JPH086048B2 - Manufacturing method of cyanoazo dye - Google Patents
Manufacturing method of cyanoazo dyeInfo
- Publication number
- JPH086048B2 JPH086048B2 JP63127001A JP12700188A JPH086048B2 JP H086048 B2 JPH086048 B2 JP H086048B2 JP 63127001 A JP63127001 A JP 63127001A JP 12700188 A JP12700188 A JP 12700188A JP H086048 B2 JPH086048 B2 JP H086048B2
- Authority
- JP
- Japan
- Prior art keywords
- dye
- ortho
- copper
- group
- azo dye
- 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.)
- Expired - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title description 13
- -1 cyanoazo Chemical group 0.000 title description 8
- 239000000987 azo dye Substances 0.000 claims description 26
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 7
- 150000008045 alkali metal halides Chemical class 0.000 claims description 6
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 5
- 239000000975 dye Substances 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- 239000005749 Copper compound Substances 0.000 description 8
- 150000001880 copper compounds Chemical class 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000007333 cyanation reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 241001628834 Orthotheres Species 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 1
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は染料の製法に関する。さらに詳しくはオルト
−シアノ−アゾ染料の製法に関する。The present invention relates to a method for producing a dye. More specifically, it relates to a method for producing an ortho-cyano-azo dye.
アゾ基に対して０−位にハロゲン原子を有するオルト
−ハロゲノ−アゾ染料にシアン化第１銅又はシアン化第
１銅を生成する化合物を反応させ対応するオルト−シア
ノ−アゾ染料を得る方法は特公昭45−785他により公知
である。A method for obtaining a corresponding ortho-cyano-azo dye by reacting an ortho-halogeno-azo dye having a halogen atom at the 0-position with respect to an azo group with cuprous cyanide or a compound which forms cuprous cyanide is described. It is known from JP-B-45-785 and others.
この方法によると反応中に生成した金属状銅及び銅化
合物が染料中に混入して染色時におけるトラブルを起す
おそれがある。又この方法で使用されるシアン化第１銅
又はシアン化第１銅を生成する化合物は通常粉末状で扱
われることが多いがこれは環境衛生上好ましいことでは
ない。なお含水のシアン化第１銅を用いた場合シアン化
反応において反応溶媒として用いられる例えばジメチル
ホルムアルデヒドのような溶媒中で樹脂化するという欠
点がある。According to this method, metallic copper and a copper compound produced during the reaction may be mixed in the dye and cause a trouble during dyeing. The cuprous cyanide or the compound that forms cuprous cyanide used in this method is usually handled in the form of powder, but this is not preferable in terms of environmental hygiene. The use of water-containing cuprous cyanide has a drawback that it is resinified in a solvent such as dimethylformaldehyde used as a reaction solvent in the cyanation reaction.
オルト−ハロゲノ−アゾ染料からシアノ化反応を経て
対応するオルト−シアノ−アゾ染料を製造するにあたり
目的染料中への銅の混入がなくかつ取り扱い中に環境汚
染を生ずるおそれのない製造法の開発が望まれている。In producing a corresponding ortho-cyano-azo dye from an ortho-halogeno-azo dye through a cyanation reaction, the development of a production method that does not involve copper in the target dye and does not cause environmental pollution during handling has been developed. Is desired.
本発明者らは前記したような課題を解決すべく鋭意研
究を重ねた結果本発明に至った。即ち本発明は有機溶媒
中、含水シアン化第１銅とアルカリ金属ハロゲン化物か
らシアン化銅錯体を生成せしめ次いで該シアン化銅錯体
とオルト−ハロゲノ−アゾ染料を反応せしめることを特
徴とするオルト−シアノ−アゾ染料の製法を提供する。The present inventors have accomplished the present invention as a result of intensive studies to solve the above problems. That is, the present invention is characterized in that a copper cyanide complex is produced from a cuprous cyanide hydrate and an alkali metal halide in an organic solvent, and then the copper cyanide complex is reacted with an ortho-halogeno-azo dye. A method for producing a cyano-azo dye is provided.
本発明の製法を詳細に説明する。 The production method of the present invention will be described in detail.
