishing (1963)

本発明は、特定化学物質第一類のジアニシジンを使用することなく製造出来、染着性及び耐光性の良好な紙・パルプ用の優れた黒色用アゾ化合物を提供する。   The present invention provides an excellent black azo compound for paper and pulp, which can be produced without using the first kind of specific chemical substance dianisidine, and has good dyeability and light resistance.

本発明者等は前記の問題点を解決すべく鋭意研究を重ねた結果、新規な黒色用アゾ化合物とそれを含む染料組成物を見出し、本発明に至ったものである。即ち、本発明は以下記載の１）〜５）に関する。   As a result of intensive studies to solve the above problems, the present inventors have found a novel azo compound for black and a dye composition containing the same, and have reached the present invention. That is, the present invention relates to the following 1) to 5).

１）下記式（１）で示されるトリスアゾ化合物又はその塩。

［式中、Ａは下記式（２）又は下記式（３）で表される置換基を示す］

1) A trisazo compound represented by the following formula (1) or a salt thereof.

[Wherein A represents a substituent represented by the following formula (2) or the following formula (3)]

２）Ａの結合位置がその結合するナフチル基の６位又は７位である前記１）に記載のトリスアゾ化合物又はその塩。
３）前記１）又は２）に記載のトリスアゾ化合物又はその塩を少なくとも１種含有する黒色用染料組成物。
４）前記３）に記載の黒色用染料組成物を用いることを特徴とするセルロース繊維材料の染色方法。
５）前記４）に記載の染色方法で染色された染色物。 2) The trisazo compound or a salt thereof according to 1) above, wherein the bonding position of A is the 6th or 7th position of the naphthyl group to which A is bonded.
3) A black dye composition containing at least one trisazo compound or salt thereof according to 1) or 2).
4) A method for dyeing a cellulose fiber material, comprising using the black dye composition as described in 3) above.
5) A dyed product dyed by the dyeing method described in 4) above.

本発明はエームズ試験が陰性であり、紙・パルプを高濃度で染色することが出来、又、染色物の耐光性が高い黒色アゾ染料として使用されるトリスアゾ化合物を提供する。   The present invention provides a trisazo compound that has a negative Ames test, can dye paper and pulp at a high concentration, and is used as a black azo dye having high light resistance of the dyed product.

以下、本発明を詳細に説明する。
本発明のトリスアゾ化合物又はその塩は、前記式（１）［式中、Ａは前記式（２）又は式（３）で表される置換基を示す］である。 Hereinafter, the present invention will be described in detail.
The trisazo compound of the present invention or a salt thereof is the formula (1) [wherein A represents a substituent represented by the formula (2) or the formula (3)].

Ａが式（２）の置換基の場合、その置換位置は結合するナフチル基の６位又は７位が好ましい。該ナフチル基のナンバーリングは前記式（１）に示す通りである。   When A is a substituent of the formula (2), the substitution position is preferably the 6th or 7th position of the naphthyl group to be bonded. The numbering of the naphthyl group is as shown in the formula (1).

Ａが式（３）の置換基の場合、その置換位置は結合するナフチル基の６位又は７位が好ましい。   When A is a substituent of formula (3), the substitution position is preferably the 6th or 7th position of the naphthyl group to be bonded.

本発明においてアゾ基は、シン型でもアンチ型でもそれらの混合物であってもよい。
本発明のアゾ化合物の塩としてはスルホン酸等の酸の塩、アミノ基等の塩基の塩が挙げられるが特に限定されない。該酸の塩としては、例えば、ナトリウム塩、カリウム塩、アンモニウム塩、アミン塩等が挙げられ、該塩基の塩としては、例えば、塩酸塩、硫酸塩、硝酸塩等の無機酸との塩、ｐ−トルエンスルホン酸塩、酢酸塩等の有機酸との塩が挙げられる。 In the present invention, the azo group may be syn type, anti type or a mixture thereof.
Examples of the salt of the azo compound of the present invention include acid salts such as sulfonic acid and base salts such as amino group, but are not particularly limited. Examples of the acid salt include sodium salt, potassium salt, ammonium salt, and amine salt. Examples of the base salt include salts with inorganic acids such as hydrochloride, sulfate, and nitrate, p. -Salts with organic acids such as toluene sulfonate and acetate.

