JPH0772255B2 - Water-soluble phthalocyanine dye - Google Patents
Water-soluble phthalocyanine dyeInfo
- Publication number
- JPH0772255B2 JPH0772255B2 JP61255216A JP25521686A JPH0772255B2 JP H0772255 B2 JPH0772255 B2 JP H0772255B2 JP 61255216 A JP61255216 A JP 61255216A JP 25521686 A JP25521686 A JP 25521686A JP H0772255 B2 JPH0772255 B2 JP H0772255B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- water
- phthalocyanine dye
- dyeing
- 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 - Lifetime
Links
- 239000001007 phthalocyanine dye Substances 0.000 title claims description 29
- 239000002253 acid Substances 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 8
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 6
- 125000004957 naphthylene group Chemical group 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 description 22
- 239000000835 fiber Substances 0.000 description 14
- 239000000975 dye Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- -1 Alkali metal salts Chemical class 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000000740 bleeding effect Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 3
- 239000000985 reactive dye Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- UNCQVRBWJWWJBF-UHFFFAOYSA-N 2-chloropyrimidine Chemical compound ClC1=NC=CC=N1 UNCQVRBWJWWJBF-UHFFFAOYSA-N 0.000 description 1
- POTQBGGWSWSMCX-UHFFFAOYSA-N 3-[2-(3-aminopropoxy)ethoxy]propan-1-amine Chemical compound NCCCOCCOCCCN POTQBGGWSWSMCX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- SAQSTQBVENFSKT-UHFFFAOYSA-M TCA-sodium Chemical compound [Na+].[O-]C(=O)C(Cl)(Cl)Cl SAQSTQBVENFSKT-UHFFFAOYSA-M 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000010016 exhaust dyeing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 125000005760 substituted naphthylene group Chemical group 0.000 description 1
- 125000005650 substituted phenylene group Chemical group 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000010981 turquoise Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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
- 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
- C09B62/20—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 pyrimidine ring
- C09B62/26—Porphyrins; Porphyrazins
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、ターキス色の水溶性フタロシアニン色素に係
り、更に詳しくは、構造中に反応基として２〜３個のハ
ロゲン原子で置換されたピリミジニル基とビニルスルホ
ン型反応基とを併有し、特にセルロース及び含窒素繊維
に対する低温域での反応固着性に優れたフタロシアニン
色素に関するものである。Description: TECHNICAL FIELD The present invention relates to a water-soluble phthalocyanine dye of turkey color, more specifically, pyrimidinyl substituted with 2 to 3 halogen atoms as a reactive group in the structure. The present invention relates to a phthalocyanine dye having both a group and a vinyl sulfone type reactive group, which is particularly excellent in reaction fixing property to cellulose and nitrogen-containing fibers at a low temperature range.
（従来の技術） セルロース及び含窒素繊維染色用の反応性染料として
は、従来、例えば下記構造式で示されるようなフタロシ
アニン系水溶性染料（特公昭38−26488号公報参照）が
知られている。(Prior Art) As a reactive dye for dyeing cellulose and nitrogen-containing fibers, a phthalocyanine-based water-soluble dye represented by the following structural formula (see JP-B-38-26488) is conventionally known. .
（発明が解決しようとする問題点） しかしながら、上記のような従来のフタロシアニン系染
料は、これを用い吸尽法により染色を行った場合、特に
低温域における反応固着性及び水に対する溶解性が不良
である上、酸ブリード性も悪いという欠点のために、染
色温度が80℃程度のときはこれらの欠点の影響は比較的
小さいが、50〜60℃程度の低温域染色では良好な染色物
は得られない、という問題点があった。従来のこのよう
な欠点は、単に温度依存性が不良であるという他に、染
色工場における省エネルギーの面でも不利に働くという
問題点があった。 (Problems to be Solved by the Invention) However, when the conventional phthalocyanine dyes as described above are dyed by the exhaust method using the dyes, the reaction fixability and the water solubility are particularly poor in a low temperature range. In addition, due to the drawback that the acid bleeding property is also poor, the influence of these drawbacks is relatively small when the dyeing temperature is about 80 ° C, but a good dyed product is obtained at low temperature dyeing at about 50-60 ° C. There was a problem that I could not get it. Such a conventional defect has a problem that the temperature dependence is simply poor and also a disadvantage in terms of energy saving in a dyeing factory.