本発明の製法において原料として用いられるオルト−
ハロゲノ−アゾ染料としてはアゾ基で結合されたフェニ
ル基上の０−位（対アゾ基）にハロゲン原子好ましくは
臭素原子、塩素原子又は沃素原子を有するものであれば
どのようなアゾ染料でも使用可能であるが殊に好ましい
オルト−ハロゲノ−アゾ染料は次の（Ｉ）式で示される
染料であり、 （但し、R1はニトロ基、メチル基、フッ素、塩素、臭
素を、R2は塩素、臭素、ヨードを、R3はシアノ基、ニト
ロ基、水素、塩素、臭素、ヨード、メチルスルホニル基
を、R4はアセチルアミノ基、プロピオニルアミノ基、メ
チル基、メチルスルホニルアミノ基、水素をR5、R6は夫
々独立にC1-4アルキル基、アラ（C1-3）アルキル基、ア
セトキシエチル基、シアノエチル基、C1-4アルコキシカ
ルボニルオキシエチル基をそれぞれ表す。） 同染料に本発明の製法を適用することにより次の（I
I）式で示される染料が得られる。Ortho used as a raw material in the production method of the present invention
As the halogeno-azo dye, any azo dye having a halogen atom, preferably a bromine atom, a chlorine atom or an iodine atom at the 0-position (relative to the azo group) on the phenyl group bonded by an azo group can be used. Possible but particularly preferred ortho-halogeno-azo dyes are the dyes of the formula (I) (However, R 1 is nitro group, methyl group, fluorine, chlorine, bromine, R 2 is chlorine, bromine, iodo, R 3 is a cyano group, nitro group, hydrogen, chlorine, bromine, iodo, methylsulfonyl group , R 4 is acetylamino group, propionylamino group, methyl group, methylsulfonylamino group, hydrogen is R 5 and R 6 are independently C 1-4 alkyl group, ara (C 1-3 ) alkyl group, acetoxyethyl group. Group, cyanoethyl group, C 1-4 alkoxycarbonyloxyethyl group respectively.) By applying the production method of the present invention to the same dye, the following (I
A dye of the formula I) is obtained.
（但し、R1、R4、R5、及びR6は前記式（Ｉ）と同じ意
味を表し、R7はニトロ基、シアノ基、水素、メチルスル
ホニル基をそれぞれ表す。） 本発明の製法でシアン化銅の錯体を生成せしめるため
に用いられる含水シアン化第１銅の水分量は通常５〜50
％（重量）、より好ましくは10〜30％（重量）でありシ
アン化すべきオルト−ハロゲノ−アゾ染料１モルに対し
て１〜1.5モルの範囲で用いられるが通常１〜1.2モルで
十分である。 (However, R 1 , R 4 , R 5 , and R 6 have the same meanings as those in formula (I), and R 7 represents a nitro group, a cyano group, hydrogen, or a methylsulfonyl group.) The water content of hydrated cuprous cyanide used to form a copper cyanide complex is usually 5 to 50
% (Weight), more preferably 10 to 30% (weight), used in the range of 1 to 1.5 mol per mol of the ortho-halogeno-azo dye to be cyanated, but usually 1 to 1.2 mol is sufficient. .
又、錯体を生成せしめるのに用いられるアルカリ金属
ハロゲン化物の例としてはNaCl,NaBr,NaI,KCl,KBr,KI等
が挙げられるが錯体の有機溶媒に対する溶解性が良好で
ある点からNaBr又はKBrの使用が好ましい。その使用量
は含水シアン化第１銅に対して0.5〜２モルの範囲で適
宜選択される。又アルカリ金属ハロゲン化物は２種以上
を混合して用いてもよい。例えば含水シアン化第１銅と
アルカリ金属臭化物にアルカリ金属ヨウ化物を添加する
ことが出来る。アルカリ金属ハロゲン化物は含水シアン
化第１銅との間でコンプレックス（錯体）を形成し、こ
のコンプレックスは有機溶媒に均一に溶解し溶媒中で安
定に存在しうるものである。又有機溶媒の中で樹脂化す
るというようなこともない。そして金属状銅及び銅化合
物は過によって反応生成物から容易に除去出来る。Further, examples of the alkali metal halide used to form the complex include NaCl, NaBr, NaI, KCl, KBr, KI, etc., but NaBr or KBr is preferable because the solubility of the complex in an organic solvent is good. Is preferably used. The amount used is appropriately selected within the range of 0.5 to 2 mol based on the hydrous cuprous cyanide. Further, two or more kinds of alkali metal halides may be mixed and used. For example, alkali metal iodide can be added to hydrous cuprous cyanide and alkali metal bromide. The alkali metal halide forms a complex with the hydrous cuprous cyanide, and this complex is uniformly dissolved in an organic solvent and can exist stably in the solvent. Moreover, there is no possibility of resinification in an organic solvent. The metallic copper and copper compound can be easily removed from the reaction product by filtration.