本発明のアゾ化合物としては、後記の実施例に記載の化合物が特に好ましい。   As the azo compound of the present invention, compounds described in Examples below are particularly preferable.

本発明のアゾ化合物を含有する染料組成物も本発明に含まれる。該染料組成物には、水等の溶剤を含有し、その他の添加剤を含有していてもよい。   A dye composition containing the azo compound of the present invention is also included in the present invention. The dye composition contains a solvent such as water, and may contain other additives.

本発明の染料組成物は、セルロース繊維材料、特に紙やパルプを染色する際に使用することが出来、特に該染料組成物溶液を用いる染色方法、及びその染色方法により染色された染色物も本発明に含まれる。該溶液としては水溶液が好ましく、本発明の黒色染料を溶解し、必要により希釈して得られる。該染色方法としては、例えば、紙・パルプを染色する通常の染色条件による染色法や、サイズプレス法、コーテイング法を包含する表面塗工染色法又は内添染色法等が挙げられる。該染色物には本発明の染色方法で染色された紙・パルプとともに、それを加工して得られる物品も含まれる。   The dye composition of the present invention can be used for dyeing cellulose fiber materials, particularly paper and pulp. Particularly, the dyeing method using the dye composition solution, and the dyed material dyed by the dyeing method are also present. Included in the invention. The solution is preferably an aqueous solution, which is obtained by dissolving the black dye of the present invention and diluting it if necessary. Examples of the dyeing method include a dyeing method under normal dyeing conditions for dyeing paper and pulp, a surface coating dyeing method including a size press method and a coating method, or an internal dyeing method. The dyed product includes paper and pulp dyed by the dyeing method of the present invention and articles obtained by processing the same.

上記式（１）で表されるアゾ化合物及びその塩は、非特許文献１に記載されるような通常のアゾ染料の製法に従い、公知のジアゾ化、カップリングを行うことにより製造出来る。
その製造方法の一例示を示す。下記式（４）で表される化合物をジアゾ化し、下記式（５）の化合物と０℃〜４０℃、好ましくは１０℃〜１５℃、ｐＨ０．５〜１１、好ましくはｐＨ４．０〜５．０でカップリング反応させ、下記式（６）で示されるモノアゾ化合物を得る。式（４）及び式（５）の化合物は自体公知の化合物であり、市販もされている。下記式（４）においてＯＴｓはｐ−トルエンスルホン酸基を示す。 The azo compound represented by the above formula (1) and a salt thereof can be produced by performing known diazotization and coupling in accordance with a conventional method for producing an azo dye as described in Non-Patent Document 1.
An example of the manufacturing method is shown. A compound represented by the following formula (4) is diazotized, and a compound of the following formula (5) and 0 to 40 ° C., preferably 10 to 15 ° C., pH 0.5 to 11, preferably pH 4.0 to 5. A coupling reaction is performed at 0 to obtain a monoazo compound represented by the following formula (6). The compounds of formula (4) and formula (5) are known per se and are also commercially available. In the following formula (4), OTs represents a p-toluenesulfonic acid group.

上記式（５）で表される化合物をジアゾ化し、下記式（７）の化合物と０℃〜４０℃、好ましくは５℃〜１０℃、ｐＨ０．５〜１１、好ましくはｐＨ３．０〜３．５でカップリング反応させ、下記式（８）で示されるモノアゾ化合物を得る。式（７）の化合物は自体公知の化合物であり、市販もされている。   The compound represented by the above formula (5) is diazotized, and the compound of the following formula (7) and 0 ° C to 40 ° C, preferably 5 ° C to 10 ° C, pH 0.5 to 11, preferably pH 3.0 to 3. 5 to obtain a monoazo compound represented by the following formula (8). The compound of formula (7) is a compound known per se and is also commercially available.