本発明は、上記の従来の問題点を解決しうるように、特
に低温域でのセルロース及び含窒素繊維に対する反応固
着性に優れ、かつ各種染色堅ろう度も良好で新規な水溶
性フタロシアニン系色素の提供を目的とする。The present invention is a novel water-soluble phthalocyanine dye which is excellent in reaction fixing property to cellulose and nitrogen-containing fibers particularly in a low temperature range and has good dye fastness so as to solve the above conventional problems. For the purpose of provision.
（問題点を解決するための手段） 本発明者らは、かかる目的を達成すべく検討を進めた結
果、本発明に到達した。すなわち、本発明は、遊離酸の
形で一般式〔Ｉ〕 〔式中、Pcは金属含有又は金属非含有のフタロシアニン
残基を表わし、R1は水素原子、メチル基又はエチル基を
表わし、Ａは置換基を有していてもよいフェニレン基又
はナフチレン基を表わし、Ｘは−SO2CH＝CH2基又は−SO
2CH2CH2W基（ここでＷはアルカリの作用によって脱離す
る基を示す。）を表わし、Ｙは （ここでｍは２〜６の整数を示す。）を表わし、Ｚは少
くとも２個のハロゲン原子を有するピリミジニル基を表
わし、また、ａは０〜２の数を表わし、ｂ及びｃは１〜
３の数を表わし、ただしa,b及びｃの合計は４以下の数
である。〕で示される水溶性フタロシアニン色素を要旨
とするものである。(Means for Solving Problems) The present inventors have arrived at the present invention as a result of conducting studies to achieve such an object. That is, the present invention provides a compound of the general formula [I] in the form of a free acid. [In the formula, Pc represents a metal-containing or metal-free phthalocyanine residue, R 1 represents a hydrogen atom, a methyl group or an ethyl group, and A represents a phenylene group or a naphthylene group which may have a substituent. Where X is —SO 2 CH═CH 2 group or —SO
2 CH 2 CH 2 W group (wherein W represents a group capable of leaving by the action of an alkali), and Y represents (Where m represents an integer of 2 to 6), Z represents a pyrimidinyl group having at least two halogen atoms, a represents a number of 0 to 2, and b and c are 1 ~
Represents a number of 3, where the sum of a, b and c is a number of 4 or less. ] The water-soluble phthalocyanine dye represented by
本発明の遊離酸の形で前示一般式〔Ｉ〕で示されるフタ
ロシアニン色素分子中、Pcで表わされるフタロシアニン
残基としては、通常金属含有又は非含有のいずれのもの
でもよいが、とりわけ銅、コバルト又はニッケル金属を
含むフタロシアニン残基が好ましい。In the phthalocyanine dye molecule represented by the general formula [I] shown above in the form of the free acid of the present invention, the phthalocyanine residue represented by Pc may be usually a metal-containing or non-metal-containing phthalocyanine residue. Phthalocyanine residues containing cobalt or nickel metal are preferred.
Ａで表わされる特に好ましい残基は非置換のフエニレン
基である。一方、Ａで表わされる置換フエニレン基とし
ては、例えばメチル基，エチル基などの低級アルキル
基、メトキシ基，エトキシ基などの低級アルコキシ基、
塩素原子，臭素原子などのハロゲン原子又はスルホン酸
基等で置換されたフエニレン基が挙げられ、これらの具
体例としては下記のようなものが挙げられる。A particularly preferred residue represented by A is an unsubstituted phenylene group. On the other hand, examples of the substituted phenylene group represented by A include a lower alkyl group such as a methyl group and an ethyl group, a lower alkoxy group such as a methoxy group and an ethoxy group,
Examples thereof include a halogen atom such as a chlorine atom and a bromine atom, or a phenylene group substituted with a sulfonic acid group. Specific examples thereof include the following.
また、Ａで表わされるナフチレン基としては、非置換の
ナフチレン基又は、例えばスルホン酸基で置換されたナ
フチレン基が挙げられ、この置換されたナフチレン基の
具体例としては下記のものなどが挙げられる。 The naphthylene group represented by A includes an unsubstituted naphthylene group or a naphthylene group substituted with, for example, a sulfonic acid group, and specific examples of the substituted naphthylene group include the following. .
Ｘで表わされる−SO2CH2CH2W基におけるＷはアルカリで
脱離する基を表わすが、この基としては通常、硫酸エス
テル基、チオ硫酸エステル基、リン酸エステル基、酢酸
エステル基又はハロゲン原子などが挙げられ、なかでも
硫酸エステル基が特に好ましい。 W in the —SO 2 CH 2 CH 2 W group represented by X represents a group capable of leaving with an alkali, and this group is usually a sulfate ester group, a thiosulfate ester group, a phosphate ester group, an acetate ester group or Examples thereof include a halogen atom, and among them, a sulfate ester group is particularly preferable.