本発明の製法において用いられる有機溶媒の例として
はジメチルホルムアミド、ジメチルアセトアミノ、Ｎ−
メチルピロリドン、ジメチルスルホキシド、イソプロパ
ノール、トリエチルホスフェート、エチレングリコー
ル、２−メトキシエタノール、２−エトキシエタノー
ル、ジエチレングリコール等が挙げられ、これらは２種
以上を混合して用いてもよい。有機溶媒の使用量は原料
のオルト−ハロゲノ−アゾ染料に対して通常２〜10倍量
より好ましくは３〜５倍量（重量比）である。Examples of the organic solvent used in the production method of the present invention include dimethylformamide, dimethylacetamino, N-
Methylpyrrolidone, dimethyl sulfoxide, isopropanol, triethyl phosphate, ethylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol and the like can be mentioned, and these may be used as a mixture of two or more kinds. The amount of the organic solvent used is usually 2 to 10 times, preferably 3 to 5 times (weight ratio) the ortho-halogeno-azo dye as a raw material.
シアノ化反応における反応温度は通常20〜150℃より
好ましくは40〜120℃である。又反応時間は原料のモル
比、反応温度、溶媒の種類によって変るが通常15分〜20
時間殊に30分〜５時間で十分である。The reaction temperature in the cyanation reaction is usually 20 to 150 ° C, preferably 40 to 120 ° C. The reaction time varies depending on the molar ratio of the raw materials, the reaction temperature, and the type of solvent, but it is usually 15 minutes to 20 minutes.
Times of 30 minutes to 5 hours are sufficient.
本発明の製法は例えば次のようにして実施される。ま
ず前記したような有機溶媒に所定量のアルカリ金属ハロ
ゲン化物次いで含水シアン化第１銅を加えて（又はこの
逆の順序）よく撹拌する。（室温）若干の発熱を伴いな
がら錯体化が進行し間もなく透明で均一な溶液となる。
これに所定量のオルト−ハロゲノ−アゾ染料を加えて前
記したような反応温度、反応時間によりシアノ化反応を
行う。反応が終了したならそのまま濾過して目的のオル
ト−シアノ−アゾ染料を得てもよいし、反応液にメタノ
ール、エタノール等の溶液、又は塩酸等の酸を加えて目
的のオルト−シアノ−アゾ染料の結晶を十分析出せしめ
てから濾過して目的物を得てもよい。コンプレックスは
安定に溶解しているので金属状銅及び銅化合物を析出す
ることがほとんどなく反応終了後の濾過工程によってほ
ぼ完全に除去出来、えられる目的のオルト−シアノ−ア
ゾ染料に含有される金属状銅又は銅化合物の量が極めて
微量である。なお、銅コンプレックスを含んだ廃液は鉄
粉で処理し析出してくる金属状銅を除去することによっ
て銅又は銅化合物を含まない廃液とすることが出来る。The manufacturing method of the present invention is carried out as follows, for example. First, a predetermined amount of an alkali metal halide and then hydrous cuprous cyanide are added to the above-mentioned organic solvent (or vice versa) and stirred well. (Room temperature) Complexation proceeds with some heat generation, and soon a transparent and uniform solution is formed.