次いで上記式（６）のモノアゾ化合物をジアゾ化し、前記式（８）の化合物と０℃〜４０℃、好ましくは２０℃〜２５℃、ｐＨ０．５〜１１、好ましくはｐＨ８．５〜９．５でカップリング反応させ、下記式（９）で示されるトリスアゾ化合物を得る。   Next, the monoazo compound of the above formula (6) is diazotized, and the compound of the above formula (8) and 0 ° C to 40 ° C, preferably 20 ° C to 25 ° C, pH 0.5 to 11, preferably pH 8.5 to 9.5. To obtain a trisazo compound represented by the following formula (9).

次いでこのトリスアゾ化合物（９）を４０℃〜１００℃、好ましくは８０℃〜８５℃、ｐＨ０．５〜１１、好ましくはｐＨ１０．５〜１１．０で脱トシル化反応に付し、下記式（１０）で示されるトリスアゾ化合物を得る。   Subsequently, this trisazo compound (9) was subjected to a detosylation reaction at 40 ° C. to 100 ° C., preferably 80 ° C. to 85 ° C., pH 0.5 to 11, preferably pH 10.5 to 11.0. ) Is obtained.

上記反応において、ジアゾ化工程はジアゾ成分の塩酸、硫酸等の鉱酸水溶液又は懸濁液に亜硝酸ナトリウム等の亜硝酸塩を混合するという順法によるか、あるいはジアゾ成分の中性若しくは弱アルカリ性の水溶液に亜硝酸塩を加えておき、これと鉱酸を混合するという逆法によって行われる。ジアゾ化の温度は、−１０℃〜４０℃が適当である。   In the above reaction, the diazotization step is performed by a conventional method of mixing a nitrite such as sodium nitrite with a mineral acid aqueous solution or suspension of diazo component such as hydrochloric acid or sulfuric acid, or a neutral or weak alkaline solution of diazo component. Nitrite is added to the aqueous solution and mixed with mineral acid. The temperature for diazotization is suitably from -10 ° C to 40 ° C.

カップリングして得られたモノアゾ化合物、ジスアゾ化合物又はトリスアゾ化合物は、そのままあるいは酸析や塩析により析出させ濾過して取り出しても、溶液又は懸濁液のまま次の工程へ進めてもよい。ジアゾニウム塩が難溶性で懸濁液となっている場合は濾過し、プレスケーキとして次のカップリング工程で使うことも出来る。又、精製が必要な場合には塩析を繰り返すか、又は有機溶媒を使用して水中から析出させればよい。精製に使用する有機溶媒としては、例えば、メタノール、エタノール等のアルコール類、アセトン等のケトン類等の水溶性有機溶媒が挙げられる。   The monoazo compound, disazo compound or trisazo compound obtained by the coupling may be used as it is, or may be precipitated by aciding out or salting out and filtered, or may proceed to the next step as a solution or suspension. If the diazonium salt is insoluble and in suspension, it can be filtered and used as a press cake in the next coupling step. If purification is required, salting out may be repeated, or it may be precipitated from water using an organic solvent. Examples of the organic solvent used for purification include water-soluble organic solvents such as alcohols such as methanol and ethanol, and ketones such as acetone.

尚、本発明において上記式（１）で表されるアゾ化合物は遊離酸として用いられるほか、アゾ化合物の塩を用いることが出来る。そのような塩としてはナトリウム塩、カリウム塩、リチウム塩のようなアルカリ金属塩や、アンモニウム塩、アミン塩等の有機塩が挙げられる。一般的にはナトリウム塩が用いられる。   In the present invention, the azo compound represented by the above formula (1) can be used as a free acid or a salt of an azo compound. Examples of such salts include alkali metal salts such as sodium salt, potassium salt and lithium salt, and organic salts such as ammonium salt and amine salt. In general, a sodium salt is used.

以下、実施例により本発明を更に詳細に説明するが、これらの実施例により本発明が限定されるものではない。実施例において特に断りがない限り、部は質量部を、％は質量％をそれぞれ意味する。各式中のスルホン酸基は遊離の形で表わす。   EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. Unless otherwise specified in the examples, “part” means “part by mass” and “%” means “% by mass”. The sulfonic acid group in each formula is represented in free form.

