JPS6390570A - Water-soluble phthalocyanine coloring matter - Google Patents

Abstract

NEW MATERIAL:A compound in the form of a free acid expressed by formula I [Pc is phthalocyanine residue; A is (substituted) phenylene; X is -SO2CH=CH2 or -SO2CH2CH2W (W is a group eliminative by action of an alkali); Y is 2-6C alkylene; Z is halogen; a is 0-2; b and c are 1-3, provided that a+b+c<=4]. EXAMPLE:A compound expressed by formula II. USE:A reactive dye, capable of dyeing cellulose, nitrogen-containing fibers, etc., to Turkish color, usable also as a coloring matter for paper, synthetic resin as well as ink jet printers and preferably applied to an exhaustion method. PREPARATION:For example, phthalocyaninesulfonyl chloride is condensed with a diamine expressed by formula III and a monoamine expressed by formula IV to provide a compound expressed by formula V, which is then condensed with a trihalogenotriazine expressed by formula VI in an aqueous medium at 0$30. deg.C and 2-8pH.

Description

[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention relates to a turquoise water-soluble phthalocyanine dye, and more specifically, the present invention relates to a turquoise water-soluble phthalocyanine dye, and more specifically, the present invention relates to a turquoise water-soluble phthalocyanine dye, and more specifically, the present invention relates to a turquoise water-soluble phthalocyanine dye having a dihalogenotriazinyl group and a vinyl sulfone group as reactive groups in its structure. type reactive groups, especially cellulose and nitrogen-containing i 11! This invention relates to phthalocyanine dyes that exhibit excellent reaction and fixation properties on fibers at low temperatures.

(Prior Art) As a reactive dye for dyeing cellulose and nitrogen-containing fibers, for example, phthalocyanine-based water-soluble dyes as shown by the following structural formula are known (Japanese Patent Publication No. 38-1989).
26488).

Q: However, when this phthalocyanine dye is used for dyeing by the exhaust method, there is a problem that the solubility in water decreases at low *ta and the reaction fixation property becomes poor. It was good when the temperature was around 50°C, but good dyeing could not be achieved when the temperature was around 50 to 60°C. Such a problem is not only due to poor temperature dependence, but is also disadvantageous in terms of energy conservation in dyeing factories.

(Problems to be Solved by the Invention) The present invention has been made in view of the above circumstances, and is based on a phthalocyanine-based product which not only has good fastness properties but also has excellent reaction and fixation properties to cellulose and nitrogen-containing fibers even at low temperatures. The purpose is to provide a pigment.

[Structure of the invention]

(Means for Solving the Problems) The present invention has been made to solve the above problems.
In the free acid form, the following general formula [! [In the formula, Po represents a phthalocyanine residue, A represents a phenylene group which may have a substituent, or -SO, C:H=CH
, a group or -SO.

CH, CH2W group (where W represents a group that leaves by the action of an alkali), Y represents an alkylene group of 02 to 6, Z represents a halogen atom,
a represents a number from O to 2, b and C each represent a number from 1 to 3, and the sum of a'-c is a number of 4 or less. This invention relates to a water-soluble phthalocyanine dye represented by ].

The present invention will be explained in detail below.

In the front nail general formula (I), the phthalocyanine residue represented by Po can usually be either metal-containing or metal-free, but among them, for example, phthalocyanine residues containing copper, cobalt or nickel gold dust can be used. Groups are preferred.

The phenylene group which may have a substituent represented by A is an unsubstituted phenylene group, a lower alkyl group such as a methyl group or an ethyl group, a lower alkoxy group such as a methoxy group or an ethoxy group, or a chlorine atom. , a phenylene group substituted with a halogen atom such as a bromine atom or a sulfonic acid group, and specific examples of the substituted phenylene group include the following.

Further, when X is a -SO, CM, CH, or W group, W represents a group that is eliminated with an alkali, and this group is usually a sulfate ester group, a thio g! Acid ester group, phosphate ester J! , , an acetate group, a halogen atom, and the like.

Examples of the alkylene group represented by Y include CH3 Branched 02~. Examples include alkylene groups.

The halogen atom represented by Z usually includes a chlorine atom, a bromine atom, or a fluorine atom.

The phthalocyanine dye of the present invention exists in the form of a free acid or a salt thereof, and the salt usually includes a lithium salt,
Alkali metal or alkaline earth metal salts such as sodium, potassium, calcium salts are preferred.

The phthalocyanine dye of the present invention can be produced, for example, in the following manner.

Phthalocyanine sulfonyl chloride has the following general formula (I
I) and (11) H, N-C, H, 0-Y-OC, Hs-NH2・(■]
H2N-A-X...Cm) (in the formula, A, X + Y t 11 g
b and C are the same as defined above) to obtain a compound represented by
Next.

To this, a trihalogenotriazine represented by the following general formula [v] (wherein Z is the same as defined above) is added to PH2 in an aqueous medium at a temperature of 0 to 30°C.
A phthalocyanine dye of the present invention can be obtained by condensation while adjusting the concentration to .about.8. Further, the following general formula (wherein Y and Z are the same as defined above) obtained by condensing the diamine represented by the prefixed general formula [■] and the trihalogenotriazine represented by the prefixed general formula (V) It can also be produced by condensing the compound represented by phthalocyanine sulfonyl chloride with a monoamine represented by the prefixed general formula (ml).

