JPS61296186A - Dyeing and printing method using reactive dye composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an industrially advantageous method for dyeing or dyeing cellulose-a silk products or textile products containing cellulose fibers using reactive dyes.

Traditionally, direct dyes, sulfur dyes, vat dyes, puchthol dyes, reactive dyes, etc. have been used for dyeing or naphdrinting cellulose fibers, but direct dyes, sulfur dyes, naphthol dyes, etc. There are problems with this, and the field of use is limited. Furthermore, dyeing or summer dyeing operations for sulfur dyes, vat dyes, and naphthol dyes are complicated. Although vat dyes have good fastness, they have various problems such as high dyeing costs and economical problems.Recently, the amount of reactive dyes used has increased and they have become widespread in a wide range of application fields.

Regarding dyeing with reactive dyes and the Narito method, the exhaust dyeing method, continuous dyeing method, cold pad patching up dyeing method, and Narito dyeing method are known, but these exhaust dyeing methods have been developed due to the recent energy situation, i.e. In today's world, where petroleum resources are decreasing and petroleum prices are rapidly increasing, low energy-consuming dyeing with a bath ratio of l:8 or less is becoming popular. dye,
All-in-one methods, in which both the material to be dyed and the dyeing aid are added, are often used.

In these low bath ratio dyeing methods, the dye solution is more concentrated than in conventional dyeing methods, so it is necessary for the dyes used to have higher solubility. Because drugs have been introduced,
It is necessary that the dyes used have higher solubility in alkaline baths and better solution stability in alkaline baths, especially at low temperatures. Also effective for dyeing natural and regenerated cellulose fibers are cold pad patch-up dyeing methods, -bath or two-bath padding dry heat methods and padding solutions such as one-bath or two-bath padding steaming methods, -phase or two-phase summer dyeing methods. Dye colored pastes also require that the dyes used have higher solubility.

The present applicant has previously reported that JP-A No. 56-111, which was proposed for the purpose of improving the chlorine fastness of conventional pyrazolone-based greenish-yellow reactive dyes,
In order to further improve the dye described in Japanese Patent Application No. 112584, a patent application (Japanese Patent Application No. 59-279450) was filed for a new monoazo compound useful as a greenish-yellow reactive dye.

The present inventors have conducted intensive studies on a method for industrially advantageous dyeing or dyeing of nalulose-based textile products using such monoazo compounds in the above-mentioned fields of application.
The present invention has now been completed.

That is, the present invention provides the following general formula (I) in the form of a free acid: represents a sulfophenyl group substituted with a maleinylamino group or a succinylamino group, or a naphthyl group substituted with 2 to 8 sulfonic acid groups, E represents a methoxy group or ' represents an ethoxy group, and X represents a The sulfonic acid group represents a rogene atom.R is a hydrogen atom or a lower alkyl group that may be replaced,
A represents a phenylene group or a naphthylene group which may have a substituent, and Y represents a group that is eliminated by fluorocarino action. ) contains two or more monoazo dyes selected from the monoazo dye group represented by A method for dyeing or dyeing a cellulose fiber product or a cellulose-containing fiber product is provided, which is characterized by using a reactive dye composition.

In the general formula (■), examples of the group that is eliminated by the action of an alkali represented by 2 include a sulfate ester group, a thiosulfate ester group, a phosphate ester i, an acetate ester group, and a halogen atom. do.

A is a phenylene group or a sulfonic acid group optionally substituted with one or two substituents, preferably selected from the group of methyl group, ethyl group, methoxy group, ethoxy group, chlorine, bromine, and sulfonic acid group. It is a naphthylene group which may be substituted by one group, and examples thereof include (in the formula, a bond indicated by an asterisk means a bond connected to the -N- group). In R, the lower alkyl group is preferably an alkyl group having 1-4 carbon atoms, and the optionally substituted groups include a hydroxy group, a cyano group, an alkoxy group, a helokene, a carboxy group, Carbamoyl group, alkoxycarbonyl group, alkylcarbonyloxy group, sulfonic acid group,
A sulfamoyl group is preferred.

