JPS5930971A - Printing and padding dyeing of cellulose and cellulose containing fiber material - 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 A reactive dye containing at least one 8-)riazinyl group having the group (wherein M represents hydrogen or an alkali metal) and sodium trichloroacetate are preferably 1ooC or more The present invention relates to a dyeing method for printing or padding cellulose and cellulose-containing fiber materials, which is characterized in that it is used at a temperature of .

Many of the known reactive dyes currently believed to bind to cellulose fibers, such as monochlorotriazinyl, trichloropyrimidinyl, difluoromonochlorohyrimidinyl, vinylsulfonyl or reactive dyes with sulfatoethylsulfonyl natono-reactive groups, are used. When dyeing cellulose fiber material t1 by a printing or padding method, generally an acid binder having a relatively high alkalinity such as sodium bicarbonate or sodium carbonate is used as an acid binder, and a printing paste or padding liquid is used. It is alkaline and dyed. When such reactive dyes are used to dye cellulose-containing fiber materials, particularly polyester/cellulose mixed fiber materials, reactive dyes and disperse dyes are used in combination. However, there are several problems in achieving dyeing by using the two types of dyes used in dyeing these two types of fiber materials in the same process.

For example, acid binders such as sodium bicarbonate and sodium carbonate commonly used in such reactive dyes have undesirable effects such as agglomeration or decomposition of large numbers of disperse dyes in order to make the printing paste or padding liquid alkaline. give. Therefore.

When a single printing paste or padding liquid containing dyes for both types of textile materials is applied and dyeing is subsequently carried out by a single heat treatment, a dyed product of high quality cannot be obtained. Therefore, dyeing of such polyester/cellulose mixed fiber materials is generally carried out by printing by applying pigments, or by a two-phase padding method in which one fiber material is treated and then the other fiber material is treated in a separate bath. is being carried out. However, when pigments are applied, the printed and dyed products have the disadvantage that the texture deteriorates due to the resin treatment performed during the processing process, and the two-phase padding method is not an efficient method.

As a result of extensive studies, the present inventors have discovered that according to the present invention, cellulose or cellulose-containing fiber materials can be dyed with an extremely high color yield. Furthermore, since the present invention uses sodium trichloroacetate, which releases the acid binder only when subjected to heat or other action, when dyeing cellulose-containing fiber materials, especially polyester/cellulose mixed fiber materials using disperse dyes, disperse dyes cannot be used. It has been found that both fiber materials can be dyed simultaneously without agglomeration or decomposition. This is an extremely advantageous dyeing method in terms of shortening dyeing time, saving energy, and reducing processing costs.

Reactive dyes containing S-) riazinyl groups with quaternary nitrogen atoms derived from nicotinic acid or isonicotinic acid applied to cellulose-containing textile materials in the presence of acid binders, e.g. bicarbonate) The method is JP-A-52-1
No. 8732. However, this method causes the disperse dye to be aggregated or decomposed to a much greater degree than the method of the present invention. This is because the printing paste or padding liquid according to the method of the present invention, which uses trichloroacetic acid as an acid binder, releases the acid binder only when heated, and the alkalinity is preferable so that the reactive dye binds to the fiber. This is because, in contrast, in the method of JP-A-52-18732, the printing paste or padding liquid has a relatively high alkalinity from the beginning.

Incidentally, the pH measurement values after heat treatment of the padding liquid and the cloth impregnated with the padding liquid when using the sodium trichloroacetate of the present invention are shown below.

a: Padding liquid: pH5, Ob:to
Cloth dried by dry heat treatment in oc for 2 minutes
: Cloth obtained by further steaming the dried cloth with pII 9.4 cab at 180C for 5 minutes : pH 9,
Cloth obtained by dry heat treatment of Od:b for 2 minutes at 180C: pH 8,9 This test was carried out using disperse dye 4.
Weight %, sodium trichloroacetate 2 parts by weight, urea 20 parts
Weight: 5%, medium viscosity sodium alginate: 0.2% by weight, water: 7%
3.8 weight, add a predetermined amount of acetic acid if necessary to adjust the pH.
This was a padding liquid with a concentration of 0.5 and a polyester/cotton mixed woven fabric was impregnated with the liquid for padding.