The phthalocyanine dye of the present invention can be widely used as a dye for dyeing fibers and cloth, as a dye for coloring synthetic resins of paper, and as a dye for inkjet printers. The invention is particularly suitable for use as a reactive dye for dyeing cellulose or nitrogen-containing fibers. The target fibers in this case are usually cotton and viscose rayon.

Examples include cellulose fibers such as cuproammonium rayon and hemp, or nitrogen-containing fibers such as polyamide, wool, and silk. Further, these fibers may be mixed fibers with, for example, polyester, triacetate, polyacrylonitrile, or the like.

The phthalocyanine dye of the present invention can also be used in combination with other reactive dyes or disperse dyes, as appropriate.

When dyeing cellulose or nitrogen-containing fibers using the phthalocyanine dye of the present invention, known dyeing methods such as the exhaust method, padding method, and textile printing method can be employed. It is particularly desirable when applied to the dyeing process because it shows good reaction fixation even at low dyeing temperatures.

For this dyeing, conventional methods are used such as sodium carbonate, potassium carbonate, caustic soda, and caustic potash.

In the presence of an acid binder such as sodium phosphate or sodium trichloroacetate and an electrolyte such as sodium sulfate, the pH of the dyeing bath is adjusted to 8-8.
12 and can be dyed at a temperature of 40 to 80°C. After dyeing, the dyed product is soaped and washed with water, then dried and collected.

(Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

Example 1 (Production example) 24 g of copper phthalocyanine tetrasulfonyl chloride was added to 150 aQ of ice water, stirred with S, 3 g of 4,7-thioxadecane-1,10-diamine and 7 g of aniline-4-β-sulfatoethyl sulfone were added, The mixture was heated to 30° C. and stirred for 18 hours while maintaining the pH at 7 with a 5% aqueous sodium hydroxide solution. Thereafter, it was cooled to 0 to 5°C, 4.5 g of cyanuric chloride was added, and the mixture was stirred at 5 to 15°C until the condensation was completed while keeping the pH at 7. The indicated compound was obtained.

M (λ, 8 (water) 670 nm) (Staining example) The above phthalocyanine dyes 0.1, 0.2 and 0.4
Dissolve each of g in 200-g of water and add mirabilite Log and cotton Log.
After adding and raising the temperature to 60° C., 4 g of sodium carbonate was added and dyeing was carried out for 1 hour, followed by washing with water, soaping, washing with water and drying to obtain a turquoise dyed product.

The reaction fixation of the dye to the fibers in this dyeing was good, and the dyed product had good various fastnesses (particularly light fastness) and build-up properties.

In addition, when similar dyeing was carried out using the above-mentioned phthalocyanine dye at a temperature of 80° C. and the characteristics of the obtained dyed products were compared, the results were almost the same.

Example 2 (Production Example) 25 g of copper phthalocyanine trisulfonyl chloride was suspended in 150 d of ice water, and 5 g of 4,7-thioxadecane-1,10-diamine and 8 g of aniline-4-β-sulfatoethyl sulfone were added. Warm up to 30℃,
The mixture was stirred for 18 hours while maintaining P I-I at 7 with a 5% aqueous sodium hydroxide solution. Thereafter, the mixture was cooled to 0 to 5°C, 7.5 g of cyanuric chloride was added, and stirred at 5 to 15°C until condensation was completed while maintaining the pH at 7. A compound was obtained.

(λmaX (Water) 670 nm) (Dyeing example) 0.2 g of the above phthalocyanine dye was dissolved in 200 d of water, and mirabilite Log and cotton Log were added. After raising the temperature to 50°C, 4 g of sodium carbonate was added and dyed for 1 hour. Dyeing was carried out, followed by washing, soaping, washing and drying to obtain a turquoise dyed product.

The reaction fixation of the dye to the fibers in this dyeing was good, and the light fastness of the obtained dyed product was also good.

Example 3 According to the method described in Example 1 or Example 2, copper phthalocyanine shown in Table 1 and nickel phthalocyanine shown in Table 2 (both expressed in the form of free acid) were synthesized. When cotton fabrics were dyed using the dye according to the method described in Example 1, each cotton fabric had good dyeability, was well-leveled, and had good build-up properties.

The color tone and λmaM of the dyed fabric obtained were as shown in Tables 1 and 2.

The following margin [Effects of the invention] The phthalocyanine dye of the present invention has a reactive group in its structure.
It is a water-soluble turquoise dye that has both a dihalogenotriazinyl group and a vinyl sulfone type reactive group, and is particularly excellent in reaction fixation to cellulose or nitrogen-containing fibers at low temperatures and solubility in water. . That is, the dyeing temperature when performing exhaust dyeing using a conventional general vinyl sulfone type phthalocyanine dye was around 80°C, but in the case of the phthalocyanine dye of the present invention, the dyeing temperature was around 50°C.
Even when the dyeing temperature is lowered to around 0.degree. C., the dye exhibits excellent reactive fixation to fibers.Furthermore, the dye of the present invention has good various fastnesses such as light fastness, and is also excellent in build-up properties.

Claims (1)

[Claims] (1) In the form of a free acid, the following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, Pc represents a phthalocyanine residue, and A even if it has a substituent. represents a good phenylene group, and X is -
SO_2CH=CH_2 group or -SO_2CH_2C
H_2W group (where W represents a group that is eliminated by the action of an alkali), Y represents an alkylene group of C_2_ to_6, and Z represents a halogen atom. Also, a
represents a number from 0 to 2, b and c each represent a number from 1 to 3, and the total of a to c is a number of 4 or less. ] Water-soluble phthalocyanine dye.