Examples of R include hydrogen atom, methyl group, ethyl &
, n-propyl group, 1so-propyl group, n-butyl group, l! to-butyl group, 5ea-butyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 8-hydroxypropyl group, so-hydroxybutyl group, 8-hydroxybutyl group, 4-hydroxybutyl group, 2,8-dihydroxy Propyl group, 8,4-dihydroxybutyl group,
Cyanomethyl group, 2-cyanoethyl group, 8-cyanopropyl group, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 8-ethoxypropyl group, 8-ethoxypropyl group, 2-hydroxy- 8-methoxypropyl group, chloromethyl group, bromomethyl group, 2-chloroethyl group, 2-bromoethyl group, 8
-Chloropropyl group, 8-bromopropyl group, 4-chlorobutyl i, 4-bromobutyl group, carboxymethyl group, 2-carboxyethyl group, 8-carboxypropyl group, 4-carboxybutyl group, 1,2-dicarboxyethyl group, carbamoylmethyl group, 2-carbamoylethyl group, 8-carbamoylpropyl group, 4-carbamoylbutyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 2-methoxycarbonylethyl group, 2-
Ethoxycarbonylethyl group, 8-methoxycarbonylpropyl group, 8-ethoxycarbonylpropyl group, 4-
Methoxycarbonylbutyl group, 4-'ethoxycarbonylbutyl group, methylcarbonyloxymethyl group, ethylcarbonyloxymethyl group, 2-methylcarbonyloxyethyl group, 2-ethylcarbonyloxyethyl group, 8-methylcarbonyloxypropyl group, 8 -Ethylcarbonyloxypropyl group, 4-methylcarbonyloxybutyl group, 4-ethylcarbonyloxybutyl group, sulfomethyl group, 2-sulfoethyl group, 8-sulfopropyl group, 4-sulfobutyl group, sulfamoylmethyl group, 2 Examples include -sulfamoylethyl group, 8-sulfamoylpropyl group, 4-sulfamoylbutyl group, etc., with hydrogen atom, methyl group, and ethyl group being particularly preferred.

Examples of the sulfophenyl group and sulfonaphthyl group represented by D include 803H8011H 80sH80sH 03H, and 808■ is particularly preferred.

As E, a methoxy group is particularly preferred.

Examples of X representing an aromatic amino residue having one or two sulfonic acid groups include 0sH 80sH80sH and the like. Particularly preferred as X is a chlorine atom.

Among the compounds represented by the general formula (I), compounds in which E is a methoxy group and X is a salt Xi are particularly preferred.

The compounds of the general formula (I) are present in the free acid form or in the native form, with particular preference being given to the alkali metal and alkaline earth metal salts, especially the soda, potash, lithium salts.

The compound represented by general formula (T) can be produced, for example, as follows.

4-methoxy-2,6-diamitbenzenesulfonic acid or 4-ethoxy-2,5-cyanobenzenesulfonic acid and diketene in an aqueous medium at a temperature of θ to 40°C and a pH of 4 to 8.
The product obtained by reacting with the amine represented by the following general formula (11) % formula % (in the formula, R, A, and Y have the above-mentioned meanings) is reacted with cyanuric chloride in any order. or cyanuric fluoride in an aqueous medium - then at a temperature of 0°C to 80°C and a pH of
While adjusting to 2 to 7, the temperature is secondarily 20℃ to 60℃.
By condensing the mixture while adjusting the pH to 4 to 7, a compound represented by the following general formula (III) (300Hs (wherein E, R, Mu, and Y have the above-mentioned 1M taste) is obtained.

Then, after diazotizing the amine represented by the following general formula (IV) DN2 (■) (wherein D has the above-mentioned meaning) by a conventional method, the compound of general formula (I) and in an aqueous medium at a temperature of 0°C to 80°C,
By performing the coupling while adjusting the pH to 4 to 8, a monoazo compound represented by the general formula (I) in which X is a chlorine atom or a fluorine atom can be obtained. In the monoazo compound represented by the general formula (T), the compound in which X is an aromatic amino residue having 1 to 2 sulfonic acid groups is further combined with a corresponding amine at a temperature of 60 to 90°C in an aqueous medium. , by reacting at pH 8 to 6.

The reactive dye composition of the present invention can be obtained by mixing two or more of the thus obtained dyes represented by the general formula (I), and each component is a dye represented by the general formula (I). At least one of , M, and Y is different, and there is no particular restriction on their mixing ratio, but preferably one component to be mixed is 5 times f1% or more.

Further, it is preferable that 2 to 4 types of dyes are mixed. The dyes to be mixed may differ in one or more of R, M, and Y in the general formula (1), but it is preferable that they differ in at least R. For example, a mixture of a dye in which L is a tree leaf and a dye in which 8 is an alkyl group, a dye in which R is a different alkyl group (1
``) Mixing of ingredients, etc.

The cellulose fiber products used in the method of the present invention include, but are not particularly limited to, regenerated cellulose such as cotton, linen, hemp, shade, hollow fiber, and viscose, or mixtures thereof with other delicate materials. Examples include.

