JPS63205367A - Metal formazan compound and method of dyeing and printing fiber material by using the same - Google Patents

Abstract

NEW MATERIAL:Compds. of formula I, wherein A1 and A2 are each a (halogen, nitro, a 1-4C alkyl (sulfonyl), a 1-4C alkoxy, sulfamoyl, etc., -substd.)phenylene or naphthylene; B is straight-chain or branched alkyl, alkenyl, phenyl, naphthyl or a heterocyclic ring and each of them may be sustituted, Me is a metal ion of atomic number 27-29; X is -0- or a group of formula II; Z is a group capable of imparting water solubility; l, m and n are each 0-3 and the sum thereof is 1-4; R1, R2 are each H or a (substd.) lower alkyl; B, and B2 are each a (CH3, C2H5, methoxy, etc. -substd.) phenylene or (sulfo-substd.) naphthylene; Y1 and Y2 are each vinyl or a group which can be removed by the action of an alkali]. EXAMPLE:Compd, of formula IV. USE:Metal formazan compds. which dye fiber material having OH or carboxylic acid amide group (reddish) blue to green. PREPARATION:Compds. of formula V to VII are reacted with cyanuric chloride or fluoride.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel metal formazan compound in the field of dyeing or printing textile materials as a reactive dye.

BACKGROUND OF THE INVENTION Dyeing or printing fiber materials blue using fiber-reactive metal formazan compounds is widely practiced.

Problems that the invention aims to solveDue to recent changes in the technological and economic situation in the demand industry, existing M-Tsugi reactive metal formazan compounds are no longer able to meet all the needs of the demand industry. . For example, even when looking at dyeing performance, which is one of the basic performance requirements for dyes, many unsatisfactory points have come to be recognized.

Means for Solving the Problems In order to find a new metal formazan compound that has performance that can meet the sophistication of the needs described above, the present inventors investigated the type and number of its pigment matrix and fiber-reactive groups. As a result of extensive research on the types of linking groups and linking sites connecting these groups, we discovered a compound that has specific performance by optimally combining specific groups, and completed the present invention. That is, the present invention, in the form of a free acid, has the following general formula (r).
alkoxy, sulfamoyl, N-mono or N,N
-diC1-C4alkylsulfamoyl, C,-C4alkylsulfonyl, phenylsulfonyl or acetylamino-substituted phenylene or naphthylene, B is straight or branched alkyl or alkenyl, phenyl, naphthyl or heterocyclic residue These alkyl, alkenyl, phenyl, naphthyl and heterocyclic residues may have a substituent.

Me is a metal ion having an atomic number of 27 to 29, X is a group -〇- or a group -C-O-1Z is a group that imparts water solubility, 1. m
and n are mutually independent classes of θ~8, and their sum is 1
~4. R1゜R1 and R3 are independently hydrogen or lower alkyl which may have a substituent, Bl and B
l is independently substituted with phenylene or sulfo, which may be substituted with one or two substituents selected from the group of methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, carboxy and sulfo; Naphthylene, Yl and Yl each independently represent vinyl or -
CH2CH,L (L is a group that is eliminated by the action of an alkali)
represents. ] The present invention provides a metal formazan compound represented by the following and a method for dyeing or printing a fiber material using the same.

In the general formula (1), when AI or A2 is substituted phenylene, it is preferably from the group consisting of chloro, bromo, nitro, methyl, ethyl, methoxy, ethoxy, sulfamoyl and N,N-dimethylsulfamoyl. 1 or 2, preferably 1 of the selected substituents
phenylene substituted by