The reduction rate at this time was 70%. The pH value of the fabric was measured as follows.

That is, cloth IJ was placed in ion exchange water 201 at 25C for 2 hours.
After immersion for 0 minutes, the p[I value of the immersion liquid was measured.

In addition, as a method for simultaneously printing or padding a polyester/cellulose mixed fiber material, for example,
Applying dyes containing one or more 8-) riazinyl groups with quaternary nitrogen substituents as known in No. 6-4784,
Methods of dyeing in the absence of acid binders are known. Compared to the density of the dyeings when this dyeing method is applied, the dyeings obtained with the method of the invention using sodium trichloroacetate as acid binder have a very high density.

6- For example, a printing paste having the composition listed in the following table is prepared.

(In the example, "1 part" is "part by weight.") Printing paste charge Printing paste round dyeing charge *44 Water 24 22
Alginate glue (5% aqueous solution) 5050 urine
20 20 Dicyandiamide 22 Total
100 parts 100 parts Printing paste Printing paste circle: The printing paste and circle of the present invention are used to print on mercerized cotton cloth. The cloth dried by a dry heat treatment at 100C for several minutes is divided into two equal parts, one part is subjected to a dry heat treatment at 200C for 1 minute, and the other part is subjected to a heated steam treatment at 180C for 10 minutes.

The printed fabric is washed in boiling water and dried.

No matter which heat treatment is applied to the resulting fabric, if a printing paste is used, it will be dyed a gray-black color, but if a printing paste is used, it will be dyed a deeper black color. .

The dyes used in the test were as follows in free acid form:

2:1 chromium-cobalt mixed complex λmax=5
8 5 nm Another advantage of the method of the present invention is that by using sulfur trichloroacetate as an acid binder, which releases the acid binder only upon heating, the printing paste or padding liquid is free from the hydrolysis of the reactive dye. It is maintained in a relatively stable PTR region, that is, neutral to weakly acidic, and the printing paste or padding liquid exhibits extremely good storage stability. This is extremely advantageous in terms of dyeing reproducibility, workability, and economic efficiency, and this feature is particularly important not only for cellulose mixed fiber materials but also for cellulose fiber materials, especially cotton printing or padding dyeing. Demonstrated.

A reactive dye containing at least one S-)riazinyl group having a group of (in the formula, M represents hydrogen or an alkali metal) is defined as R is a hydrogen atom or C1-C3 alkyl) and represents a chromophore having at least one water-soluble group bonded to a triazinyl nucleus, and A is a substituted or unsubstituted amine residue, an alkoxy group, or a phenoxy represents a group 9-1L,,M represents a hydrogen atom or an alkali metal, especially thorium or potassium; ] A dye represented by

Alternatively, the formula represents a chlorine atom; ] A dye represented by

Alternatively, the formula [wherein X, Y and Y2 are the dye formula [I] and 1
0- Represents the same meaning as the definition of [■]. ] A dye represented by

Alternatively, A, Yl and Y2 have the same meanings as in the formulas [■] and [■] of the dye. ] It is a dye represented by

Examples of the chromophore represented by D in the formulas [■] to (1) include azo-based, metal-containing azo-based, formazan-based, phthalocyanine-based, and anthraquinone-based chromophores, which contain at least one sulfonic acid or carboxylic acid. It has a water-soluble group such as

Examples of the unsubstituted or substituted amine, alkoxy or phenoxy which do not react with the dye represented by A include the following.