Ｙで表わされるジイミノ基、そのなかでも特に好ましい
基としては、例えば−NHC3H6OC2H4OC3H6NH−基等が挙げ
られる。Diimino group represented by Y, a particularly preferred group among them, for example, -NHC 3 H 6 OC 2 H 4 OC 3 H 6 NH- group and the like.
また、Ｚで表わされる２〜３個のハロゲン原子を有する
ピリミジニル基としては、通常、下記一般式〔II〕 （式中、T1〜T3の少なくとも２個はフッ素原子、塩素原
子又は臭素原子で、残りはシアノ基、ニトロ基、低級ア
ルキルスルホニル基、トリクロロメチル基又は低級アル
キル基を示す。）で表わされるピリミジニル基が挙げら
れ、特に好ましい具体例としては、 等が挙げられる。Further, the pyrimidinyl group having 2 to 3 halogen atoms represented by Z is usually the following general formula [II] (In the formula, at least two of T 1 to T 3 are a fluorine atom, a chlorine atom or a bromine atom, and the rest are a cyano group, a nitro group, a lower alkylsulfonyl group, a trichloromethyl group or a lower alkyl group.). Examples of the pyrimidinyl group include Etc.
本発明のフタロシアニン色素は、遊離酸の形又はその塩
の形で存在するが、通常、その塩としてはリチウム塩、
ナトリウム塩、カリウム塩、カルシウム塩などのアルカ
リ金属塩又はアルカリ土類金属塩が好ましい。The phthalocyanine dye of the present invention is present in the form of a free acid or a salt thereof, but usually, as the salt, a lithium salt,
Alkali metal salts or alkaline earth metal salts such as sodium salts, potassium salts and calcium salts are preferred.
本発明のフタロシアニン色素は、例えば次のようにして
製造することができる。The phthalocyanine dye of the present invention can be produced, for example, as follows.
フタロシアニンスルホニルクロリドに、下記一般式〔II
I〕及び〔IV〕 （式中、A,X,Y及びR1は前示一般式〔Ｉ〕におけると同
一の意義を有する。）で示されるジアミンとモノアミン
とを縮合させて得られる下記一般式〔Ｖ〕 （式中、Pc,A,X,Y,R1,a,b及びｃは前示一般式〔Ｉ〕に
おけると同一の意義を有する。）で示される化合物を
得、次いでこれと、下記一般式〔VI〕 T4−Ｚ ……〔VI〕 （式中、T4はハロゲン原子を表わし、Ｚは前示一般式
〔Ｉ〕におけると同一の意義を有する。）で示されるピ
リミジン化合物とを、水性媒体中、０〜30℃の温度下、
pH2〜８に調整しながら縮合させることにより本発明の
フタロシアニン色素を得ることができる。Phthalocyanine sulfonyl chloride has the following general formula [II
I] and [IV] (In the formula, A, X, Y and R 1 have the same meanings as in the general formula [I] shown above.) The following general formula [V] obtained by condensing the diamine and the monoamine (In the formula, Pc, A, X, Y, R 1 , a, b and c have the same meaning as in the general formula [I] shown above.) A pyrimidine compound represented by the formula [VI] T 4 -Z ... [VI] (wherein T 4 represents a halogen atom, and Z has the same meaning as in the general formula [I] shown above). , In an aqueous medium at a temperature of 0 to 30 ° C,
The phthalocyanine dye of the present invention can be obtained by condensation while adjusting the pH to 2-8.
また、前示一般式〔III〕で示されるジアミンと前示一
般式〔VI〕で示されるピリミジン化合物とを縮合させて
得られる下記一般式〔VII〕 Ｈ−Ｙ−Ｚ ……〔VII〕 （式中、Ｙ及びＺは前示一般式〔Ｉ〕におけると同一の
意義を有する。）で示される化合物を、前示一般式〔I
V〕で示されるモノアミンと共に、フタロシアニンスル
ホニルクロリドと縮合させることによっても、本発明の
フタロシアニン色素を製造することができる。Further, the following general formula [VII] HYZ ... [VII] (VII) obtained by condensing the diamine represented by the general formula [III] shown above with the pyrimidine compound represented by the general formula [VI] shown above. In the formula, Y and Z have the same meaning as in the general formula [I] shown above.