［実施例１］

水２００部中に１−アミノ−８−（４−メチルフェニルスルホニルオキシ）ナフタレン−３，６−ジスルホン酸（４）を１０部投入後、４８％水酸化ナトリウム溶液を滴下してｐＨを６．０〜７．０に調整して溶解した。得られた溶液に亜硝酸ソーダ１．６部を加え、水９０部に３５％塩酸８．８部を加えた溶液に１０℃〜１５℃にて加え、１時間攪拌しジアゾ化した。水５００部中、８−アミノ−２−ナフタレンスルホン酸（５）４．７部を４８％水酸化ナトリウム溶液にてｐＨ４．５〜５．０に調整して溶解し、ジアゾ化した懸濁液を１０℃〜１５℃の温度で約３０分かけて滴下した。この滴下の間、反応液のｐＨ値を炭酸ナトリウム水溶液の添加でｐＨ４．０〜５．０に保持した。滴下終了後、５℃〜１０℃、ｐＨ４．０〜５．０で５時間、更に１０℃〜１５℃で終夜撹拌し反応を終結させた。次いで、反応液に塩化ナトリウムを加えて塩析し、濾過、単離、乾燥して式（６）のモノアゾ化合物を１４．２部得た。 [Example 1]

After adding 10 parts of 1-amino-8- (4-methylphenylsulfonyloxy) naphthalene-3,6-disulfonic acid (4) in 200 parts of water, a 48% sodium hydroxide solution was added dropwise to adjust the pH to 6. It adjusted to 0-7.0 and melt | dissolved. 1.6 parts of sodium nitrite was added to the resulting solution, and the mixture was added to 90 parts of water and 8.8 parts of 35% hydrochloric acid at 10 ° C. to 15 ° C. and stirred for 1 hour to diazotize. Diazotized suspension obtained by dissolving 4.7 parts of 8-amino-2-naphthalenesulfonic acid (5) in 500 parts of water by adjusting the pH to 4.5 to 5.0 with a 48% sodium hydroxide solution. Was added dropwise at a temperature of 10 ° C. to 15 ° C. over about 30 minutes. During the dropping, the pH value of the reaction solution was maintained at pH 4.0 to 5.0 by adding an aqueous sodium carbonate solution. After completion of the dropwise addition, the reaction was terminated by stirring at 5 ° C. to 10 ° C. at pH 4.0 to 5.0 for 5 hours and further at 10 ° C. to 15 ° C. overnight. Next, sodium chloride was added to the reaction solution for salting out, followed by filtration, isolation and drying to obtain 14.2 parts of a monoazo compound of the formula (6).

次いで、水２００部中に８−アミノ−２−ナフタレンスルホン酸（５）を１．５部投入後、４８％水酸化ナトリウム溶液を滴下してｐＨを６．０〜７．０に調整して溶解した。得られた溶液に亜硝酸ソーダ０．４部を加え、水９０部に３５％塩酸１．７部を加えた溶液に１０℃〜１５℃にて加えて１時間攪拌しジアゾ化した。水５００部中、４−アミノ−５−ヒドロキシナフタレン−１，７−ジスルホン酸（７）２．２部を４８％水酸化ナトリウム溶液にてｐＨ４．５〜５．０に調整して溶解し、得られたジアゾ化した懸濁液を０℃〜８℃の温度で約６０分かけて滴下した。この滴下の間、反応液のｐＨ値を炭酸ナトリウム水溶液の添加でｐＨ２．０〜３．０に保持した。滴下終了後、５℃〜１０℃、ｐＨ３．０〜３．５で５時間、更に１５℃〜２０℃で終夜撹拌し反応を終結させた。次いで、反応液に塩化ナトリウムを加えて塩析し、濾過、単離、乾燥して式（８）のモノアゾ化合物を３．０部得た。

