JPH0440476B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for pad dyeing textile products consisting wholly or partly of cellulose fibers with direct or preferably reactive dyes.

The method of the present invention uses, in addition to the dye, a graft polymer obtained from an adduct of an alkylene oxide to at least trihydric aliphatic alcohol having 3 to 10 carbon atoms and methacrylamide or preferably acrylamide. It is characterized in that the fiber material to be dyed of the type mentioned above is padded with the aqueous dyeing liquid contained therein, and then the fixation of the dye is carried out by heat treatment or by the cold patch method.

A preferred graft polymer is an adduct obtained by adding 4 to 100 moles of propylene oxide, preferably 40 to 80 moles, to a trivalent to hexavalent alkanol having 3 to 6 carbon atoms, and graft polymerizing methacrylamide or particularly preferably acrylamide. This is what was obtained. The alkanol may be linear or branched. Examples include glycerin, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, mannitol, sorbitol, and the like.

Other suitable graft polymers are those produced by graft polymerizing methacrylamide or acrylamide onto the above-mentioned polyhydric alcohol, a mixture of ethylene oxide and propylene oxide, or an adduct of only ethylene oxide.

40 to 1 mole of glycerin to propylene oxide
Graft polymers of 80 mol adducts and acrylamide are particularly suitable.

The graft polymers used according to the invention preferably contain from 2.5 to 50% by weight of the adducts defined above as the main chain and from 50 to 97.5% by weight of the grafted acrylamide as the side chain.

The alkylene oxide adduct defined above is
Graft polymers containing 2.5 to 30% by weight and 70 to 97.5% by weight of methacrylamide or especially acrylamide are preferred. Preferably, the amide moiety is 80 to 80% based on the graft polymer.
97.5% by weight, more preferably 90 to 97.5% by weight.

Among these graft polymers, 40 to 80% of propylene oxide is added to 1 mole of glycerin as the main chain.
Particularly preferred are those containing 4 to 10% by weight of molar adduct and 90 to 96% by weight of acrylamide.

The percentage values given above are based on the total amount of graft polymer.

The graft polymers used according to the invention are produced by methods known per se. A suitable method involves the presence of a catalyst and advantageously a temperature between 40 and 100°C.
This is a method of polymerizing (1) an adduct of at least trivalent aliphatic alcohol having 3 to 10 carbon atoms and alkylene oxide and (2) acrylamide or methacrylamide at a temperature of . This produces predominantly graft polymers in which the alkylene oxide adduct forms the main chain and the grafted acrylamide or methacrylamide is attached to each carbon atom in the form of a side chain. .

As catalysts it is advantageous to use free radical-forming organic or preferably inorganic initiators.
Organic initiators suitable for carrying out free-radical polymerization are, for example, symmetrical peroxydicarbonates, butyl peroctoate, butyl perbenzoate,
Peracetate or peroxydicarbamate. Suitable inorganic initiators are hydrogen peroxide, perborates, persulfates or peroxydisulfates. A preferred initiator or activator is potassium peroxydisulfate (K ₂ S ₂ O ₈ ).

These catalysts may be used in amounts of 0.05 to 5 weight percent, advantageously 0.05 to 2 weight percent and most preferably 0.1 to 1 weight percent, based on the starting materials.

The graft polymerization is advantageously carried out in an inert atmosphere, for example in the presence of nitrogen.

The graft polymer is advantageously obtained in the form of a highly viscous solution. By dissolving and diluting with water, gel-like products with a solids content of, for example, 0.5 to 20% by weight, preferably 2 to 20% by weight, can be produced. In order to improve the storage and/or storage stability of the aqueous graft polymer solution obtained, preservatives such as chloroacetamide, N-hydroxymethylchloroacetamide, pentachlorophenolate, alkali metal nitrites, triethanolamine or preferably hydroquinone are added. Monomethyl ether or also bactericides such as sodium azide or surface-lubricious quaternary ammonium compounds having one or two fatty alkyl groups can be added. Mixtures of such preservatives and fungicidal compounds may also be preferably used.