Amino, alkylamino (methylamine, ethylamino, propylamino, butylamino, dimethylamino, diethylamine, methylethylamino, octylamino,
dichlorohexylamino), hydroxyalkylamino (
monoethanolamino, jetanolamino), cyanoalkylamino (β-cyanoethylamino, di-β-cyanoethylamino), β-sulfoethylamino, taurine residue, glycine residue, anilino, sulfo, chloro, lower alkyl, lower Anilino (o-, m- or p-sulfoanilino, 2.5-disulfoanilino, 0-1m or p-)luidino, o-, m- or p-methoxyanilino, 0-9m substituted with alkoxy, nitrocarboxy, etc.
- or p-chloroanilino, 2-methyl-4-sulfoanilino, 2-methoxy-4-sulfoanilino, p-nitroanilino, 2-sulfo-4-methylanilino, 4-lyp-2-sulfoanilino, o-, m-matahal -carboxyanilino, 2-carboxy-4-sulfoanilino), N-methylanilino, N-ethyl-4-chloroanilino, alkoxy (methoxy, ethoxy, propoxy, butoxy), alkoxyalkoxy (methoxyethoxy, ethoxyethoxy, methoxypropoxy), Phenoxy substituted with phenoxy, chloro, nitro, methyl, sulfo, carboxy, etc. (o-, m- or p-chlorophenoxy, o-, m- or ha-nitrophenoxy, o-, m- or p-sulfophenoxy , o−, m=
or p-carboxyphenoxy, morpholino, piperidino, piperazino.

Examples of the diamino residue represented by X include the following.

Alkylene diamino (ethylene diamino, 1°3-propylene diamino, 1,6-hexylene diamino, 2-hydroxy-1,3-propylene diamino, NHCH2
CH20CH2CH2NH-)arylenediamino(1
,4-phenylenediamino, l-methyl-2,6-)unilenediamino, 1,3-phenylenediamino, 4-sulfo-1,3-phenylenediamino, 4,6-disulfo-1,3-13=- Phenylene diamino, 2-sulfo-1,4-phenylene diamino, 2,5-disulfo-1,4-phenylene diamino, 5-carboxy-1,3-phenylene diamino, 2,5-dimethoxy-1,4-phenylene diamino ,
4-N-methylaminoanilino, 1,2-phenylenediamino, 2.4,6-trimethyl-5-sulbo 1,4
-phenylenedi2-methyl-5-sulfo-1,3-phenylenediamino, 4-methyl-1,2-phenylenediami or M includes lithium, sodium or potassium 14-rum.

In the present invention, the dyes of formulas [I] to [Seki] may be directly added to the printing paste or padding liquid. The nicotinic acid or isonicotinic acid shown above, or an alkali metal salt thereof, may be added to the printing paste or padding liquid to form the dyes of the formulas [■] to (2). Alternatively, perform appropriate processing in advance and use the formula [■
The dyes [1] to [2] may be applied to the printing paste or padding liquid in a solution or dispersed state.

Compounds of formula M have 0,5
~10 times the molar amount, preferably 1 to 5 times the molar amount.

Many known disperse dyes can be used for dyeing the polyester/cellulose mixed fiber material according to the method of the present invention. Advantageously, the following disperse dyes can be mentioned.

C, 1, Disbirds Yellow 226. C, 1, Jisper thread 332. C, 1, Jisper thread 221,
C, 1, Jispers Blue 341. C, 1, Jispers Yellow 126. C, 1, Jispers Orange 12
7. C,L dispers thread 278, C,I.

Jisper Red 288. C, 1, Jispers Brown 19. C, 1, Jispers Blue 106. C.I.

Jispers Blue 147. C, 1, Jispers Blue 285. C, 1, Jispers Yellow 224, C,
I.

Jispers Yellow 164. , C,1, Jispers Orange 73. C, 1, Jisper thread 221,
C.I.

Jisper thread 153, C, T, Jisper thread 145. C, 1, Jisper thread 258. C,
I.

