JP6198349B2 - Black trisazo compound, black dye composition containing the same, and use thereof - Google Patents
Black trisazo compound, black dye composition containing the same, and use thereof Download PDFInfo
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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
- C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
- C09B33/18—Trisazo or higher polyazo dyes
- C09B33/22—Trisazo dyes of the type A->B->K<-C
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/02—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes
- D06P1/04—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes not containing metal
- D06P1/06—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes not containing metal containing acid groups
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/39—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using acid dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/6008—Natural or regenerated cellulose using acid dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/62—Natural or regenerated cellulose using direct dyes
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Description
本発明は、黒色用トリスアゾ化合物又はその塩、それを含有する黒色用染料組成物、並びに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 black 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．Ｄｉｒｅｃｔ Ｂｌａｃｋ １９やＣ．Ｉ．Ｄｉｒｅｃｔ Ｂｌａｃｋ １６８等がよく使用されている。しかし、これらの染料は耐光性が低かったり、変異原性試験として知られるエームズ（Ａｍｅｓ）試験が陽性であったりする。エームズ試験が陽性であれば、その使用により人体や環境へ悪影響を与える恐れがあると考えられ、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の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, many direct dyes having good dyeability are 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 are positive in the Ames test known as the mutagenicity test. If the Ames test is positive, it is considered that there is a risk of adverse effects on the human body and the environment, and the use and production must be performed under extremely strict protective equipment. There are many problems in terms of production efficiency.
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ために、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、現状では満足できる染料や染料組成物は見出されていない（特許文献１乃至３、非特許文献１参照）。 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 thereof are required to have improved light resistance, but no satisfactory dye or dye composition has been found at present. (See Patent Documents 1 to 3 and Non-Patent Document 1).
エームズ試験が陰性であり、さらに染着性及び耐光性の良好なセルロース繊維材料用、特に紙・パルプ用の優れた黒色用アゾ染料が求められている。 There is a need for an excellent black azo dye for cellulose fiber materials, particularly for paper and pulp, which has a negative Ames test and has good dyeability and light fastness.
本発明者等は上記の問題点を解決すべく鋭意研究を重ねた結果、エームズ試験が陰性である新規な黒色用アゾ染料とそれを含む染料組成物とを見出し、本発明に至った。すなわち、本発明は以下記載の１）〜８）に関する。 As a result of intensive studies to solve the above problems, the present inventors have found a novel black azo dye having a negative Ames test and a dye composition containing the same, and have reached the present invention. That is, the present invention relates to the following 1) to 8).
１）下記式（１）で表されるトリスアゾ化合物又はその塩。
２）Ｒ１の結合位置がその結合するナフチル基の１位又は２位である上記１）に記載のトリスアゾ化合物又はその塩。
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位である上記１）又は２）に記載のトリスアゾ化合物又はその塩。
４）Ｒ２の結合位置がその結合するフェニル基の３位又は４位である上記１）乃至３）のいずれか一項に記載のトリスアゾ化合物又はその塩。2) The trisazo compound or salt thereof according to 1) above, wherein the bonding position of R 1 is the 1- or 2-position of the naphthyl group to which R 1 is bonded.
3) The trisazo compound or a salt thereof according to 1) or 2) above, wherein the bonding position of A is the 6- or 7-position of the naphthyl group to which A is bonded.
4) The trisazo compound or a salt thereof according to any one of 1) to 3) above, wherein the bonding position of R 2 is the 3-position or 4-position of the phenyl group to which R 2 is bonded.
５）上記１）乃至４）のいずれか一項に記載のトリスアゾ化合物又はその塩を含有する染料組成物。
６）さらに、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｏｒａｎｇｅ ３９、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｙｅｌｌｏｗ ８６、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ２２５、及びＣ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ８３：１よりなる群から選ばれる１種又は２種の染料を、該染料組成物中０．０４〜２０質量％含有する上記５）に記載の染料組成物。5) A dye composition containing the trisazo compound or a salt thereof according to any one of 1) to 4) above.