Next, 1.5 parts of 8-amino-2-naphthalenesulfonic acid (5) was added to 200 parts of water, and then a 48% sodium hydroxide solution was added dropwise to adjust the pH to 6.0 to 7.0. Dissolved. To the obtained solution, 0.4 part of sodium nitrite was added, 90 parts of water and 1.7 parts of 35% hydrochloric acid were added at 10 ° C. to 15 ° C. and stirred for 1 hour to diazotize. In 500 parts of water, 2.2 parts of 4-amino-5-hydroxynaphthalene-1,7-disulfonic acid (7) was adjusted to pH 4.5 to 5.0 with 48% sodium hydroxide solution and dissolved, The resulting diazotized suspension was added dropwise at a temperature of 0 ° C. to 8 ° C. over about 60 minutes. During the dropping, the pH value of the reaction solution was maintained at pH 2.0 to 3.0 by adding an aqueous sodium carbonate solution. After completion of the dropwise addition, the reaction was terminated by stirring at 5 ° C. to 10 ° C., pH 3.0 to 3.5 for 5 hours, and further at 15 ° C. to 20 ° C. overnight. Next, sodium chloride was added to the reaction solution for salting out, followed by filtration, isolation and drying to obtain 3.0 parts of a monoazo compound of the formula (8).

前記式（６）の化合物３．８部を水２００部に投入し、４８％水酸化ナトリウム溶液を滴下してｐＨを８．０〜９．０に調整して溶解した。その溶液に亜硝酸ソーダ２．４部を添加し、水１００部中に３５％塩酸を１０部添加した水溶液に１０℃〜１５℃にて滴下して、１時間攪拌しジアゾ化した。水５００部中、式（８）の化合物３．０部を４８％水酸化ナトリウム溶液にてｐＨ９．５〜１０．０に調整して溶解した。その溶解液に式（１２）の化合物をジアゾ化した懸濁液を２０℃〜２５℃の温度で約３０分かけて滴下した。この滴下の間、反応液のｐＨ値を炭酸水素ナトリウム水溶液の添加でｐＨ８．５〜９．５に保持した。滴下終了後、ｐＨ９．０〜９．５、２０℃〜２５℃で３時間、更に２０℃〜２５℃で終夜撹拌し反応を終結させた。

3.8 parts of the compound of the formula (6) was added to 200 parts of water, and a 48% sodium hydroxide solution was added dropwise to adjust the pH to 8.0 to 9.0 and dissolved. To the solution, 2.4 parts of sodium nitrite was added, and the mixture was added dropwise to an aqueous solution obtained by adding 10 parts of 35% hydrochloric acid in 100 parts of water at 10 ° C. to 15 ° C., followed by stirring for 1 hour to diazotize. In 500 parts of water, 3.0 parts of the compound of the formula (8) were dissolved by adjusting the pH to 9.5 to 10.0 with a 48% sodium hydroxide solution. A suspension obtained by diazotizing the compound of formula (12) was dropped into the solution at a temperature of 20 ° C. to 25 ° C. over about 30 minutes. During the dropwise addition, the pH value of the reaction solution was maintained at pH 8.5 to 9.5 by adding an aqueous sodium hydrogen carbonate solution. After completion of the dropping, the reaction was terminated by stirring at pH 9.0 to 9.5, 20 ° C. to 25 ° C. for 3 hours, and further at 20 ° C. to 25 ° C. overnight.

式（９）の化合物を含有する反応液を引続き２４％水酸化ナトリウム溶液でｐＨ１０．５〜１１．０に調整した後、炭酸ナトリウム水溶液にてｐＨ１０．５〜１１．０に保持して、８０℃〜８５℃の温度で５〜１２時間攪拌した。次いで２０℃〜２５℃まで冷却し、３５％塩酸でｐＨを７．０〜８．０とし、塩化ナトリウムを加えて塩析若しくは３５％塩酸で酸析し、濾過、単離、乾燥して、式（１０）のトリスアゾ化合物を４．７部得た。得られた化合物の水中での吸収極大波長λ_ｍａｘ＝６７０ｎｍであった。

The reaction solution containing the compound of formula (9) was subsequently adjusted to pH 10.5 to 11.0 with a 24% sodium hydroxide solution, and then maintained at pH 10.5 to 11.0 with an aqueous sodium carbonate solution. The mixture was stirred at a temperature of from C to 85C for 5 to 12 hours. Next, it is cooled to 20 ° C. to 25 ° C., adjusted to pH 7.0 to 8.0 with 35% hydrochloric acid, salted out with sodium chloride or acidified with 35% hydrochloric acid, filtered, isolated, dried, 4.7 parts of the trisazo compound of the formula (10) was obtained. The absorption maximum wavelength λ _max of the obtained compound in water was 670 nm.