The phthalocyanine dye of the present invention can also be produced by condensing the phthalocyanine sulfonyl chloride together with the monoamine represented by V].
かくして得られる本発明のフタロシアニン色素は、繊
維、布を染色するための染料として、紙、合成樹脂を着
色するための色素として、更に、インクジエット式プリ
ンターなどの色素として広く利用することができるが、
本発明のフタロシアニン色素にあっては、特にセルロー
ス又は含窒素繊維を染色するための反応性染料として用
いた場合の適性が優れている。この場合の対象繊維とし
ては、通常、木綿、ビスコースレーヨン、キユプラアン
モニウムレーヨン、麻などのセルロース繊維、又は、ポ
リアミド、羊毛、絹などの含窒素繊維が挙げられる。ま
た、これらの繊維と、例えばポリエステル、トリアセテ
ート、ポリアクリロニトリルなどとの混合繊維でも差し
支えない。なお、本発明のフタロシアニン色素は、その
他の反応性染料又は分散染料と、適宜、併用することも
可能である。The phthalocyanine dye of the present invention thus obtained can be widely used as a dye for dyeing fibers and cloths, a dye for coloring papers and synthetic resins, and a dye for ink jet printers. ,
The phthalocyanine dye of the present invention is particularly suitable when used as a reactive dye for dyeing cellulose or nitrogen-containing fibers. Examples of the target fiber in this case include cellulosic fibers such as cotton, viscose rayon, Kyupra ammonium rayon and hemp, and nitrogen-containing fibers such as polyamide, wool and silk. Further, mixed fibers of these fibers with, for example, polyester, triacetate, polyacrylonitrile, etc. may be used. The phthalocyanine dye of the present invention can be used in combination with other reactive dyes or disperse dyes as appropriate.
本発明の水溶性フタロシアニン色素を用いて、セルロー
ス又は含窒素繊維を染色する場合には、吸尽法、パデイ
ング法、捺染法などの公知の染色法を採用することがで
きる。なかでも、本発明のフタロシアニン色素は、これ
を吸尽法に適用した場合には、染色温度が低くても良好
な反応固着性を示すので、特に好ましいものである。こ
の染色に際しては、常法に従って、例えば炭酸ソーダ、
炭酸カリ、苛性ソーダ、苛性カリ、リン酸ソーダ、トリ
クロロ酢酸ソーダなどの酸結合剤と芒硝、食塩などの電
解質の存在下、染色浴のpHを８〜12とし、40〜80℃の温
度で染色することができる。そして、染色後の染色物は
ソーピング及び水洗処理した後、乾燥して回収される。When dyeing cellulose or nitrogen-containing fibers with the water-soluble phthalocyanine dye of the present invention, known dyeing methods such as an exhaust method, a padding method, and a printing method can be employed. Among them, the phthalocyanine dye of the present invention is particularly preferable because when it is applied to the exhaust method, it exhibits good reaction fixability even at a low dyeing temperature. In this dyeing, according to a conventional method, for example, sodium carbonate,
Dyeing at a temperature of 40-80 ° C with the pH of the dyeing bath set to 8-12 in the presence of an acid binder such as potassium carbonate, caustic soda, caustic potash, sodium phosphate, sodium trichloroacetate, etc. and an electrolyte such as mirabilite or salt. You can Then, the dyed product after dyeing is subjected to soaping and washing with water, then dried and collected.
（実施例） 次に、本発明を実施例により更に具体的に説明するが、
本発明は、その要旨を超えない限り、以下の実施例に限
定されるものではない。(Examples) Next, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to the following examples unless it exceeds the gist.
実施例１ （製造例） 銅フタロシアニンテトラスルホニルクロリド24gを氷水1
50mlに入れて懸濁し、4,7−ジオキサデカン−1,10−ジ
アミン3gとアニリン−３−β−スルフアートエチルスル
ホン7gを添加し、30℃まで加温して18時間撹拌し、その
間、５％水酸化ナトリウム水溶液によりpH7に保った。
しかる後、０〜５℃に冷却し、2,3,6−トリフロロ−５
−クロロピリミジン4.0gを添加し、pH7に保ちながら５
〜15℃で縮合が完了するまで撹拌して、遊離酸の形で下
記構造式： で示される本発明の銅フタロシアニン色素を得た。Example 1 (Production Example) 24 g of copper phthalocyanine tetrasulfonyl chloride was added to ice water 1
Put in 50 ml and suspend, add 4,7-dioxadecane-1,10-diamine 3 g and aniline-3-β-sulfate ethyl sulfone 7 g, warm to 30 ° C. and stir for 18 hours, while The pH was maintained at 7 with a 5% aqueous sodium hydroxide solution.