A particularly preferred solution of the graft polymer has a molecular weight of 3,000 to 150,000, preferably 15,000 to 15,000 at 25°C.
120000 especially preferably 40000 to 80000mPas
It is a 2 or 3 to 5% solution with a viscosity of (milli Pascal seconds). The polyalkylene oxide adducts used for the preparation of the graft polymers generally have a molecular weight of 400 to 6000, preferably 3000 to 4500.

The amount of graft polymer used in the dyeing solution can be selected within a wide range. Suitable amounts are 3 to 40 g, preferably 5 to 40 g, and particularly preferably 8 to 20 g per staining solution in the form of a 3 to 10% aqueous solution.
It is g.

The method according to the invention is suitable for dyeing textile fabrics made of or containing cellulose. It is suitable for dyeing methods in which the cellulose material to be dyed is subjected to a heat treatment process after patching in order to fix the applied dye. Fixation of the dye can also be conveniently carried out by the cold patch batch method.

The thermofix process can be carried out by the steam method, the hot residence method, the thermosol method or preferably by microwave treatment.

In the case of the steam method, the dyed object patched with the dyeing liquor is heated in steam or superheated steam, preferably at a temperature of 98 to 130°C, preferably at a temperature of 102 to 110°C, for fixation of the dye. will be processed.

In the case of the hot dwell method, the patched dyeing material is dwelled in a wet state, preferably at a temperature of 85 DEG to 102 DEG C., for example for 15 to 120 minutes. In this case, the part to be dyed is treated with infrared rays to
It can also be preheated to 102°C. The residence temperature is
95 to 100°C is preferred.

Dye fixation by the so-called thermosol method can be carried out after or without intermediate drying, for example at temperatures in the range from 100 to 210°C. In the thermosol method, the patched material to be dyed is intermediately dried at 80 to 120℃, and then heated to 120 to 210℃.
C., preferably in the temperature range of 140 to 180.degree. Depending on the temperature, this thermosol treatment is carried out for 20 seconds to 5 minutes, preferably 30 to 60 minutes.
It can be seconds.

Preferably, the dye is thermally fixed using microwaves. In this case, the article to be dyed is impregnated with the dye liquor and, after squeezing out the excess dye liquor, it is preferably wound up into a roll and treated with microwaves in a chamber.

Microwave treatment time can range from 2 to 120 minutes. Here, microwave refers to radio waves having a frequency band of 300 to 100,000 MHz, preferably 1,000 to 30,000 MHz.

Fixation of the dye can also be carried out by a cold patch batch method in which the patched, preferably rolled, dyed article is left at room temperature (15 to 30°C) for, for example, 3 to 24 hours. In this case, the standing time at room temperature depends on the dye as is known. Depending on the case, it may be left at a slightly elevated temperature (30 to 80°C).

Suitable cellulose materials to be dyed are those made of regenerated cellulose or especially natural cellulose. Materials made of mixed fibers such as, for example, viscose staple fiber, viscose rayon, hemp, flax, jute and preferably cotton, or also polyamide/cotton or especially polyester/cotton, are suitable. In the case of mixed fibers, the polyester parts can be dyed beforehand, simultaneously or afterwards with disperse dyes.

The cellulosic material may be in various stages of processing, with particular preference being given to woven or knitted forms such as cloth. These cellulose products may be crude or pretreated.

The dyes used in the method of the invention are direct dyes or preferably reactive dyes commonly used for dyeing cellulose textile products.

As direct dyes, commonly used direct dyes are used, such as those listed as "Direct Dyes" in Color Index, 3rd edition (1971), Volume 2, pp. 2005-2478. be done.

Reactive dyes include commonly used dyes that form covalent bonds with cellulose, such as Color Index No. 3.
Edition (1971), Volume 3, pp. 3391-3560 and No. 6
Dyes listed as "Reactive Dyes" in Vol. (Revised 3rd Edition, 1975) pages 6268-6345 are used.

The amount of dye in the dye liquor is generally determined by the desired color density, and is generally 0.1 per dye liquor.
Suitable amount is from 100g to 100g, preferably from 5 to 60g/.