6) Further, C.I. I. Direct Orange 39, C.I. I. Direct Yellow 86, C.I. I. Direct Red 225, and C.I. I. The dye composition according to 5) above, wherein 0.04 to 20% by mass of one or two dyes selected from the group consisting of Direct Red 83: 1 is contained in the dye composition.
７）上記５）又は６）に記載の染料組成物を使用してセルロース繊維材料を染色する工程を含むセルロース繊維材料の染色方法。
８）上記７）に記載の染色方法により得られる染色物。7) A method for dyeing a cellulose fiber material, comprising a step of dyeing the cellulose fiber material using the dye composition described in 5) or 6) above.
8) A dyed product obtained by the dyeing method described in 7) above.
黒色用染料として使用できる本発明のトリスアゾ化合物又はその塩は、エームズ試験が陰性で、セルロース繊維材料、特に紙・パルプを高濃度で染色することができる。また、該染料や該染料を含む染料組成物を用いて染色した染色物は耐光性にも優れる。 The trisazo compound of the present invention or a salt thereof which can be used as a black dye has a negative Ames test and can dye cellulose fiber materials, particularly paper and pulp, at high concentrations. Moreover, the dyed material dye | stained using this dye and the dye composition containing this dye is excellent also in light resistance.
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、上記式（１）で表されるトリスアゾ化合物又はその塩であり、式中のＡは上記式（２）で表される。Hereinafter, the present invention will be described in detail.
The trisazo compound of the present invention or a salt thereof is a trisazo compound represented by the above formula (1) or a salt thereof, and A in the formula is represented by the above formula (2).
上記式（１）におけるＲ１の結合位置は、その結合するナフチル基の結合可能な位置であれば特に限定されないが、１位又は２位が好ましく、２位がより好ましい。
上記式（１）におけるＡの結合位置は、その結合するナフチル基の結合可能な位置であれば特に限定されないが、６位又は７位が好ましく、７位がより好ましい。
上記式（２）におけるＲ２の結合位置は、その結合するフェニル基の結合可能な位置であれば特に限定されないが、３位又は４位が好ましく、特に水素原子又は４−カルボキシ基が好ましく、水素原子がより好ましい。
なお、置換基の置換位置は、前記各化学式に添え字で表示した通りである。The bonding position of R 1 in the above formula (1) is not particularly limited as long as the bonding position of the naphthyl group to be bonded is, but is preferably 1-position or 2-position, and more preferably 2-position.
The bonding position of A in the above formula (1) is not particularly limited as long as the naphthyl group to be bonded can be bonded, but the 6-position or 7-position is preferable, and the 7-position is more preferable.
The bonding position of R 2 in the above formula (2) is not particularly limited as long as the bonding phenyl group can be bonded, but the 3- or 4-position is preferable, and a hydrogen atom or 4-carboxy group is particularly preferable. A hydrogen atom is more preferable.
The substitution position of the substituent is as indicated by a subscript in each chemical formula.
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もよい。
本発明において上記式（１）で表されるトリスアゾ化合物は、遊離酸として用いてもトリスアゾ化合物の塩として用いてもよい。該トリスアゾ化合物の塩としては、スルホン酸基等の酸性基の塩が挙げられる。該酸性基の塩としては、例えば、リチウム塩、ナトリウム塩、カリウム塩等のアルカリ金属塩、アンモニウム塩、アミン塩等の有機塩が挙げられる。塩の中ではナトリウム塩が好ましい。In the present invention, the azo group may be syn type, anti type or a mixture thereof.
In the present invention, the trisazo compound represented by the above formula (1) may be used as a free acid or a salt of a trisazo compound. Examples of the salt of the trisazo compound include salts of acidic groups such as sulfonic acid groups. Examples of the salt of the acidic group include alkali metal salts such as lithium salt, sodium salt and potassium salt, and organic salts such as ammonium salt and amine salt. Among the salts, sodium salt is preferable.
本発明のトリス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 trisazo compound of the present invention, compounds described in Examples below are particularly preferable.