Jispers Blue 266, C, 1, Jispers Blue 1
04. C, 1, Disperse Blue 60° Staining according to the present invention is generally carried out as follows. The dye or its precursor and the compound of formula M are usually applied to the textile material from an aqueous medium.

That is, it may be in the form of a padding liquid or a printing paste. Such printing pastes or padding liquids generally contain 0.1 to 10% by weight of sodium trichloroacetate, preferably 0.5 to 5% by weight, as well as auxiliaries necessary for good dyeing results, such as thickening agents. May contain.

In the present invention, the printing or padding is preferably 100%
For example, before heating the printed or padded textile material to a temperature of 100 IZ" or higher,
Dry at 110C.

Heating at 100 C or higher is usually carried out by dry heat, heating, pressurization, or normal pressure steam treatment. For example 150~220C
Dry heat treatment for several minutes at 120~180C
Heat or pressurized steam treatment is performed for 20 minutes, or treatment is performed with normal pressure saturated steam for 5 to 20 minutes. After heating, the dyed textile material is subjected to the usual washing treatment.

An advantageous embodiment of the invention is the use of urea together with a 17-dye of the formula [(2)] or a precursor thereof and a compound of 2M. The amount of urea is typically 2 to 30 parts by weight of the aqueous composition used to apply the dye or precursor to the textile material. Urea has the effect of increasing staining density.

For example, dicyandiamide may be contained in an amount of 1 to 4% by weight instead of urea or together with urea. Dicyandiamide, like urea, has the effect of increasing the density of staining. In addition, the pH of the printing paste or padding liquid is preferably in the neutral to weakly acidic range, and if necessary, for example, acetic acid O to 0.
．． 1 weight width may be included.

The method of the invention is particularly useful for dyeing the cellulose component of polyester/cellulose mixed fiber materials. A disperse dye for dyeing polyester fiber materials may be included in advance in the printing paste or padding liquid used in the method of the present invention. The above-mentioned printing paste or padding liquid composition of the present invention does not have as bad an effect as the disperse dye and has extremely little adverse effect, and the above-mentioned heating conditions of the present invention are the heating conditions when dyeing polyester fiber materials with the disperse dye -18=. This is convenient because it is similar to

This is because both fiber materials are dyed simultaneously by the same heat treatment by application of a single printing paste or padding liquid containing the reactive dye and the disperse dye.

Advantageous cleaning after dyeing or printing when disperse dyes are applied at the same time is the usual washing with water, hot water followed by an alkaline agent such as carbonic acid (IJum or sodium hydroxide 0.1).
~0.5% by weight and a surfactant such as an anionic or nonionic surfactant for several minutes to 20 minutes at a temperature of 60 to 100C using a bath containing 0.1 to 0.5% by weight. , followed by washing with hot water and/or water.

Preferred fiber materials that can be applied to the present invention include cellulose fiber materials such as cotton, viscose rayon, cuproammonium rayon, hemp, and mixed fibers containing cellulose fiber materials with polyester, polyacrylonitrile, polyamide, wool, etc. materials, especially
It is a polyester/cellulose mixed fiber material.

Next, examples of the present invention will be described, in which "1 part" in all examples is "-part by weight."

Example 1 Mercerized cotton broadcloth was mixed with 40 parts of the dye of the following formula (1).・Lichloroacetic acid sl.lium 20 parts, R
150 ilt, 10 parts of sodium metanitrobenzenesulfonate, 2 parts of medium viscosity sodium alginate, 7 parts of water
It was impregnated with a padding liquid consisting of 78 parts and padded at a squeezing rate of 70%. After drying at 100C for 2 minutes, this cloth was divided into two equal parts, one part was dry heat treated at 150C for 2 minutes, and the other part was heated with steam at 1500C for 5 minutes. . Wash this cloth with regular water, hot water,
A boiling saw pink was applied, followed by washing and drying.

Regardless of the heat treatment, the dyed product was a deep red color with very good fastness properties.