［実施例２］

水２００部中に４−アミノ安息香酸（１１）を３．５部投入後、４８％水酸化ナトリウム溶液を滴下してｐＨを６．０〜７．０に調整して溶解した。得られた溶液に亜硝酸ソーダ０．６部を加え、水９０部に３５％塩酸２．８部を加えた溶液に１０℃〜１５℃にて加えて１時間攪拌しジアゾ化した。水５００部中、４−アミノ−５−ヒドロキシナフタレン−１，７−ジスルホン酸（７）８．１部を４８％水酸化ナトリウム溶液にてｐＨ４．５〜５．０に調整して溶解し、得られたジアゾ化した懸濁液を０℃〜８℃の温度で約６０分かけて滴下した。この滴下の間、反応液のｐＨ値を炭酸ナトリウム水溶液の添加でｐＨ２．０〜３．０に保持した。滴下終了後、５℃〜１０℃、ｐＨ３．０〜３．５で５時間、更に１０℃〜１５℃で終夜撹拌し反応を終結させた。次いで、反応液に塩化ナトリウムを加えて塩析し、濾過、単離、乾燥して式（１２）のモノアゾ化合物を９．３部得た。 [Example 2]

After adding 3.5 parts of 4-aminobenzoic acid (11) in 200 parts of water, 48% sodium hydroxide solution was added dropwise to adjust the pH to 6.0 to 7.0 and dissolved. To the obtained solution, 0.6 part of sodium nitrite was added, and a solution obtained by adding 2.8 parts of 35% hydrochloric acid to 90 parts of water was added at 10 ° C. to 15 ° C. and stirred for 1 hour to diazotize. In 500 parts of water, 8.1 parts of 4-amino-5-hydroxynaphthalene-1,7-disulfonic acid (7) was adjusted to pH 4.5 to 5.0 with 48% sodium hydroxide solution and dissolved. The resulting diazotized suspension was added dropwise at a temperature of 0 ° C. to 8 ° C. over about 60 minutes. During the dropping, the pH value of the reaction solution was maintained at pH 2.0 to 3.0 by adding an aqueous sodium carbonate solution. After completion of the dropwise addition, the reaction was terminated by stirring at 5 ° C. to 10 ° C., pH 3.0 to 3.5 for 5 hours, and further at 10 ° C. to 15 ° C. overnight. Next, sodium chloride was added to the reaction solution for salting out, followed by filtration, isolation and drying to obtain 9.3 parts of a monoazo compound of the formula (12).

実施例１と同様の方法で得られた式（６）の化合物１４．１部を水２００部に投入し、４８％水酸化ナトリウム溶液を滴下してｐＨを８．０〜９．０に調整して溶解した。その溶液に亜硝酸ソーダ２．４部を添加し、水１００部中に３５％塩酸を１０部添加した水溶液に１０℃〜１５℃にて滴下して、１時間攪拌しジアゾ化した。水５００部中、前記式（１２）の化合物９．３部を４８％水酸化ナトリウム溶液にてｐＨ９．５〜１０．０に調整して溶解した。その溶解液に式（６）の化合物をジアゾ化した懸濁液を２０℃〜２５℃の温度で約３０分かけて滴下した。この滴下の間、反応液のｐＨ値を炭酸水素ナトリウム水溶液の添加でｐＨ８．５〜９．５に保持した。滴下終了後、ｐＨ９．０〜９．５、２０℃〜２５℃で３時間、更に２０℃〜２５℃で終夜撹拌し反応を終結させ式（１３）の化合物を含有する溶液を得た。