本発明のトリスアゾ化合物又はその塩を含有する染料組成物も本発明に含まれる。該染料組成物は、例えば、水等の溶剤や通常の染料組成物に使用される添加剤を含有してもよい。該添加剤としては、例えば、エタノール、トリエタノールアミン、ジエタノールアミン、プロクセルＧＸＬ、尿素等が挙げられる。 A dye composition containing the trisazo compound of the present invention or a salt thereof is also included in the present invention. The dye composition may contain, for example, a solvent such as water and an additive used in a normal dye composition. Examples of the additive include ethanol, triethanolamine, diethanolamine, proxel GXL, urea and the like.
本発明の染料組成物は、本発明の効果を損なわなければ他の直接染料を含有していてもよい。該直接染料としては特に限定されないが、中でもＣ．Ｉ．Ｄｉｒｅｃｔ Ｏｒａｎｇｅ ３９、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｙｅｌｌｏｗ ８６、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ２２５、及びＣ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ８３：１よりなる群から選ばれる１種又は２種の染料を配合するのが好ましい。これらの染料は染料組成物中に０．０４〜２０質量％程度配合するのが好ましい。これらの染料は公知文献に従い製造することができるが、市販されている染料を使用することもできる。 The dye composition of the present invention may contain other direct dyes as long as the effects of the present invention are not impaired. The direct dye is not particularly limited. I. Direct Orange 39, C.I. I. Direct Yellow 86, C.I. I. Direct Red 225, and C.I. I. It is preferable to blend one or two dyes selected from the group consisting of Direct Red 83: 1. These dyes are preferably blended in the dye composition in an amount of about 0.04 to 20% by mass. These dyes can be produced according to known literature, but commercially available dyes can also be used.
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でき、特に該染料組成物の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。溶液としては水溶液が好ましく、本発明のトリスアゾ化合物又はその塩やそれを含有する染料組成物を溶解又は希釈して得られる。該染色方法とは、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、内添染色法等である。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, and in particular, a dyeing method using a solution of the dye composition, and a dyed product dyed by the dyeing method It is included in the present invention. The solution is preferably an aqueous solution, and can be obtained by dissolving or diluting the trisazo compound of the present invention or a salt thereof or a dye composition containing it. 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, an internal dyeing method, and the like. 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）で表されるトリスアゾ化合物又はその塩は、例えば、非特許文献１に記載されているような通常のアゾ染料の製法に倣い、ジアゾ化反応、カップリング反応を行うことにより製造される。 The trisazo compound represented by the above formula (1) or a salt thereof is produced, for example, by performing a diazotization reaction and a coupling reaction in accordance with a conventional azo dye production method as described in Non-Patent Document 1. Is done.
本発明のトリスアゾ化合物の製造法を一例示により説明する。なお、下記式（７），（９），（１０）で適宜使用されるＲ１、Ａは、上記と同じ意味を示す。
まず、下記式（３）で表される化合物をジアゾ化し、下記式（４）で表される化合物と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（５）で表されるモノアゾ化合物を得る。The method for producing the trisazo compound of the present invention will be described by way of example. R 1 and A used as appropriate in the following formulas (7), (9), and (10) have the same meaning as described above.
First, the compound represented by the following formula (3) is diazotized, and the compound represented by the following formula (4) and 0 to 40 ° C., preferably 10 to 15 ° C., pH 0.5 to 11, preferably pH 4.0. A coupling reaction is carried out at ˜5.0 to obtain a monoazo compound represented by the following formula (5).
一方、下記式（６）で表される化合物をジアゾ化し、下記式（７）で表される化合物と０〜４０℃、好ましくは２０〜２５℃、ｐＨ０．５〜１１、好ましくはｐＨ８．０〜８．５でカップリング反応させ、下記式（９）で表されるモノアゾ化合物を得る。 On the other hand, the compound represented by the following formula (6) is diazotized, and the compound represented by the following formula (7) and 0 to 40 ° C., preferably 20 to 25 ° C., pH 0.5 to 11, preferably pH 8.0. A coupling reaction is carried out at ˜8.5 to obtain a monoazo compound represented by the following formula (9).