The dyeing or summer method in the method of the present invention may be any known method, but in the exhaust dyeing method, known inorganic neutral salts such as anhydrous sodium sulfate and common salt, and known inorganic neutral salts such as sodium carbonate, caustic soda, and sodium triphosphate can be used. A method of dyeing using an acid binder is exemplified. In the cold patching up staining method,
An example is a method of padding using a known inorganic neutral salt such as anhydrous sodium sulfate or common salt, and a known acid binder such as caustic soda or sodium silicate, followed by dyeing by leaving it in a sealed packaging material at a constant temperature. . Continuous dyeing methods include the one-bath padding method, in which a known acid binder such as soda carbonate or bicarbonate is mixed with a dye padding solution, and after padding using a known method, dyeing is done by dry heat or steam heat; An example is a two-bath bagging process in which the dye is padded with a known inorganic neutral salt such as NaCl, and a known acid binder such as caustic soda or sodium silicate, and then dyed by dry heat or steam heat in a known manner. In the Nari dyeing method, after printing a Nari dye paste containing a known acid binder such as iris soda soda, there is a one-phase Nari dyeing method in which Nari dyeing paste is dyed using dry heat or steam heat. Examples include a two-phase dyeing method in which an inorganic neutral salt and a known acid binder such as caustic soda or sodium silicate are added to a high temperature of 90° C. or higher for dyeing.

According to the method of the present invention, there is no problem in terms of practical solubility,
In color dyeing and round dyeing, it is possible to obtain dyed or round dyed goods with good level dyeing properties and good reproducibility.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. In the examples, parts and % mean parts of MiIt and weight %, respectively.

Example 1 15 parts of the dye represented by the formula (1-1), 15 parts of the dye represented by the formula (1-2) (t), 80 parts of the dye represented by the formula (1-8), and the formula (1-4) Thoroughly mix 40 parts of the dye shown below.

(a) Dissolve the obtained dye composition 100F in hot water and
Cool to ℃. To this, 82.6N caustic soda aqueous solution 16
- and 150j' of water glass of 60 degrees Baume are added,
Immediately after adding water to bring the total volume to 1/2 at 26°C, this liquid is used as a padding liquid to pad a cotton fabric. The padded cotton fabric is rolled up, sealed with a polyethylene film and left at room temperature of 20° C. for 20 hours, after which the dyed product is washed and dried in a conventional manner for finishing. The dyed product obtained was a deep greenish yellow color with no spots.

(b) Even after leaving the padding liquid in item (a) above at 25°C for 120 minutes, no dye precipitation or gelation of the padding liquid was observed. When this was carried out, a uniform, spotless, deep greenish yellow dyed product was obtained.

Comparative Example 1 (a) Formulas (1-1) and (1-2) in Example 1, (1
-8) and (1-43) had poor solubility when used alone, and 80? of each dye could not be dissolved in hot water of 17.

(b) Each of the dyes in item (a) above has an IOF of 800
- It was possible to dissolve the solution at a temperature of 25°C.
℃, then add 15ml of 82.5% caustic soda aqueous solution.
When water glass 150F with 1 and 50 degrees Baume is added and further water is added to bring the total amount to 11 at 25°C, the dye represented by formula (1) immediately becomes gel-like, and the dye represented by formula (2) Immediate precipitation of the dye was observed. It was not possible to dye using this dye solution.

Example 2 60 parts of the dye represented by the formula (1-1) in Example 1 are sufficiently mixed with 50 parts of the dye represented by the formula (2-11 <2-1).

(a) Set 4 on the knitted fabric 100 made of Yallose fiber in a low bath ratio jet dyeing machine, set the bath ratio 1 rich 6 and the water temperature 80°C.
Make it.

After putting 6 noodles of dye obtained above and 46 noodles of anhydrous sodium sulfate dissolved in advance into a bath by a known method, they were heated at this temperature for 2 hours.
Treat the knitted fabric for 0 minutes and use a known method to add carbonated soda IL! II
into the bath. Next, the temperature of the dye bath is raised to 60° C. over 80 minutes, and the knitted fabric is treated at this temperature for 60 minutes to complete the dyeing. The dyed product thus obtained is washed and finished in a conventional manner. The dyed product obtained was a uniform deep greenish yellow color with no deposits.

(b) No precipitation of dye or gelation of the dye solution was observed in the dye bath of item (a) above.

Comparative Example 2 The dyes represented by formulas (1-1) and (2-1) in Example 2 were able to dissolve 8114 and 6001 in boiling water, respectively, but in this solution, 45Kf of anhydrous sodium sulfate and 45Kf of anhydrous sodium salt were added. When 12Kt of soda carbonate was added, the dye represented by formula (1) immediately gelled, and the dye represented by formula (2) gelled after 20 minutes.

It was not possible to dye using this dye #4 solution.

Example 8 20 parts of the dye represented by the formula (8-1), 60 parts of the dye represented by the formula (8-2) '(8-2), 16 parts of the dye represented by the formula (8-8), and the formula ( Thoroughly mix 15 parts of the dye shown in 8-4).