The linear or branched alkyl or alkenyl represented by B preferably has 1 to 8 carbon atoms and 2 to 8 carbon atoms, respectively, and the substituents thereof include methyl, ethyl, methoxy, ethoxy, halogeno, and 1 moyl sulfur. Examples include phenyl optionally substituted with a substituent selected from the group. Substituents of phenyl or naphthyl represented by B include hydroxy, nitro, halogeno, C] ~
Examples include C4 alkyl, C] to C4 alkoxy, and the like. Furthermore, examples of the heterocyclic (lO) residue represented by B include residues such as furan, thiophene, virol, imidazole, indole, pyrazole, pyridine, pyrimidine, quinoline, and benzimidazole, and aromatic compounds constituting these heterocycles are exemplified. Group carbons include chloro,
It may be substituted with phenyl, methyl, ethyl, methoxy, ethoxy, etc., and the hydrogen of the -NH- group in the heterocycle may be substituted with a substituent such as methyl, ethyl or benzyl. Among these, B is phenyl or naphthyl which may be substituted with one or two substituents selected from the group consisting of chloro, methyl, ethyl, methoxy, ethoxy, carbomethoxy, carboethoxy and nitro. is preferred.

Among the metal ions having an atomic number of 27 to 29 represented by Me, a preferable metal ion is a copper ion.

Examples of the group imparting water solubility represented by 2 include sulfonic acid groups, carboxylic acid groups, and phosphonic acid groups, and these include phenylene, naphthylene, alkyl, alkenyl 1 phenyl, naphthyl represented by A, , A2, and B. or is substituted with an aromatic carbon or aliphatic carbon of a heterocyclic residue or a substituent thereof. A sulfonic acid group is suitable as the group that imparts water solubility.

In the general formula (I), when R, R2 and R3 are lower alkyl which may independently have a substituent, such a group is, for example, the group shown in JP-A-59-176855. Groups fall under this category. Preferably, R] and R2 are independently hydrogen, methyl or ethyl;
3 is hydrogen or methyl.

B1 and B! In this case, known groups are applicable, such as the groups shown in the same publication, in particular unsubstituted or methyl, methoxy, chloro or sulfo-substituted phenylene, or unsubstituted, Or β-naphthylene substituted with one sulfo is preferred.

When Yl or Y2 is -CH2CH2L, groups known to have the ability to be eliminated by the action of alkali fall under this category, such as sulfate, thiosulfate, and thiosulfate.
chloro, acetoxy and chloro. Preferred Yl
and Y2 are both β-sulfatoethyl, and some vinyl may be mixed therein.

Although X is a group -0- or a group -C-O-, it is usually preferred that it be a postfix.

Among the metal formazan compounds represented by the above general formula (I), a preferable compound is a compound represented by the following general formula (n) in the form of a free acid [wherein X, B, . have the same meaning and R4 and R5 are each independently a hydrogen atom, methyl, chloro, nitro or methoxy.

R6 and R7 are each independently hydrogen, methyl or ethyl;
p, q and r each independently represent 0 or 1, p +
q and +r are 1.2 or 8. ] This is a compound represented by

These metal formazan compounds are preferably alkali metal or alkaline earth metal salts, particularly sodium or potassium salts.

The compound of the present invention has the following formula (no to (V) [wherein A1, A2, B, Me, X, Z
, R3.

(1.

In the condensation reaction, the order is not particularly limited and the reaction conditions are not particularly limited either, but generally the pH
It can be carried out at a temperature of 2 to 8, preferably 8 to 6 and about θ to 80°C.

Considering the reaction yield and the quality of the obtained metal formazan compound, first, among the compounds represented by the above general formulas (1), (5), and (to), those having low reactivity with cyanuric chloride or cyanuric fluoride are selected. Preferably, the compounds are condensed and then the remaining compounds are condensed. In this case, the initial condensation reaction conditions can be appropriately determined depending on the stability of the starting materials and reaction products, but a relatively low pH range and temperature can be selected, for example, pH 8 to 4, -5° It can be carried out at ~10°C.

The reaction conditions for the second condensation can also be determined as appropriate depending on the raw materials used and the stability of intermediate and final products, but it is preferable to use a relatively high pH range and temperature, e.g. pH 4 to 6.3.
It can be carried out at 0 to 40°C.

The reaction conditions for the third condensation can also be determined as appropriate depending on the raw materials used and the stability of intermediate and final products, but it is preferable to use a relatively high pH range and temperature, e.g. pH 4 to 6.50.
It can be carried out at ~80°C.