次いで、上記式（５）で表されるモノアゾ化合物をジアゾ化し、上記式（９）で表されるモノアゾ化合物と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、本発明の下記式（１０）で表されるトリスアゾ化合物（１０）を得る。 Next, the monoazo compound represented by the above formula (5) is diazotized, and the monoazo compound represented by the above formula (9) and 0 to 40 ° C., preferably 20 to 25 ° C., pH 0.5 to 11, preferably pH 8 The trisazo compound (10) represented by the following formula (10) of the present invention is obtained by a coupling reaction at 0.5 to 9.5.
上記のジアゾ化反応は、ジアゾ化する成分の塩酸、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、ジアゾ化する成分の中性又は弱アルカリ性の水溶液に亜硝酸塩を加えておき、これに鉱酸を混合するという逆法によって行われる。ジアゾ化反応は−１０〜４０℃で行えばよい。 The above diazotization reaction may be carried out by a conventional method in which a nitrite such as sodium nitrite is mixed in a mineral acid aqueous solution or suspension of the component to be diazotized, such as hydrochloric acid or sulfuric acid, or the diazotized component is neutral. Alternatively, the nitrite is added to a weakly alkaline aqueous solution, and a mineral acid is mixed with the nitrite. The diazotization reaction may be performed at −10 to 40 ° C.
カップリング反応により得られたアゾ化合物は、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よく、溶液又は懸濁液のまま次の工程へ進んでもよい。ジアゾニウム塩が難溶性で懸濁液となっている場合は、濾過してプレスケーキとして次のカップリング反応に使用することもできる。また、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て行えばよい。該有機溶媒としては、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 azo compound obtained by the coupling reaction may be taken out as it is or precipitated by aciding out or salting out and filtered, or it may proceed to the next step as a solution or suspension. When the diazonium salt is hardly soluble and is in a suspension, it can be filtered and used as a press cake for the next coupling reaction. If purification is necessary, salting out may be repeated or precipitated from water using an organic solvent. Examples of the organic solvent include water-soluble organic solvents such as alcohols such as methanol and ethanol, and ketones such as acetone.
以下、実施例により本発明をさら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酸の形で表す。 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 the form of a free acid.
［実施例１］
（工程１）
(Process 1)
水２００部中に３−アミノ−１，５ナフタレンジスルホン酸（上記式（３）で表される化合物）１０部を投入後、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３．５部を加え、水９０部に３５％塩酸１２部を加えた溶液に１０〜１５℃にて加え、１時間撹拌してジアゾ化した。
水５００部中に８−アミノ−２−ナフタレンスルホン酸（上記式（４）で表される化合物）７．３部を４８％水酸化ナトリウム溶液にてｐＨ４．５〜５．０に調整して溶解した溶液に、得られたジアゾ化物の懸濁液を１０〜１５℃の温度で約３０分間かけて滴下した。この滴下の間、反応液のｐＨを炭酸ナトリウム水溶液の添加で４．０〜５．０に保持した。滴下終了後、５〜１０℃、ｐＨ４．０〜５．０で５時間撹拌し、さらに終夜撹拌し、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、水洗、乾燥して、上記式（５）で表される化合物１５部を得た。After adding 10 parts of 3-amino-1,5-naphthalenedisulfonic acid (compound represented by the above formula (3)) in 200 parts of water, a 48% sodium hydroxide solution was added dropwise to adjust the pH to 6.0-7. Adjusted to 0.0 and dissolved. To the obtained solution, 3.5 parts of sodium nitrite was added, and the mixture was added to 90 parts of water and 12 parts of 35% hydrochloric acid at 10 to 15 ° C. and stirred for 1 hour to diazotize.
