JPH07316453A - Water-soluble phthalocyanine colorant - Google Patents

Abstract

PURPOSE:To obtain a colorant which is excellent esp. in reactivity with and fixability to cellulose and nitrogen-contg. fibers at low temps. by condensing a pyrimidine compd. with a condensate of a diamine with a monoamine in an aq. medium. CONSTITUTION:A water-sol. phthalocyanine colorant of which the free acid form is represented by formula I. The compd. of formula I is obtd. by condensing phthalocyaninesulfonyl chloride with diamine compds. of formulas II and III and condensing the resulting compd. of formula IV with a pyrimidine compd. of formula V in an aq. medium at 0-30 deg.C at a pH of 2-8. In those formulas, Pc is an optionally metal-contg. phthalocyanine residue; R<1> is H, methyl, or ethyl; A is phenylene or naphthylene; X is -SO2CH=CH2, etc.; Y is a group of formula VI (R<2> and R<3> are each H, methyl, etc.; and n is 0-6); Z is pyrimidinyl; a is 0-2; b and c are each 1-3 provided that a+b+c<=4; and T<4> is halogen.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble phthalocyanine dye of turkis color, more specifically, a pyrimidinyl group substituted with 2 to 3 chlorine atoms as a reactive group in the structure and a vinyl sulfone type reactive group. The present invention relates to a phthalocyanine dye which has both of the following properties, and is particularly excellent in the reaction fixing property to cellulose and nitrogen-containing fibers in a low temperature range.

[0002]

2. Description of the Related Art As a reactive dye for dyeing cellulose and nitrogen-containing fibers, a phthalocyanine-based water-soluble dye represented by the following structural formula (Japanese Patent Publication No. 38-264) is conventionally used.
No. 88) is known.

[0003]

[Chemical 2]

[0004]

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 poor, when the dyeing temperature is about 80 ° C., the influence of these drawbacks is relatively small, but 50 to 6
A good dyed product cannot be obtained by dyeing in a low temperature range of about 0 ° C.
There was a problem. 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.

In order to solve the above-mentioned conventional problems, the present invention is a novel water-soluble phthalocyanine which is excellent in reaction fixability to cellulose and nitrogen-containing fibers particularly in a low temperature range and has good fastness to various dyes. The purpose is to provide a system dye.

[0006]

Means for Solving the 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.

[0007]

[Chemical 3]

[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 which may have a substituent or Represents a naphthylene group, 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.) The , A methyl group or an ethyl group, and n represents an integer of 0 to 6. Z represents a pyrimidinyl group having no fluorine atom and at least two chlorine atoms, a represents a number of 0 to 2, and b and c represent a number of 1 to 3. However, the sum of a, b and c is a number of 4 or less. ] The water-soluble phthalocyanine dye represented by

In the phthalocyanine dye molecule represented by the above-mentioned general formula [I] in the form of the free acid of the present invention, the phthalocyanine residue represented by P _c may be either metal-containing or non-metal-containing. Especially preferred are phthalocyanine residues containing copper, cobalt or nickel metals.

A particularly preferred residue represented by A is an unsubstituted phenylene group. On the other hand, the substituted phenylene group represented by A is, for example, 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, a halogen atom such as a chlorine atom or a bromine atom, or a sulfonic acid group. And substituted phenylene groups,
Specific examples thereof include the following.

[0011]

[Chemical 4]

Examples of the naphthylene group represented by A include an unsubstituted naphthylene group and a naphthylene group substituted with, for example, a sulfonic acid group. Specific examples of the substituted naphthylene group include the following. Is mentioned.

[0013]

[Chemical 5]

[0014] Although W in the _{-SO 2 CH} 2 _CH 2 W groups represented by X represents a group capable of leaving with an alkali, usually as the group, sulfuric ester group, thiosulfuric acid ester group,
Examples thereof include a phosphoric acid ester group, an acetic acid ester group, a halogen atom and the like, and among them, a sulfuric acid ester group is particularly preferable.

The diimino group represented by Y, and among them, particularly preferable groups are, for example, --NHNH-- group, --N
HC ₂ H ₄ NH- group and the like.

The pyrimidinyl group having 2 to 3 chlorine atoms represented by Z is usually the following general formula [II]

[0017]

[Chemical 6]

(Wherein at least two of T ^{1 to} T ³ are chlorine atoms, and the rest are cyano groups, nitro groups, lower alkylsulfonyl groups, trichloromethyl groups or lower alkyl groups). The following groups are mentioned as particularly preferable specific examples.

[0019]

[Chemical 7]

The phthalocyanine dye of the present invention exists in the form of a free acid or a salt thereof. Usually, the salt is an alkali metal salt such as lithium salt, sodium salt, potassium salt, calcium salt or alkaline earth salt. Metal salts are preferred.

The phthalocyanine dye of the present invention can be produced, for example, as follows. The phthalocyanine sulfonyl chloride is added to the following general formulas [III] and [I]
V]

[0022]

[Chemical 8]

(Wherein A, X, Y and R ¹ have the same meanings as in the above-mentioned general formula [I]) and the diamine represented by the following general formula [V ]

[0024]

[Chemical 9]

(Where Pc, A, X, Y, R ¹ , a, b
And c have the same meaning as in the general formula [I] shown above. A compound represented by the following general formula [VI] T ⁴ -Z [VI] (wherein T ⁴ represents a halogen atom, Z is the same as in the general formula [I] shown above). The phthalocyanine dye of the present invention can be obtained by condensing with a pyrimidine compound represented by the formula (1) in an aqueous medium at a temperature of 0 to 30 ° C. while adjusting the pH to 2 to 8.