To obtain this dye in the form of the free acid, 8.8 parts of the following formula 1 in the form of the free acid are dissolved in 150 parts of water, into which 0.8 parts of 100% sodium hydroxide and nicotinic acid are added. An aqueous solution of sodium nicotinate in which 2.5 parts were dissolved in 30 parts of water was strained, the temperature of this mixed solution was raised to 80C, and stirring was continued at this temperature for about 16 hours, followed by salting out with sodium chloride. The mixture was filtered and dried to obtain the target S-)riazinyl reactive dye substituted with nicotinic acid. This dye was a nicotinic acid substituted dye with a purity of 93% by H8LC (high performance liquid chromatography).

21 - Example 2 20 parts of the dye of the following formula (2), 20 parts of the dye of the formula (3), 30 parts of sodium acetate, 100 parts of urea, 20 parts of dicyandiamide, 10 parts of sodium metanitrobenzenesulfonate, medium Mercerized cotton broadcloth was printed using a printing paste containing 500 parts of viscosity sodium alginate (5% aqueous solution) and 300 parts of water. After drying this cloth for 2 minutes at 1000, divide the cloth into two equal parts.
One part was subjected to dry heat treatment at 180CK for 2 minutes, and the other part was subjected to heating steam treatment at 130C for 5 minutes.

It was washed with water, hot water and boiling soap as usual, then washed with water and dried.

The dyeings were treated with hot steam to give a darker green dyeing and to show good fastness properties. In the form of free acid In the form of free acid Example 3 Mercerized cotton broad was mixed with 50 parts of the dye of the following formula (4), 10 parts of sodium nicotinate, 25 parts of sodium trichloroacetate, 200 parts of urea, and metanitrobenzenesulfonic acid. It was impregnated with a padding liquid consisting of 10 parts of sodium, 2 parts of medium viscosity sodium alginate, and 703 parts of water, and padded at a squeezing rate of 80%. After drying at 100C for 2 minutes, heated steam treatment was performed at 180C for 5 minutes. The fabric was washed in regular water, hot water, boiled so-pink, then washed in water and dried.

The dyed product obtained was dyed bright red.

Example 4 Polyester/cotton (65%/35%) mixed woven fabric was treated with 40 parts of dye of the following formula (5) in the form of free acid, C.1, Dysper Red 332
40 parts, sodium trichloroacetate 20 parts, urea 50 parts
30 parts of dicyandiamide, 10 parts of sodium metanitrobenzenesulfonate, 2 parts of medium-viscosity sodium alginate, and 808 parts of water, and padded at a squeezing rate of 70%. After drying at 100C for 2 minutes, the cloth was divided into two equal parts, one part was subjected to a dry heat treatment at 2000C for 1 minute, and the other part was subjected to a heated steam treatment at 180C for 5 minutes. The cloth was washed with water, hot water, carbonated, treated at 100C for 10 minutes in a cleaning bath containing 2 parts of IJum, 2 parts of nonionic surfactant, and 996 parts of water, washed with water, and then dried. .

Regardless of the heat treatment, the dyed product was a deep red color with very good fastness properties.

In the form of free acid, λmax = 536 nm Example 5 Dye 40 of the following formula (6) was prepared by the method described in Example 4.
When applied to pad dyeing of polyester/cotton (65%/35%) mixed fabric using 40 parts of C,1, Dysperse Yellow 226, the dyeings obtained have very good lightfastness and wet fastness A deep yellow dyeing with a reddish tinge was obtained, which had a characteristic of viscosity.

In the form of free acid, 40 parts of dye of the following formula (7), 40 parts of C,1, Disperse Blue 341, 20 parts of sodium trichloroacetate, 100 M urine, 20 parts of sodium metanitrobenzenesulfonate, A printing paste with a pH of 5 containing 0.5 parts of acetic acid, 500 parts of alginic acid paste (5% aqueous solution), and 279.5 parts of water was prepared and printed on a polyester/cotton (50% 150%) interwoven fabric. After drying this cloth at 1000C for 2 minutes, it was subjected to dry heat treatment at 200C for 1 minute.