Alkali used for fixing the reactive dyes include, for example, sodium carbonate, sodium bicarbonate, sodium hydroxide, disodium phosphate, trisodium phosphate, borax, aqueous ammonium or alkali donors such as sodium trichloroacetate. It will be done. As the alkali, a mixture of water glass and a 30% aqueous sodium hydroxide solution is particularly preferred. The pH of the alkaline dye liquor is generally 7.5 to 13.2, preferably 8.5 to 11.5.

It is convenient to prepare the patch solution by dissolving the dye and adding the graft polymer and alkali. Depending on the type of dye used, the liquor may contain customary additives such as electrolytes such as sodium chloride or sodium sulfate, as well as urea, glycerin and/or sodium formate. Optionally, it is also possible to contain glue agents such as alginates, starch ethers or locust bean powder ethers.

It has been found to be very advantageous to additionally incorporate, in addition to the graft polymer, the known and customary alkali-resistant wetting agents into the patch solution. Examples of such wetting agents include the following. : Sulfonates of polycarboxylic acid esters, such as dihexylsulfosuccinate or dioctylsulfosuccinate; alkylarylsulfonates with a straight or branched alkyl chain having at least 6 carbon atoms, such as dodecylbenzenesulfonate or its alkyl chain. Alkyl sulfonates containing from 8 to 20 carbon atoms, such as dodecyl sulfonate or pentadecyl sulfonate. Preferably alkyl sulfonates are used. These sulfonates exemplified as wetting agents are generally alkali metal salts, particularly sodium or ammonium salts.

The amount of wetting agent added to the patch solution is suitably 1 to 10 g per dye solution, preferably 1.5 to 5 g.

In a preferred embodiment of the invention, the cellulosic material to be dyed is impregnated with a dye liquor containing a graft polymer as defined above in combination with a wetting agent consisting of components (A) and (B): I am made to do so.

Component (A): an alkyl sulfonate whose alkyl chain has from 8 to 20 carbon atoms; component (B): to 1 mole of fatty alcohol or fatty acid having from 8 to 22 carbon atoms, or to its alkyl moiety. Adduct of 2 to 40 moles of ethylene oxide to 1 mole of alkylphenol having a total of 4 to 12 carbon atoms.

Components (A) and (B) are generally present in a weight ratio of 5:1 to 1:1, preferably 5:1 to 2:1, particularly preferably 4:1 to 3:1.

The preferred ethylene oxide adduct (B) is 8 to
It is obtained by adding 2 to 10 moles of ethylene oxide to 1 mole of fatty alcohol having 12 carbon atoms.

The above-mentioned combination of graft polymer and wetting agent can also be used in the form of a pre-prepared aqueous formulation. Such a pre-formulation can be easily prepared by adding the above components (A) and (B) to an aqueous solution of the gel-like graft polymer and stirring the mixture. Upon addition of water and optionally further sodium chloride solution and silicone oil and/or silicone surfactant, the formulation is obtained as a homogeneous mixture.

Advantageously, this aqueous formulation contains at least the following composition (percentages are based on the weight of the aqueous formulation): 1 to 10% by weight of graft polymer as defined above 8 to 25% by weight of alkyl sulfonate (A) % Ethylene oxide adduct (B) 3 to 10% by weight Water 65 to 88% by weight Other auxiliary agents 0 to 3% by weight The amount of this aqueous preparation added to the dye liquor is 1
It is appropriate to select a weight in the range of 10 to 30g per serving.

At the end of the dyeing process, the dyed cellulosic material is washed in a conventional manner to wash away the unfixed dye. For this purpose, the dyed substrate is washed at 40°C, for example, in a solution containing soap or synthetic detergent.
Processing at temperatures ranging from to boiling temperature. A subsequent treatment with a fixing agent can also be carried out to improve the wet fastness.

Using the method of the invention, an improvement in the dye liquor absorption of the order of 40% is achieved and the dyeing yield is accordingly increased accordingly. By adding the graft polymer according to the present invention, the dyeing yield is clearly improved even if the amount added is minute.

Compared to the use of previously known acrylamide homopolymers or copolymers of acrylamide with other ethylenically unsaturated polymerizable monomers, such as those described in DE 2918607, Therefore, according to the method of the present invention, a higher dye absorption rate can be obtained by using a smaller amount of graft polymer. Further, according to the method of the present invention, a dyed product which is evenly dyed and deeply dyed can be obtained. Moreover, the dye fastness properties, such as light fastness, rub fastness and wet fastness, are in no way adversely affected by the use of the particular graft polymers according to the invention.