(a) Dissolve the obtained dye composition 100F in hot water.
Cool to 6°C. To this was added sodium alginate IF, sodium metanitrobenzenesulfonate IOP, and 20 tons of sodium hydrogen carbonate, and further water was added to bring the total amount to 26°C.
Immediately after setting the solution to 12, this solution is used as a padding solution to pad a cotton fabric. 120 padded cotton fabrics
Dry at 100°C for 2 minutes, then steam at 100°C for 6 minutes to fix the dye.・The obtained dyed product is washed and dried using conventional methods. The dyed product obtained was a deep greenish yellow color with no spots.

(b) Even after leaving the padding solution in item (a) above at 26°C for 120 minutes, no precipitation of dye or gelation of the padding liquid was observed.Similar to item (a), padding dyeing of cotton fabrics was observed. A uniform, spotless, deep greenish yellow dyed product was obtained.

Comparative Example 8 (a) The dyes represented by formulas (8-, 1) to (8-4) in Example 8 have poor solubility when used alone;
), and the dyes of formulas (B-2) and (8-4) were unable to dissolve 5(1-) in 1/1 boiling water, respectively.

(The dyes represented by formulas (8-1) to (8-4) in Example 8 were each 20%) were able to be dissolved in 900°C hot water, but this solution was cooled to 25°C. Next, sodium alginate 1? , metanitrobenzenesulfonic acid soda I
O? and 201 sodium hydrogen carbonate, and further water to bring the total amount to 17 at 26°C. After 80 minutes, heat ζ
Dye precipitation was observed. Further, when pad dyeing was performed using this dye solution, the dyed product obtained was a pale greenish yellow color with many dyed spots.

Example 4 40 parts of the dye represented by formula (4-1), 80 parts of the dye represented by formula (4-2), and 80 parts of the dye represented by formula (4-8) are thoroughly mixed.

(a) The resulting dye composition 50F is dissolved in hot water, followed by 20F of sodium alginate, 20F of sodium metanitrobenzenesulfonate, and 20F of sodium bicarbonate. Immediately after adding water and bringing the total amount to IKf at 20°C,
Use this as a dyeing paste to make marks on wood and brocade/9Q1 items and dry. Next, steaming is performed at 100° C. for 8 minutes to fix the dye. The resulting dyed fabric is washed and dried using conventional methods. The resulting animal had a uniform dark greenish-yellow color.

(b) No precipitation of dye was observed at all even after leaving the summer-dyed paste in item (a) above at 20°C for 180 minutes, and when dyeing cotton fabric in the same manner as in item (a), A uniform yellow dyed product with a deep greenish tinge was obtained.

Comparative Example 4 (a) The dyes represented by formulas (4-1) to (4-8) in Example 4 had poor solubility when used alone, and
It was not possible to dissolve 17 in boiling water.

(b) Using 5f of each of the dyes represented by formulas (4-1) to (4-8) in Example 4, sodium alginate 201
1. A dyeing paste containing 1 kg of sodium metanitrobenzenesulfonate (1, 1 kg of sodium carbonate water) was prepared at 20°C, but precipitation of the dye was observed immediately after preparation. It was not possible to dye with summer using.

Examples 6 to 18 Dyeing and dyeing were carried out using the dyes shown in Tables 1 to 8 according to the methods described in Examples 1 to Φ4.

When using each dye alone, the dye precipitates during the dyeing and dyeing process or becomes gel-like, making it impossible to obtain industrially useful dyed products or dyed products.

However, with the dyes shown in Tables 1 to 1,
When dyes in which one or both of Y) have different groups are mixed in the proportions shown in Tables 1 to 4, the solubility of the dyes is good, and the dye has a dark greenish tint that is industrially useful. A yellow dyed product and a dyed product could be obtained.

In the table, D, E,

Claims (1)

[Claims] In the form of a free acid, there are the following general formulas (I), ▲mathematical formulas, chemical formulas, tables, etc.▼(I) (wherein, D is a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a phenoxy group). a sulfophenyl group substituted with a group, an acetylamino group, a propionylamino group, a maleinylamino group or a succinylamino group, or a naphthyl group substituted with 2 to 8 sulfonic acid groups, and E is a methoxy group. or represents an ethoxy group, X represents an aromatic amino residue having one or two sulfonic acid groups, or a halogen atom, R represents a hydrogen atom or a lower alkyl group that may be substituted, and A represents a substituent. represents an optional phenylene or naphthylene group, and Y is -SO_2CH_=CH_2 or -SO_
2CH_2CH_2Z, where Z represents a group that is eliminated by the action of an alkali. ) contains two or more monoazo dyes selected from the monoazo dye group represented by A method for dyeing or cross-dying cellulose fiber products or cellulose fiber-containing fiber products, the method comprising using a reactive dye composition.