14.1 parts of the compound of the formula (6) obtained in the same manner as in Example 1 was added to 200 parts of water, and a 48% sodium hydroxide solution was added dropwise to adjust the pH to 8.0 to 9.0. And dissolved. To the solution, 2.4 parts of sodium nitrite was added, and the mixture was added dropwise to an aqueous solution obtained by adding 10 parts of 35% hydrochloric acid in 100 parts of water at 10 ° C. to 15 ° C., followed by stirring for 1 hour to diazotize. In 500 parts of water, 9.3 parts of the compound of the formula (12) was adjusted to pH 9.5 to 10.0 with a 48% sodium hydroxide solution and dissolved. A suspension obtained by diazotizing the compound of formula (6) was added dropwise to the solution at a temperature of 20 ° C. to 25 ° C. over about 30 minutes. During the dropwise addition, the pH value of the reaction solution was maintained at pH 8.5 to 9.5 by adding an aqueous sodium hydrogen carbonate solution. After completion of dropping, the reaction was terminated by stirring at pH 9.0 to 9.5, 20 ° C. to 25 ° C. for 3 hours, and further at 20 ° C. to 25 ° C. overnight to obtain a solution containing the compound of formula (13).

式（１３）の化合物を含有する水溶液を２４％水酸化ナトリウム溶液でｐＨ１０．５〜１１．０に調整し、炭酸ナトリウム水溶液にてｐＨ１０．５〜１１．０に保持し、８０℃〜８５℃で５〜１２時間攪拌した。次いで２０℃〜２５℃まで冷却し、３５％塩酸でｐＨを７．０〜８．０とし、塩化ナトリウムを加えて塩析あるいは３５％塩酸で酸析し、濾過、単離、乾燥して式（１４）の化合物を１６部得た。得られた化合物の水中での吸収極大波長λ_ｍａｘ＝６６６ｎｍであった。

The aqueous solution containing the compound of the formula (13) is adjusted to pH 10.5 to 11.0 with a 24% sodium hydroxide solution, maintained at pH 10.5 to 11.0 with an aqueous sodium carbonate solution, and 80 ° C to 85 ° C. For 5-12 hours. Next, it is cooled to 20 ° C. to 25 ° C., adjusted to pH 7.0 to 8.0 with 35% hydrochloric acid, added with sodium chloride, salted out or acidified with 35% hydrochloric acid, filtered, isolated and dried. 16 parts of the compound (14) were obtained. The absorption maximum wavelength λ _max of the obtained compound in water was 666 nm.

［実施例３］
実施例１又は２で得られた染料１．０００部を水１０００部に溶解して染浴を調製し、この染浴に叩解クラフトパルプ３００部（絶乾パルプ３０部、叩解度３５ＳＲ）を加えて、室温で１５分間攪拌した後、ロジンサイズ（３０％水溶液）１部を加え、更に１０分間攪拌後、結晶硫酸アルミニウム３部を加えて２０分間攪拌した。染色したパルプを抄紙し、乾燥して黒色の染色物を得た。 [Example 3]
A dye bath is prepared by dissolving 1.000 parts of the dye obtained in Example 1 or 2 in 1000 parts of water, and 300 parts of beating kraft pulp (30 parts of absolutely dry pulp, beating degree 35 SR) is added to the dye bath. After stirring at room temperature for 15 minutes, 1 part of rosin size (30% aqueous solution) was added, and after further stirring for 10 minutes, 3 parts of crystalline aluminum sulfate was added and stirred for 20 minutes. The dyed pulp was paper-made and dried to obtain a black dyed product.

［染色性試験］
実施例３で得られた染色物をＣＯＬＯＲ ＥＹＥ ＣＥ３０００（Ｍａｃｂｅｔｈ社）及び目視による測色を行い、測色機器判定及び変退色用グレースケール比較による目視判定を行った。以下に、公知の染料Ａ、Ｂと本発明実施例１、２の染料について、上記の方法に従ってパルプを染色し抄紙した染色物の染色性について比較した結果を表１に示す。 [Dyeability test]
The dyed product obtained in Example 3 was subjected to COLOR EYE CE3000 (Macbeth) and visual colorimetry, and colorimetric device determination and visual determination based on gray scale comparison for fading color were performed. Table 1 shows the results of comparing the dyeing properties of the dyes obtained by dyeing pulp according to the above-described method and making paper for the dyes A and B of the present invention and Examples 1 and 2 of the present invention.