7.3 parts of 8-amino-2-naphthalenesulfonic acid (compound represented by the above formula (4)) in 500 parts of water was adjusted to pH 4.5 to 5.0 with 48% sodium hydroxide solution. The obtained suspension of diazotized product was added dropwise to the dissolved solution at a temperature of 10 to 15 ° C. over about 30 minutes. During the dropwise addition, the pH of the reaction solution was maintained at 4.0 to 5.0 by adding an aqueous sodium carbonate solution. After completion of the dropwise addition, the mixture was stirred at 5 to 10 ° C. and pH 4.0 to 5.0 for 5 hours, and further stirred overnight to complete the reaction.
Next, sodium chloride was added to the reaction solution for salting out, followed by filtration, washing with water, and drying to obtain 15 parts of a compound represented by the above formula (5).
（工程２）
水２００部中に２−アミノ−５−ヒドロキシ−１，７−ナフタレンジスルホン酸（上記式（６）で表される化合物）１０部を投入し、４８％水酸化ナトリウム溶液を滴下してｐＨを７．０〜８．０に調整して溶解した。その溶液に亜硝酸ソーダ３．５部を添加し、水１００部に３５％塩酸１２部を加えた溶液に１０〜１５℃にて滴下し、１時間撹拌してジアゾ化した。
水５００部中に４−ヒドロキシ−７−（フェニルアミノ）ナフタレン−２−スルホン酸（上記式（８）で表される化合物）９．８部を４８％水酸化ナトリウム溶液にてｐＨ８．５〜９．０に調整して溶解した溶液に、得られたジアゾ化物の懸濁液を１８〜２０℃の温度で約３０分間かけて滴下した。この滴下の間、反応液のｐＨを炭酸水素ナトリウム水溶液の添加でｐＨ８．５〜９．０に保持した。滴下終了後、２０〜２５℃、ｐＨ８．５〜９．０で３時間撹拌し、さらに終夜撹拌し、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、水洗、乾燥して、上記式（１２）で表される化合物１８部を得た。To 200 parts of water, 10 parts of 2-amino-5-hydroxy-1,7-naphthalenedisulfonic acid (compound represented by the above formula (6)) is added, and a 48% sodium hydroxide solution is added dropwise to adjust the pH. It adjusted to 7.0-8.0 and melt | dissolved. To the solution was added 3.5 parts of sodium nitrite, and the mixture was added dropwise to a solution obtained by adding 12 parts of 35% hydrochloric acid to 100 parts of water at 10 to 15 ° C., followed by stirring for 1 hour to diazotize.
In 500 parts of water, 9.8 parts of 4-hydroxy-7- (phenylamino) naphthalene-2-sulfonic acid (compound represented by the above formula (8)) was added at pH 8.5 to 48% sodium hydroxide solution. The obtained suspension of diazotized product was dropped into the solution adjusted to 9.0 and dissolved at a temperature of 18 to 20 ° C. over about 30 minutes. During the dropwise addition, the pH of the reaction solution was maintained at pH 8.5 to 9.0 by adding an aqueous sodium hydrogen carbonate solution. After completion of the dropwise addition, the mixture was stirred at 20 to 25 ° C. and pH 8.5 to 9.0 for 3 hours, and further stirred overnight to complete the reaction.
Next, sodium chloride was added to the reaction solution for salting out, followed by filtration, washing with water and drying to obtain 18 parts of a compound represented by the above formula (12).
（工程３）
上記式（５）で表される化合物１５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５．３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時間撹拌し、ジアゾ化した。
水５００部中に上記式（１２）で表される化合物１８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溶液に、得られたジアゾ化物の懸濁液を２０〜２５℃の温度で約３０分間かけて滴下した。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、２０〜２５℃、ｐＨ９．０〜９．５を保持したまま３時間撹拌し、さらに終夜撹拌し、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、又は３５％塩酸で酸析し、濾過、水洗、乾燥して、上記式（１３）で表される化合物２８部を得た。この化合物の水中の最大吸収波長はλｍａｘ＝５９１ｎｍであった。15 parts of the compound represented by the above formula (5) 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, 5.3 parts of sodium nitrite was added, and the mixture was added dropwise to an aqueous solution in which 10 parts of 35% hydrochloric acid was added to 100 parts of water at 10 to 15 ° C., followed by stirring for 1 hour to diazotize.