Then, cool to 0 to 5 ° C, and use 2,3,6-trifluoro-5.
-Add 4.0 g of chloropyrimidine and add 5 while keeping the pH at 7.
Stir at ~ 15 ° C until the condensation is complete, and in the form of the free acid, the following structural formula: To obtain the copper phthalocyanine dye of the present invention.
（染色剤） 上記で得られたフトロシアニン色素0.1g、0.2g又は0.4g
をそれぞれ水200mlに溶解し、これら３種の色素水溶液
のおのおのに芒硝10gと木綿10gを加え、60℃に昇温した
後炭酸ナトリウム4gを添加して１時間染色を行い、次い
で水洗、ソーピング、水洗、乾燥して、３種のターキス
色の染色物を得た。(Staining agent) 0.1 g, 0.2 g or 0.4 g of the phthalocyanine dye obtained above
Is dissolved in 200 ml of water, and 10 g of Glauber's salt and 10 g of cotton are added to each of these three types of aqueous dye solutions, and after heating to 60 ° C., 4 g of sodium carbonate is added and dyeing is carried out for 1 hour, followed by washing with water, soaping, It was washed with water and dried to obtain three kinds of Turkis dyed products.
これら３種の染色における繊維に対する色素の反応固着
性はいずれも良好であり、また、得られた各染色物の酸
ブリード性、ビルドアップ性及び耐光堅ろう度もすべて
良好であった。The reaction fixation of the dye to the fiber in these three types of dyeing was good, and the acid bleeding property, build-up property and light fastness of each of the obtained dyeings were also good.
なお、上記のフタロシアニン色素を用い、80℃の温度で
同様な染色を実施し、得られた染色物の各特性を対比し
たところ、両者の結果は遜色ないものであった。When the same dyeing was carried out at a temperature of 80 ° C. using the above phthalocyanine dye and the respective properties of the dyed product obtained were compared, the results of both were comparable.
実施例２ 実施例１に記載の方法に準じて、遊離酸の形で下記３種
の構造式： で示される本発明の銅フタロシアニン色素及びニッケル
フタロシアニン色素を合成した。Example 2 According to the method described in Example 1, the following three structural formulas in the form of free acid: The copper phthalocyanine dye and the nickel phthalocyanine dye of the present invention represented by
かくして得られたフタロシアニン色素のおのおのにつ
き、実施例１記載の染色法により綿布の染色試験を行っ
たところ、綿布は均一にターキス色に染色されて均染性
が良好、かつ得られた各染色綿布のビルドアップ性及び
酸ブリード性も良好であった。Each of the thus-obtained phthalocyanine dyes was subjected to a dyeing test on a cotton cloth by the dyeing method described in Example 1. The cotton cloth was uniformly dyed in a turquoise color and had good levelness, and each dyed cotton cloth obtained. Also had good build-up properties and acid bleeding properties.
また、得られた各染色綿布のλmaxは、銅フタロシアニ
ン色素では670nm（水）、ニッケルフタロシアニン色素
では660nm（水）であった。The λmax of each dyed cotton cloth obtained was 670 nm (water) for the copper phthalocyanine dye and 660 nm (water) for the nickel phthalocyanine dye.