Compounds represented by the general formulas (B), (I) and (V) used as starting compounds are, for example, disclosed in JP-A-59-154.
This includes the compounds shown in Publication No. 51, or compounds synthesized using these as raw materials according to the method shown in the publication.

The above starting compounds can be acids and/or salts, depending on the reaction conditions.
In particular they are used in the form of alkali metal or alkaline earth metal salts.

In order to obtain the desired counter ion in the metal formazan compound of the present invention, the type of counter ion in the starting compound, the type of alkaline agent used to neutralize the acid during the production process, or, if necessary, the This is possible by selecting the type of electrolyte.

The metal formazan compound produced according to the present invention can be made into a liquid quantity by removing inorganic salts and adding a stabilizer or dyeability improver as necessary, or this liquid quantity or reaction solution can be made into a liquid quantity. A powder quantity can be obtained by evaporation, for example by spray drying, and a liquid or powder quantity can also be produced by salting out separation by addition of an electrolyte using generally known methods.

The metal formazan compounds according to the invention can be used as fiber-reactive dyes and can dye textile materials, for example materials containing hydroxy groups or carboxylic acid amide groups.

Hydroxy group-containing materials are natural or synthetic hydroxy group-containing materials, such as cellulose fiber materials or their recycled products and polyvinyl alcohol. The cellulosic fiber material is preferably cotton, but also other vegetable fibers such as linen, hemp, jute and ramie fibers. Regenerated cellulose fibers are, for example, viscose stable and filament viscose.

Materials containing carbonamide groups are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other animal hairs, silk, leather, polyamide-6,6
, polyamide-6, polyamide-11 and polyamide-
It is 4.

For dyeing, methods depending on the reactive group of the fiber-reactive dye can be applied.

For example, in the case of cellulosic fibers, dyeing is carried out using the dye according to the invention and an acid binder such as caustic soda, sodium carbonate, phosphate, silicate or sodium bicarbonate. The dyeing method can be selected depending on the properties and physical shape of the fiber.
For example, an exhaustion method, a printing method, a cold pad batch up method, etc. can be employed.

In the case of exhaustion method, sodium carbonate, trisodium phosphate,
It is carried out at relatively low temperatures in a dye bath containing mirabilite or common salt in the presence of an acid binder such as caustic soda. In the case of printing processes, pastes such as starch alginate or starch ethers or emulsifying pastes and sodium carbonate, sodium bicarbonate, caustic soda, sodium triphosphate, sodium trichloroacetate or corresponding potassium or alkaline earth compounds are used. along with alkaline or alkali-releasing agents, if desired with the addition of customary printing aids or dispersants, such as urea, on the fibers, dried and subjected to heat treatment, especially in the presence of water vapor. It can be dyed by attaching it. In the case of cold pad patch up dyeing, caustic soda alone or in combination with sodium silicate, sodium carbonate or trisodium phosphate is used as the acid binder, optionally with the addition of Glauber's salt or common salt, and if desired with the addition of urea or the like. It is padded onto fibers at room temperature with the addition of solubilizers or penetrants, rolled up into rolls,
Dyeing can be done by leaving it for 8 hours or overnight, washing with water, and drying.

The metal formazan compound of the present invention is characterized in that it exhibits excellent performance when dyeing fiber materials, and among them, the copper formazan compound is particularly remarkable, and is suitable for dyeing cellulose fibers, producing a clear blue tone. Excellent build-up and level dyeing properties, good light fastness, sweat resistance, sunlight resistance and abrasion resistance, as well as excellent moisture resistance, such as washing resistance, chlorine water resistance, chlorine bleach resistance, alkali resistance, and sweat resistance. sex,
It has acid hydrolysis resistance, peroxide washing resistance, and good ironing resistance. It is also superior to anthraquinone dyes in that it can be discharged very well, and is also suitable as a blue dye for the three primary colors. Moreover, the temperature during dyeing, bath ratio 1,
It is characterized by being unaffected by changes in salt concentration etc., producing dyed products of stable quality, high exhaustion rate and fixation rate, improved water solubility and improved solubility after addition of alkali. has.