Suspension of the diazo compound obtained in a solution obtained by adjusting 18 parts of the compound represented by the above formula (12) in 500 parts of water by adjusting the pH to 9.5 to 10.0 with a 48% sodium hydroxide solution. The solution was added dropwise at a temperature of 20 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 dropwise addition, the mixture was stirred for 3 hours while maintaining 20 to 25 ° C. and pH 9.0 to 9.5, and further stirred overnight to complete the reaction.
Next, sodium chloride was added to the reaction solution for salting out, or acid precipitation with 35% hydrochloric acid, filtration, washing with water and drying to obtain 28 parts of the compound represented by the above formula (13). The maximum absorption wavelength of this compound in water was λmax = 591 nm.
［微生物を用いるエームズ試験］
以下の条件でエームズ試験を行った結果、エームズ試験は陰性であった。試験結果を表１に示す。
染料純度：１００ｗｔ％
使用菌株：Ｓａｌｍｏｎｅｌｌａ ｔｙｐｈｉｍｕｒｉｕｍ ＴＡ１００、Ｓａｌｍｏｎｅｌｌａ ｔｙｐｈｉｍｕｒｉｕｍ ＴＡ９８
溶媒及び陰性対照：注射用水（５０ｍｇ／ｍＬ溶解）
被験物質容量：２０、７８、３１３、１２５０、５０００μｇ／プレート
本試験：２０、７８、３１３、１２５０、５０００μｇ／プレート[Ames test using microorganisms]
As a result of conducting the Ames test under the following conditions, the Ames test was negative. The test results are shown in Table 1.
Dye purity: 100 wt%
Strains used: Salmonella typhimurium TA100, Salmonella typhimurium TA98
Solvent and negative control: Water for injection (50 mg / mL dissolved)
Test substance volume: 20, 78, 313, 1250, 5000 μg / plate Main test: 20, 78, 313, 1250, 5000 μg / plate
Ｂ［ａ］Ｐ：ベンゾ［ａ］ピレン
（備考）（）内の数字は２枚のプレートの平均を示す。
［実施例２］
実施例１で合成した染料０．２１０部を水１０００部に溶解して染浴を調製した。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分間撹拌した後、ロジンサイズ（３０％水溶液）１部を加え、さらに１０分間撹拌後、結晶硫酸アルミニウム３部を加えて２０分間撹拌した。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 2]
A dye bath was prepared by dissolving 0.210 parts of the dye synthesized in Example 1 in 1000 parts of water. After adding 300 parts of beating kraft pulp (30 parts of absolutely dry pulp, beating degree 35SR) to this dyeing bath and stirring for 15 minutes at room temperature, 1 part of rosin size (30% aqueous solution) is added and stirring is further performed for 10 minutes. 3 parts of aluminum sulfate was added and stirred for 20 minutes. The dyed pulp was paper-made and dried to obtain a black dyed product.
［染色試験］
得られた染色物についてＣＯＬＯＲ ＥＹＥ ＣＥ３０００（Ｍａｃｂｅｔｈ社）及び目視による測色を行い、測色機器判定及びブルースケール比較による目視判定を行った。結果を表２に示す。なお、下記の公知の染料Ａを基準対象として評価した。[Dyeing test]
COLOR EYE CE3000 (Macbeth) and visual color measurement were performed on the obtained dyed product, and color measurement device determination and visual determination by blue scale comparison were performed. The results are shown in Table 2. The following known dye A was evaluated as a reference object.
［耐光試験］
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、染色紙に１０時間又は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た。結果を表２に示す。等級が大きいほど光照射によって退色しにくいことを意味し、好ましい。なお、時間により耐光性に差はなかった。[Light resistance test]
Using a carbon arc fade meter (manufactured by Suga Test Instruments Co., Ltd.), the dyed paper was irradiated for 10 hours or 20 hours. The judgment grade was determined according to the blue scale grade defined in JIS L-0841. The results are shown in Table 2. Larger grades are preferred, meaning that they are less likely to fade by light irradiation. There was no difference in light resistance with time.