A predetermined amount of ortho-halogeno-azo dye is added to this and the cyanation reaction is carried out at the above reaction temperature and reaction time. When the reaction is completed, the desired ortho-cyano-azo dye may be obtained by filtration as it is, or the desired ortho-cyano-azo dye may be obtained by adding a solution such as methanol or ethanol or an acid such as hydrochloric acid to the reaction solution. The target compound may be obtained by sufficiently precipitating the crystals of (3) and then filtering. Since the complex is stably dissolved, metal copper and copper compounds are scarcely deposited and can be almost completely removed by the filtration step after the reaction is completed. The metal contained in the desired ortho-cyano-azo dye is obtained. The amount of copper or copper compound is extremely small. The waste liquid containing the copper complex can be made into a waste liquid containing no copper or a copper compound by treating the waste liquid with iron powder to remove the precipitated metallic copper.
本発明の製法による場合には含水のシアン化第１銅が
使用出来るので粉塵発生による環境汚染のおそれが小さ
く、使用する有機溶媒の中で樹脂化するようなこともな
く又目的物のオルト−シアノ−アゾ染料に含まれる銅又
は銅化合物の含有量を十分に小さく出来るという利点が
ある。又本発明の製法における廃液中に含まれる銅又は
銅化合物を除去が容易である。In the case of the production method of the present invention, since water-containing cuprous cyanide can be used, there is little risk of environmental pollution due to generation of dust, there is no possibility of resinification in the organic solvent used, and the target ortho- There is an advantage that the content of copper or copper compound contained in the cyano-azo dye can be made sufficiently small. Further, the copper or copper compound contained in the waste liquid in the production method of the present invention can be easily removed.
本発明の製法で得られたオルト−シアノ−アゾ染料は
耐光堅牢度に優れた染料として有用な染料であり殊に分
散染料タイプのオルト−シアノ−アゾ染料は合成繊維の
染色用又はプラスチック成形物の着色用として重要であ
る。The ortho-cyano-azo dye obtained by the process of the present invention is a dye useful as a dye excellent in light fastness. In particular, the disperse dye type ortho-cyano-azo dye is used for dyeing synthetic fibers or molded plastics. It is important for coloring.
以下実施例によって本発明を具体的に説明する。実施
例中「部」及び「％」は夫々重量部、重量％を意味す
る。The present invention will be specifically described below with reference to examples. "Parts" and "%" in the examples mean parts by weight and% by weight, respectively.
実施例1. ジメチルホルムアミド100部中に臭化ナトリウム15.1
部及びシアン化第１銅含水物15.3部（乾燥分として13.2
部、水分率13.7％）を加え撹拌すると均一な淡緑色液が
得られた。この時発熱を伴いながら複塩が生成した。又
シアン化第１銅含水物の仕込みは粉塵が立たず仕込み易
く作業性は良好であった。Example 1. Sodium bromide 15.1 in 100 parts dimethylformamide
Parts and cuprous cyanide hydrate 15.3 parts (13.2 as dry matter)
Part, water content 13.7%) and stirred to obtain a uniform pale green liquid. At this time, a double salt was formed with heat generation. Further, when the cuprous cyanide hydrous material was charged, no dust was generated and it was easy to charge, and the workability was good.
次にアゾ染料 35.9部を仕込み、90乃至95℃で２時間反応させた。次い
で10％塩酸50部を加え、吸引濾過した。更にケーキを５
％塩酸60部で洗浄、その後中性迄水洗した。かくして下
記式の染料25.5部を得た。Then azo dye 35.9 parts were charged and reacted at 90 to 95 ° C for 2 hours. Then, 50 parts of 10% hydrochloric acid was added and suction filtration was performed. 5 more cakes
It was washed with 60 parts of hydrochloric acid and washed with water until neutral. Thus, 25.5 parts of the dye of the following formula was obtained.
本染料中の銅分（金属状銅及び銅化合物、以下同じ）
は200ppmであった。 Copper in this dye (Metallic copper and copper compounds, the same below)
Was 200 ppm.
本染料はポリエステル布を鮮明青色に染色した。 This dye dyed polyester cloth in a vivid blue color.