Next, the present invention will be explained in more detail with reference to Examples. In the text, parts indicate parts by weight.

Example I N-(2-carboxy-4-sulfophenyl)-N-(
59.7 parts of 2'-hydroxy-8'-amino-5'-sulfophenyl)-ms-phenylformazane copper complex were mixed with 18.5 parts of cyanuric chloride and then 1-N-ethylaminopenzene-8- β-sulfatoethyl sulfone 81.
After condensation with 0 part according to a conventional method, condensation with 28.5 parts of 1-aminobenzene-4-β-sulfatoethylsulfone at 60 to 70'C under weak acidity, salting out, and release A copper formazan compound represented by the following formula (%) was obtained in acid form.

Example 2 Preparation of the N-(2-carboxy-4-sulfophenyl)-N-(2'- and droxy-8'-amino-5'-sulfophenyl)-ms-phenylformazane copper complex used in Example 1. Instead, □The compound in column 1 of the table below, 1-N
-ethylaminobenzene-8-β-sulfatoethyl sulfone is replaced by the compound of column ①, and 1-aminobenzene-4-β-sulfatoethyl sulfone is replaced by the compound of column ①. Corresponding copper formazan compounds were obtained in the same manner, and the color tones of these compounds on cotton are shown in column ①.

Example 8 0.1, 0.8 and 0.6 parts of each of the copper formazan compounds described in Examples 1 and 2 were added to 200 parts of water.
10 parts of Glauber's salt and 10 parts of cotton were added, the temperature was raised to 60°C, 4 parts of soda carbonate was added, and the mixture was dyed at the same temperature for 1 hour.

Then, by washing with water, soaping, rinsing with water and drying, a bright reddish to greenish blue dyed product with high build-up properties and excellent various fastnesses was obtained. It has excellent discharge printing properties,
Furthermore, it is also excellent in that it provides a stable and noble dyed product that is resistant to the effects of fluctuations in dyeing temperature.

Example 4 N-(2-hydroxy-5-sulfophenyl)-N-(
56.9 parts of 2'-hydroxy-81-amino-5I-sulfophenyl-ms-phenylformasan copper complex was mixed with 18.5 parts of cyanuric chloride and then 1-aminobenzene-4-β.
- Condensation with 28.5 parts of sulfatoethyl sulfone in a conventional manner, followed by condensation with 28.5 N of 1-aminobenzene-3-β-sulfatoethyl sulfone under weak acidity for 60 parts.
Condensation was carried out at ~70°C and salting out to obtain a copper formazan compound represented by the following formula (%) in the form of free acid.

Example 6 Substitute for N-(2-hydroxy-5-sulfophenyl)-N-(2'-hydroxy-8'-amino-5'-sulfophenyl)-ms-phenylformazane copper complex used in Example 4 First, the compound in column 1 of the table below, the compound in column 2 in place of l-aminobenzene-4-β-sulfatoethylsulfone, and l-aminobenyne-8-β
Corresponding copper formazan compounds were obtained in the same manner using the compounds in column ① in place of sulfate ethyl sulfone, and the color tones of these compounds on cotton are shown in column N411.

Example 6 Copper formazan compound described in Examples 4 and 5 0.110
．． Dissolve 8 parts and 0.6 parts in 200 parts of water, and add 10 parts of Glauber's salt.
and 10 parts of cotton, heated to 60°C, added 4 parts of soda carbonate, and dyed for 1 hour. After washing with water, soaping, washing with water and drying, a bright blue dyed product was obtained which had excellent test fastness, especially fastness to sunlight, sweat, sunlight and chlorine, and had extremely good build-up properties and excellent discharge properties.