［比較例］
公知の染料Ａ、Ｂを０．３００部使用し、実施例２の方法にて染色した染色物について上記の試験と同様に染色性及び耐光性について試験した。なお、染料ＡはＣ．Ｉ．Ｄｉｒｅｃｔ Ｂｌａｃｋ １９、染料ＢはＣ．Ｉ．Ｄｉｒｅｃｔ Ｂｌａｃｋ １６８であり、いずれも現在多用されている黒色染料である。結果を表２に示す。[Comparative example]
Using 0.300 parts of known dyes A and B, the dyed product dyed by the method of Example 2 was tested for dyeability and light resistance in the same manner as the above test. Dye A is C.I. I. Direct Black 19, dye B is C.I. I. Direct Black 168, both of which are currently widely used black dyes. The results are shown in Table 2.
表２より、本発明のエームズ試験が陰性である黒色用トリスアゾ化合物は、エームズ試験が陽性である従来の染料Ａと比較してやや良好な染色性と同等の耐光性とを示し、現在多用されている公知の染料Ｂと比較してやや良好な染色性と優れた耐光性とを示している。 From Table 2, the trisazo compound for black whose Ames test of the present invention is negative shows slightly better dyeability and light resistance equivalent to the conventional dye A whose Ames test is positive, and is currently widely used. Compared to the known dye B, it shows slightly better dyeability and excellent light resistance.
［実施例３］
実施例１で合成した染料０．１０８部と０．０７８部のＣ．Ｉ．Ｄｉｒｅｃｔ Ｏｒａｎｇｅ ３９とを配合して水１０００部に溶解して染浴を調製した。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分間撹拌した後、ロジンサイズ（３０％水溶液）１部を加え、さらに１０分間撹拌後、結晶硫酸アルミニウム３部を加えて２０分間撹拌した。染色したパルプを抄紙し、乾燥して黒色の染色物を得た。
得られた染色物についてＣＯＬＯＲ ＥＹＥ ＣＥ３０００（Ｍａｃｂｅｔｈ社）及び目視による測色を行い、測色機器判定及びブルースケール比較による目視判定を行った。また、実施例２と同様に耐光試験を行った。なお、時間により耐光性に差はなかった。染色性及び耐光性の結果を表３に示す。表３には、上記の比較例により得られた染色物の染色性及び耐光性の結果も併せて示す。[Example 3]
0.108 parts of the dye synthesized in Example 1 and 0.078 parts of C.I. I. Direct Orange 39 was blended and dissolved in 1000 parts of water to prepare a dye bath. After adding 300 parts of beating kraft pulp (30 parts of absolutely dry pulp, beating degree 35SR) to this dyeing bath and stirring for 15 minutes at room temperature, 1 part of rosin size (30% aqueous solution) is added and stirring is further performed for 10 minutes. 3 parts of aluminum sulfate was added and stirred for 20 minutes. The dyed pulp was paper-made and dried to obtain a black dyed product.
COLOR EYE CE3000 (Macbeth) and visual color measurement were performed on the obtained dyed product, and color measurement device determination and visual determination by blue scale comparison were performed. Further, a light resistance test was conducted in the same manner as in Example 2. There was no difference in light resistance with time. Table 3 shows the results of dyeability and light resistance. Table 3 also shows the results of dyeability and light resistance of the dyed product obtained by the above comparative example.