Further, the following general formula [VII] HYZ [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 meanings as in the general formula [I] shown above.)
The phthalocyanine dye of the present invention can also be produced by condensing with a phthalocyanine sulfonyl chloride together with the monoamine represented by V].

The thus obtained phthalocyanine dye of the present invention can be widely used as a dye for dyeing fibers and cloths, a dye for coloring paper and synthetic resins, and further as a dye for ink jet printers and the like. However, the phthalocyanine dye of the present invention is particularly suitable when used as a reactive dye for dyeing cellulose or nitrogen-containing fibers. In this case, the target fibers generally include cellulosic fibers such as cotton, viscose rayon, cupra ammonium rayon and hemp, or 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. Incidentally, the phthalocyanine dye of the present invention, other reactive dyes or disperse dyes, as appropriate,
It is also possible to use together.

When dyeing cellulose or nitrogen-containing fibers with the water-soluble phthalocyanine dye of the present invention, known dyeing methods such as exhaustion method, padding method and 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, potassium carbonate, caustic soda, caustic potash, sodium phosphate, sodium trichloroacetate and the like acid binder and Glauber's salt,
In the presence of an electrolyte such as salt, the pH of the dyeing bath can be adjusted to 8 to 12, and dyeing can be performed at a temperature of 40 to 80 ° C. Then, the dyed product after dyeing is subjected to soaping and washing treatment,
It is dried and collected.

[0029]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 (Production Example) Copper phthalocyanine trisulfonyl chloride 2
5 g was suspended in 150 ml of ice water, 2.5 g of ethylenediamine and 8 g of aniline-4-β-sulfatoethyl sulfone were added thereto, and the mixture was heated to 30 ° C and heated to 18 ° C.
Stir for a period of time while maintaining pH 7 with 5% aqueous sodium hydroxide. Then, cool to 0-5 ° C,
8.1 g of 3,6-trichloro-5-cyanopyrimidine was added and stirred at 5 to 15 ° C. while maintaining pH 7 until the condensation was completed, and in the form of the free acid the following structural formula:

[0031]

[Chemical 10]

A copper phthalocyanine dye of the present invention represented by the following formula was obtained.

(Dyeing example) 0.2 g of the phthalocyanine dye obtained above was dissolved in 200 ml of water, 10 g of Glauber's salt and 10 g of cotton were added, the temperature was raised to 50 ° C., and then sodium carbonate 4 was added.
g 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. In this dyeing, the reaction fixing property of the dye to the fiber was good, and the dyed product obtained had good acid bleeding property and light fastness.

Example 2 (Production Example) According to the method described in Example 1, the following structural formula in the form of a free acid:

[0035]

[Chemical 11]

A copper phthalocyanine dye of the present invention represented by

(Dyeing Example) 0.1 g, 0.2 g or 0.4 g of the phthalocyanine dye obtained above was added to 20 parts of water.
Dissolve in 0 ml, add 10 g of Glauber's salt and 10 g of cotton to each of these 3 types of aqueous dye solutions, raise the temperature to 60 ° C., add 4 g of sodium carbonate and dye for 1 hour, then wash with water, soap, wash and dry. By doing so, three types of Turkis dyed products were obtained.

The reaction fixability of the dye to the fiber in each of these three types of dyeing was good, and the acid bleeding property, build-up property and light fastness of each of the resulting dyeings were also good. When the above phthalocyanine dye was used to carry out similar dyeing at a temperature of 80 ° C. and the respective properties of the resulting dyed product were compared, the results of both dyes were comparable.

Example 3 (Production Example) According to the method described in Example 1, the following structural formula in the form of the free acid of Chemical formula 4 is:

[0040]

[Chemical 12]

A nickel phthalocyanine dye of the present invention represented by

(Dyeing Example) Using the phthalocyanine dye obtained above, according to the method described in the dyeing example of Example 2,
A turquoise dyeing was obtained. In this dyeing, the reaction fixing property of the dye to the fiber was good, and the resulting dyed product had good acid bleeding property, build-up property and light fastness.

[0043]

As is clear from the above results, the novel water-soluble phthalocyanine dye of the present invention does not have a fluorine atom as a reactive group in the molecule and has a pyrimidinyl group having at least two chlorine atoms. Since it is a water-soluble turquis type dye having both a vinyl sulfone type reactive group and a vinyl sulfone type reactive group, the vinyl sulfone which has been conventionally known in terms of its reaction sticking property to cellulose and nitrogen-containing fibers in a low temperature range and its solubility in water are particularly known. It is significantly superior to water-soluble phthalocyanine dyes having type-reactive groups. That is, the dyeing temperature was about 80 ° C. when exhaust dyeing was performed using such a conventionally known water-soluble phthalocyanine dye, while it was around 50 ° C. when the water-soluble phthalocyanine dye of the present invention was used. 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)

[Claims] 1. 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. represents, X is _-SO 2 CH = CH
₂ groups or a —SO ₂ CH ₂ CH ₂ W group (wherein W represents a group capable of leaving by the action of an alkali). , A methyl group or an ethyl group, and n represents an integer of 0 to 6. Z represents a pyrimidinyl group having no fluorine atom and at least two chlorine atoms, a represents a number of 0 to 2, and b and c represent a number of 1 to 3. However, the sum of a, b and c is a number of 4 or less. ] The water-soluble phthalocyanine dye shown by these.