This compound has excellent solubility and good level dyeing (88 yuan)

Claims (1)

[Scope of Claims] (I) In the form of a free acid, it has the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [In the formula, A_1 and A_2 are independently unsubstituted, , C_1-C_4 alkyl, C_1
-C_4 alkoxy, sulfamoyl, N-mono- or N,N-diC_1-C_4 alkylsulfamoyl,
C_1-C_4 alkylsulfonyl, phenylsulfonyl or acetylamino substituted phenylene or naphthylene, B is a linear or branched alkyl or alkenyl, phenyl, naphthyl or heterocyclic residue, and these alkyl, alkenyl, phenyl, Naphthyl and heterocyclic residues may have substituents. Me is a metal ion with an atomic number of 27 to 29, X is a group -O- or a group -C-
O- and Z are groups imparting water solubility, l, m and n are each independently an integer of 0 to 8, and the sum thereof is 1 to 4. R
_1, R_2 and R_3 are each independently hydrogen or lower alkyl which may have a substituent, B_1 and B_2 are each independently methyl, ethyl, methoxy, ethoxy,
phenylene optionally substituted with one or two substituents selected from the group of chloro, bromo, nitro, carboxy and sulfo, or naphthylene optionally substituted with sulfo, Y_1 and Y_2 are each independently vinyl or -
CH_2CH_2L (L is a group that is eliminated by the action of an alkali). ] A metal formazan compound represented by (2) The compound according to claim 1, wherein Z is sulfo and B is phenyl or naphthyl which may have a substituent. (3) The compound according to claim 1 or 2, wherein Me is a copper ion. (4) The compound according to any one of claims 1 to 3, wherein R_1 and R_2 are independently hydrogen, methyl, or ethyl. (5) The compound according to any one of claims 1 to 4, wherein R_3 is hydrogen or methyl. (6) In the form of a free acid, there are the following general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (II) [In the formula, X, B_1, B_2, Y_1 and Y_2 have the same meaning as in claim 1. However, R_4 and R_5 independently represent hydrogen, methyl, chloro, nitro or methoxy, R_6 and R_7 independently represent hydrogen, methyl or ethyl, p, q and each independently represent 0 or 1, and p+q+r represents 1.2 or 3. ] The compound according to claim 1, which is represented by: (7) Y_1 and Y_2 are independently vinyl or β-
Claims 1 to 6 which are ethyl sulfate
A compound according to any of the paragraphs. (8) B_1 and B_2 are, independently of each other, phenylene optionally substituted with one substituent selected from the group of methyl, methoxy, chloro, and sulfo, or naphthyl optionally substituted with one sulfo group; A compound according to any one of claims 1 to 7. (9) Claims 1 to 3 in which X is a group -C-O-
A compound according to any of Clause 8. (10) In the form of free acid, there are the following general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, A_1 and A_2 are independently of each other, unsubstituted or halogeno, nitro, C_1-C_4 alkyl, C_1
-C_4 alkoxy, sulfamoyl, N-mono- or N,N-diC_1-C_4 alkylsulfamoyl,
C_1-C_4 alkylsulfonyl, phenylsulfonyl or acetylamino substituted phenylene or naphthylene, B is a linear or branched alkyl or alkenyl, phenyl, naphthyl or heterocyclic residue, and these alkyl, alkenyl, phenyl, Naphthyl and heterocyclic residues may have substituents. Me is a metal ion with an atomic number of 27 to 29, X is a group -O- or a group -C-
O- and Z are groups imparting water solubility, l, m and n are each independently an integer of 0 to 3, and the sum thereof is 1 to 4. R
_1, R_2 and R_3 are each independently hydrogen or lower alkyl which may have a substituent, B_1 and B_2 are each independently methyl, ethyl, methoxy, ethoxy,
phenylene optionally substituted with one or two substituents selected from the group of chloro, bromo, nitro, carboxy and sulfo, or naphthylene optionally substituted with sulfo, Y_1 and Y_2 are each independently vinyl or -
CH_2CH_2L (L is a group that is eliminated by the action of an alkali). ] A method for dyeing or printing a fiber material, characterized by using a metal formazan compound shown in the following.