The cloth was washed with water, washed with hot water, and then treated with hydroxide in a washing bath containing 2 parts of IJum, 2 parts of nonionic surfactant, and 996 parts of water at 800 °C for 10 minutes, washed with water, and then dried. went.

The dyeings obtained have very good fastness properties,
A deep greenish blue staining was given.

26 - λmax = 6] in the form of the free acid 5 parts m Example 7 50 parts of the dye of formula (8),
C, 1, 35 parts of Jispers Yellow 226, and C,
1. When applied to the printing of a polyester/cotton (50% 750%) interwoven fabric using 15 parts of Dysper Red 332, the dyeing obtained was given a deep orange dyeing with good fastness properties. .

In the form of free acid, Example 8 Polyester/cotton (65%/35%) mixed woven fabric was treated with 40 parts of dye of the following formula (9), C.1, Dysper Red 221
40 parts of sodium nicotinate, 20 parts of sodium trichloroacetate, 100 parts of urea, 10 parts of sodium metanitrobenzenesulfonate, 2 parts of medium viscosity sodium alginate, and 768 parts of water, and the squeezing rate was 60%. I was buzzing. After drying at 110C for 1 minute, it was heated and steamed at 180C for 7 minutes. The cloth was washed as described in Example 4 and then dried.

The resulting dyeing was a deep red color with very good fastness properties.

In place of the dyes used in Examples 9 to II in the form of free acids, 40 parts of each of the dyes listed in the table below were used and treated in the same manner as in Example 2, resulting in good results in all cases. A dyeing with the fastness properties and the shades listed in the table below was obtained.

Patent Applicant: Nippon Kayaku Co., Ltd. 29 - Procedural Amendment September 14, 1980 Kazuo Wakasugi, Commissioner of the Patent Office 1 Display of the case 1982 Patent Application No. 116127 2 Name of the invention Cellulose and cellulose-containing fibrous materials Printing or 3
Person making the amendment'Relation to the Rising Color Law Case Patent Applicant No. 2-1 Marunouchi-chome, Chiyo 11-ku, Tokyo (40B) Representative of Nippon Kayaku Co., Ltd. President and CEO Tsunekazu Sakano 4th Director Tokyo 2-1-5, Marunouchi-chome, Chiyoda-ku Date of amendment order (voluntary) 6 No number of inventions increased by amendment 7 Detailed description of the invention in the specification to be amended 8 Contents of amendment Amended as per attached sheet Contents 1. On the 6th line from the top of page 4 of the specification, there is a further description of the present invention.
The statement should be corrected to read, "In the method of the present invention."

2゜In the 6th line from the bottom of page 4, the statement ``Reactive dye acid binder'' is corrected to ``Using a reactive dye, acid binder.''

3. On the 6th line of page 6, the phrase "1pHo,s was set" was replaced with "p
Hs, o,” he corrected.

4. Correct the formula in line 7 on page 9 as follows.

5. On the 8th line of page 10, the statement "1 represents a chlorine atom" is corrected to "1 represents a halogen atom."

6. On page 17, line 9, the phrase "padding is" is corrected to "padding dyeing is".

7. In the 5th line of page 18, the phrase ``dying density'' is corrected to ``the density of the dyed material.''

8. On page 24, line 4 and page 26, line 8, the words "mixed woven fabric" should be corrected to "blended fabric."

10. Example of the table on page 29? Correct the formula as follows.

[

Claims (1)

[Claims] (1) A cellulose characterized by using a reactive dye containing at least one S-)riazinyl group having a group of the formula (wherein M represents hydrogen or an alkali metal) and sodium trichloroacetate. and a printing or padding dyeing method for cellulose-containing fiber materials.