（発明の効果） 以上の結果から明らかなように、本発明の新規な水溶性
フタロシアニン色素は、分子中に反応基としてハロゲン
原子を２〜３個有するピリミジニル基とビニルスルホン
型反応基との両方を有する水溶性のターキス系色素であ
ることから、特にそのセルロース及び含窒素繊維に対す
る低温域での反応固着性並びに水に対する溶解性につい
ては、従来公知のビニルスルホン型反応基を有する水溶
性フタロシアニン色素に比べ格段に優れている。すなわ
ち、かかる従来公知の水溶性フタロシアニン色素を用い
て吸尽染色を行う場合の染色温度は80℃付近であったの
に対し、本発明の水溶性フタロシアニン色素を用いる場
合には、50℃付近に染色温度を低下させても前記繊維に
対して優れた反応固着性を示し、得られた染色物は酸ブ
リード性及びビルドアップ性に優れ、かつ耐光堅ろう度
などの各種染色堅ろう度も良好である、という工業的価
値ある顕著な効果を奏するものである。(Effect of the invention) As is clear from the above results, the novel water-soluble phthalocyanine dye of the present invention has both a pyrimidinyl group having 2 to 3 halogen atoms as a reactive group in the molecule and a vinyl sulfone type reactive group. The water-soluble phthalocyanine dye having a vinyl sulfone type reactive group, which is conventionally known, has a water-soluble turocyanine dye having a vinylsulfone-type reactive group, which has a known reaction fixing property to cellulose and nitrogen-containing fibers at low temperature and solubility to water. Is far superior to. That is, while the dyeing temperature in the case of performing exhaust dyeing using such a conventionally known water-soluble phthalocyanine dye was around 80 ° C., when using the water-soluble phthalocyanine dye of the present invention, around 50 ° C. Even when the dyeing temperature is lowered, it shows excellent reaction fixing property to the fiber, the obtained dyed product has excellent acid bleeding property and build-up property, and also various dyeing fastnesses such as light fastness. , Which has a remarkable effect with industrial value.
Claims (1)
残基を表わし、R1は水素原子、メチル基又はエチル基を
表わし、Ａは置換基を有していてもよいフェニレン基又
はナフチレン基を表わし、Ｘは−SO2CH＝CH2基又は−SO
2CH2CH2W基（ここでＷはアルカリの作用によって脱離す
る基を示す。）を表わし、Ｙは （ここでｍは２〜６の整数を示す。）を表わし、Ｚは少
くとも２個のハロゲン原子を有するピリミジニル基を表
わし、また、ａは０〜２の数を表わし、ｂ及びｃは１〜
３の数を表わし、ただしa,b及びｃの合計は４以下の数
である。〕で示される水溶性フタロシアニン色素。1. A compound of the general formula [I] in the form of a free acid. [In the formula, P c represents a metal-containing or metal-free phthalocyanine residue, R 1 represents a hydrogen atom, a methyl group or an ethyl group, and A represents a phenylene group or a naphthylene group which may have a substituent. And X is -SO 2 CH = CH 2 group or -SO
2 CH 2 CH 2 W group (wherein W represents a group capable of leaving by the action of an alkali), and Y represents (Where m represents an integer of 2 to 6), Z represents a pyrimidinyl group having at least two halogen atoms, a represents a number of 0 to 2, and b and c are 1 ~
Represents a number of 3, where the sum of a, b and c is a number of 4 or less. ] The water-soluble phthalocyanine dye shown by these.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61255216A JPH0772255B2 (en) | 1986-10-27 | 1986-10-27 | Water-soluble phthalocyanine dye |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61255216A JPH0772255B2 (en) | 1986-10-27 | 1986-10-27 | Water-soluble phthalocyanine dye |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7053125A Division JP2657783B2 (en) | 1995-02-06 | 1995-02-06 | Water-soluble phthalocyanine dye |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63110260A JPS63110260A (en) | 1988-05-14 |
| JPH0772255B2 true JPH0772255B2 (en) | 1995-08-02 |
Family
ID=17275634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61255216A Expired - Lifetime JPH0772255B2 (en) | 1986-10-27 | 1986-10-27 | Water-soluble phthalocyanine dye |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0772255B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5527886A (en) * | 1989-12-16 | 1996-06-18 | Sandoz Ltd. | Dyes containing 5-cyano-2,4 or 4,6-dichloropyrimidyl fiber-reactive groups |
| GB2239024B (en) * | 1989-12-16 | 1993-04-21 | Sandoz Ltd | Fibre-reactive dyestuffs |
| DE19517503A1 (en) * | 1995-05-12 | 1996-11-14 | Bayer Ag | Phthalocyanine reactive dye mixture |
| GB9520491D0 (en) * | 1995-10-07 | 1995-12-13 | Zeneca Ltd | Compounds |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0126026B1 (en) * | 1983-04-20 | 1987-12-02 | Ciba-Geigy Ag | Process for dyeing silk or silk-containing fibrous material blends |
| DE3465104D1 (en) * | 1983-07-29 | 1987-09-03 | Ciba Geigy Ag | Reactive dyes, their preparation and their use |
| EP0167490A1 (en) * | 1984-07-05 | 1986-01-08 | Ciba-Geigy Ag | Reactive dyestuffs, their preparation and their use |
-
1986
- 1986-10-27 JP JP61255216A patent/JPH0772255B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63110260A (en) | 1988-05-14 |
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