実施例2. ジメチルホルムアミド100部中に臭化ナトリウム15.1
部、ヨウ化ナトリウム3.3部及びシアン化第１銅含水物1
5.3部（乾燥分として13.2部、水分率13.7％）を加え撹
拌すると均一な淡緑色液が得られた。この時若干の発熱
を伴いながら複塩が生成した。この際シアン化第１銅含
水物の仕込みにおける作業性が良好であった。Example 2. Sodium bromide 15.1 in 100 parts dimethylformamide.
Parts, sodium iodide 3.3 parts and cuprous cyanide hydrate 1
A uniform pale green liquid was obtained by adding 5.3 parts (13.2 parts as a dry matter and a water content of 13.7%) and stirring. At this time, a double salt was formed with some heat generation. At this time, the workability in the preparation of the cuprous cyanide hydrous material was good.
次にアゾ染料 32.9部を仕込み120℃で３時間反応させた。Then azo dye 32.9 parts were charged and reacted at 120 ° C for 3 hours.
以下実施例１と同様に操作し、下記式の染料を20.3部
得た。λmaxは605nm（アセトン中）であった。Then, the same operation as in Example 1 was carried out to obtain 20.3 parts of a dye of the following formula. λmax was 605 nm (in acetone).
本染料中の銅分は500ppmであった。 The copper content in this dye was 500 ppm.
本染料はポリエステル布を帯赤青色に染色した。 This dye dyed polyester cloth reddish blue.
実施例３〜14. 実施例１に準じて下記表に示される置換基をもったオ
ルト−シアノ−アゾ染料を合成し、その染料を用いてポ
リエステル布（PET）を染色した時の色相を示した。Examples 3 to 14. According to Example 1, ortho-cyano-azo dyes having the substituents shown in the following table were synthesized, and the dyes were used to show the hue when dyeing a polyester cloth (PET). It was
〔発明の効果〕 有機溶媒中において、オルト−ハロゲノ−アゾ染料よ
りオルト−シアノ−アゾ染料を製造する方法において使
用する有機溶媒中で樹脂化することがなく、目的染料中
への銅の混入量が少なく、シアン化第１銅による環境汚
染のおそれが少なくかつ廃液処理の容易な製法が確立さ
れた。 [Effects of the Invention] In an organic solvent, the amount of copper mixed into the target dye without resinification in the organic solvent used in the method of producing an ortho-cyano-azo dye from an ortho-halogeno-azo dye. In addition, a manufacturing method has been established in which the waste liquid is less likely to cause environmental pollution due to cuprous cyanide and the waste liquid can be easily treated.
Claims (1)
リ金属ハロゲン化物とからシアン化銅錯体を生成せしめ
次いで該シアン化銅錯体とオルト−ハロゲノ−アゾ染料
を反応せしめることを特徴とするオルト−シアノ−アゾ
染料の製法。1. A method of producing a copper cyanide complex from a cuprous cyanide hydrate and an alkali metal halide in an organic solvent, and then reacting the copper cyanide complex with an ortho-halogeno-azo dye. Process for making ortho-cyano-azo dyes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63127001A JPH086048B2 (en) | 1988-05-26 | 1988-05-26 | Manufacturing method of cyanoazo dye |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63127001A JPH086048B2 (en) | 1988-05-26 | 1988-05-26 | Manufacturing method of cyanoazo dye |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01297467A JPH01297467A (en) | 1989-11-30 |
| JPH086048B2 true JPH086048B2 (en) | 1996-01-24 |
Family
ID=14949222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63127001A Expired - Fee Related JPH086048B2 (en) | 1988-05-26 | 1988-05-26 | Manufacturing method of cyanoazo dye |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH086048B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5216140A (en) * | 1990-06-25 | 1993-06-01 | Cassella Aktiengesellschaft | Monoazo dye and preparation and use thereof |
| KR950006948B1 (en) * | 1992-02-18 | 1995-06-26 | 주식회사엘지화학 | Blue-dye composition |
| KR101984771B1 (en) * | 2018-02-07 | 2019-05-31 | 대영산업 주식회사 | Black disperse dye composition for textile printing |
-
1988
- 1988-05-26 JP JP63127001A patent/JPH086048B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01297467A (en) | 1989-11-30 |
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