［耐光性試験］
カーボンアークフェードメーター（スガ試験機社製）を用い、公知の染料Ａ、Ｂと本発明実施例１、２の染料について、上記の方法に従ってパルプを染色し抄紙した染色物に１０時間若しくは２０時間照射した。判定級はＪＩＳ Ｌ−０８４１に規定されたブルースケールの等級に準じて決定し、結果を表１に示す。なお、照射時間による耐光性には差がなかった。 [Light resistance test]
Using a carbon arc fade meter (manufactured by Suga Test Instruments Co., Ltd.), with respect to the known dyes A and B and the dyes of Examples 1 and 2 of the present invention, the dyed product obtained by dyeing pulp according to the above method and making paper is 10 hours or 20 hours. Irradiated. The judgment grade is determined according to the blue scale grade defined in JIS L-0841, and the results are shown in Table 1. There was no difference in light resistance depending on the irradiation time.

［表１］

染料Ａ・・Ｃ．Ｉ．ダイレクトブラック １９（現在多用されている黒色染料）
染料Ｂ・・Ｃ．Ｉ．ダイレクトブラック １６８（現在多用されている黒色染料） [Table 1]

Dye A ・ ・ C. I. Direct Black 19 (currently used black dye)
Dye B ・ ・ C. I. Direct Black 168 (currently used black dye)

表１から明らかなように、本発明のジアニシジンを使用しない黒色用アゾ化合物は、ジアニシジンを使用する従来の黒色染料と比べて同等以上の耐光性を示している。現在多用されている公知の染料Ａは、染色性はよいが、製造にジアニシジンを使用する。現在多用されている公知の染料Ｂは、染料Ａと同等の染色性であるが耐光性が低く、製造にジアニシジンを使用する。一方、本発明実施例１、２の染料は、染料Ａと同等の染色性であり、耐光性が染料Ａ、Ｂより優れている。本発明のジアニシジンを使用せずに製造可能な黒色用アゾ染料化合物は、染色性、耐光性共に優れた実用性の高い染料である。   As is clear from Table 1, the azo compound for black that does not use the dianisidine of the present invention exhibits a light resistance equal to or higher than that of the conventional black dye using dianisidine. The known dye A, which is widely used at present, has good dyeability but uses dianisidine for production. A known dye B, which is widely used at present, has a dyeability equivalent to that of the dye A, but has a low light resistance, and uses dianisidine for production. On the other hand, the dyes of Examples 1 and 2 of the present invention have dyeability equivalent to that of Dye A, and light resistance is superior to Dyes A and B. The black azo dye compound that can be produced without using the dianisidine of the present invention is a highly practical dye excellent in both dyeability and light resistance.

Claims (5)

下記式（１）で示されるトリスアゾ化合物又はその塩。

［式中、Ａは下記式（２）又は下記式（３）で表される置換基を示す］

A trisazo compound represented by the following formula (1) or a salt thereof.

[Wherein A represents a substituent represented by the following formula (2) or the following formula (3)]

Ａの結合位置がその結合するナフチル基の６位又は７位である請求項１に記載のトリスアゾ化合物又はその塩。 The trisazo compound or a salt thereof according to claim 1, wherein the bonding position of A is the 6th or 7th position of the naphthyl group to which A is bonded. 請求項１又は２に記載のトリスアゾ化合物又はその塩を少なくとも１種含有する黒色用染料組成物。 A black dye composition comprising at least one trisazo compound or a salt thereof according to claim 1 or 2. 請求項３に記載の黒色用染料組成物を用いることを特徴とするセルロース繊維材料の染色方法。 A method for dyeing a cellulose fiber material, wherein the dye composition for black according to claim 3 is used. 請求項４に記載の染色方法で染色された染色物。 A dyed product dyed by the dyeing method according to claim 4.