［実施例４］
実施例１で合成した染料０．１０８部と０．０６６部のＣ．Ｉ．Ｄｉｒｅｃｔ Ｏｒａｎｇｅ ３９と０．００６部のＣ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ８３：１とを配合して水１０００部に溶解して染浴を調製した。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分間撹拌した後、ロジンサイズ（３０％水溶液）１部を加え、さらに１０分間撹拌後、結晶硫酸アルミニウム３部を加えて２０分間撹拌した。染色したパルプを抄紙し、乾燥して黒色の染色物を得た。
得られた染色物についてＣＯＬＯＲ ＥＹＥ ＣＥ３０００（Ｍａｃｂｅｔｈ社）及び目視による測色を行い、測色機器判定及びブルースケール比較による目視判定を行った。また、実施例２と同様に耐光試験を行った。なお、時間により耐光性に差はなかった。染色性及び耐光性の結果を表３に示す。[Example 4]
0.108 parts of the dye synthesized in Example 1 and 0.066 parts of C.I. I. Direct Orange 39 and 0.006 parts C.I. I. Direct Red 83: 1 was blended and dissolved in 1000 parts of water to prepare a dye bath. After adding 300 parts of beating kraft pulp (30 parts of absolutely dry pulp, beating degree 35SR) to this dyeing bath and stirring for 15 minutes at room temperature, 1 part of rosin size (30% aqueous solution) is added and stirring is further performed for 10 minutes. 3 parts of aluminum sulfate was added and stirred for 20 minutes. The dyed pulp was paper-made and dried to obtain a black dyed product.
COLOR EYE CE3000 (Macbeth) and visual color measurement were performed on the obtained dyed product, and color measurement device determination and visual determination by blue scale comparison were performed. Further, a light resistance test was conducted in the same manner as in Example 2. There was no difference in light resistance with time. Table 3 shows the results of dyeability and light resistance.
［実施例５］
実施例１で合成した染料０．１０８部と０．０４２部のＣ．Ｉ．Ｄｉｒｅｃｔ Ｏｒａｎｇｅ ３９と０．００３部のＣ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ２２５とを配合して水１０００部に溶解して染浴を調製した。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分間撹拌した後、ロジンサイズ（３０％水溶液）１部を加え、さらに１０分間撹拌後、結晶硫酸アルミニウム３部を加えて２０分間撹拌した。染色したパルプを抄紙し、乾燥して黒色の染色物を得た。
得られた染色物についてＣＯＬＯＲ ＥＹＥ ＣＥ３０００（Ｍａｃｂｅｔｈ社）及び目視による測色を行い、測色機器判定及びブルースケール比較による目視判定を行った。また、実施例２と同様に耐光試験を行った。なお、時間により耐光性に差はなかった。染色性及び耐光性の結果を表３に示す。[Example 5]
0.108 parts of the dye synthesized in Example 1 and 0.042 parts of C.I. I. Direct Orange 39 and 0.003 parts C.I. I. Direct Red 225 was blended and dissolved in 1000 parts of water to prepare a dye bath. After adding 300 parts of beating kraft pulp (30 parts of absolutely dry pulp, beating degree 35SR) to this dyeing bath and stirring for 15 minutes at room temperature, 1 part of rosin size (30% aqueous solution) is added and stirring is further performed for 10 minutes. 3 parts of aluminum sulfate was added and stirred for 20 minutes. The dyed pulp was paper-made and dried to obtain a black dyed product.
COLOR EYE CE3000 (Macbeth) and visual color measurement were performed on the obtained dyed product, and color measurement device determination and visual determination by blue scale comparison were performed. Further, a light resistance test was conducted in the same manner as in Example 2. There was no difference in light resistance with time. Table 3 shows the results of dyeability and light resistance.
表３より、本発明のエームズ試験が陰性である黒色用トリスアゾ化合物は、エームズ試験が陽性である従来の染料Ａと比較してやや良好以上の染色性の結果を示し、同等の耐光性を示している。また、現在多用されている公知の染料Ｂと比較してやや良好以上の染色性の結果を示し、優れた耐光性を示している。 From Table 3, the trisazo compound for black whose Ames test of the present invention is negative shows a slightly good dyeing result as compared with the conventional dye A whose Ames test is positive, and shows the same light resistance. Yes. In addition, the dyeing result is slightly better than that of the known dye B, which is widely used at present, and the light resistance is excellent.
Claims (8)
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