Hereinafter, the present invention will be explained in more detail with reference to manufacturing examples and usage examples. Percentages in production examples and usage example names are by weight unless otherwise specified. The amounts are, in the case of dyes, the amounts as commercially available, ie diluted commercial products, and in the case of auxiliaries, the amounts as pure substances. The 5-digit Color Index (DI) number is based on the Color Index 3rd Edition.

Production example of graft polymer Production example 1 22.5 g of acrylamide, 2.5 g of an adduct of 52 moles of propylene oxide added to 1 mole of glycerin,
and 200g of potassium peroxydisulfate 0.04g
of water and the solution is heated to 50° C. with stirring under a room atmosphere and maintained at this temperature for 3 hours. Thereafter, a solution of 0.03 g of potassium peroxydisulfate in 40 g of water is added dropwise over 60 minutes. A very viscous solution is produced, so the viscous solution is
Dilute by adding 300ml of water for minutes. Subsequently, the reaction mixture is kept at 50° C. for 5 hours. After adding 0.6 g of hydroquinone monomethyl ether and 0.12 g of sodium azide, the mixture is cooled to room temperature while stirring. However, gel 565 with a polymer content of 4.4%
g is obtained. The viscosity of this gel measured at 25℃ is
It was 112957 mPas.

Production Example 2 71.25 g of acrylamide, 3.75 g of an adduct of propylene oxide added to glycerin with an average molecular weight of 4200, and 0.09 g of potassium peroxydisulfate
A solution of 600 g of water is heated to 50° C. with stirring under a nitrogen atmosphere and kept at this temperature for 3 hours. The viscosity of this solution increases gradually. A solution of 0.06 g of potassium peroxydisulfate in 120 g of water is added dropwise to the viscous solution over a period of 60 minutes. Approximately 10 minutes after the start of dropping, the viscosity of the solution becomes very high, so 600 g of water is added over the next 20 minutes to dilute it. After the addition of the potassium peroxydisulfate solution has ended, the reaction mixture, whose viscosity increases, is kept at 50° C. for a further 5 hours. At this time, add 400g of water little by little to dilute. After this, 1.7 g of hydroquinone monomethyl ether is added and the mixture is cooled to room temperature while stirring. 1794 g of free-flowing gel with a polymer content of 4.3% are thus obtained.
The viscosity of this gel measured at 25°C was 64202 mPas.

Production example 3 71.25g of acrylamide, the average molecular weight of pentaerythritol with propylene oxide added is
3.75 g of the adduct of 3550 and 0.09 g of potassium peroxydisulfate are dissolved in 600 g of water, the solution is heated to 50° C. with stirring under a nitrogen atmosphere and kept at 50° C. for 3 hours. The viscosity of this solution increases gradually. A solution of 0.06 g of potassium peroxydisulfate in 120 g of water is added dropwise over 60 minutes. Approximately 30 minutes after dropping, the viscosity of the solution will increase, so 600
Dilute by adding g of water. After this, the solution, whose viscosity continued to increase, was kept at 50°C for another 4 hours.
Then add another 400g of water to dilute.
After adding 3.4 g of triethanolamine, the mixture is cooled to room temperature while stirring. This gives 1793 g of still fluid gel with a solids content of 4.0%.
The viscosity of this gel measured at 25°C was 75300 mPas.

Production Example 4 A solution of 17.8 g of acrylamide, 0.94 g of an adduct of 70 moles of propylene oxide and 6 moles of ethylene oxide added to 1 mole of glycerin, and 0.025 g of potassium peroxydisulfate in 250 g of water was stirred under a nitrogen atmosphere. Heat to 50℃,
It is then held at this temperature for 3 hours. The temperature of this solution is then increased to 60-63°C for 20 minutes and cooled to 55°C once the viscosity has clearly increased. After this solution, whose viscosity increases further, is held at 50° C. for a further 5 hours, a solution of 0.45 g of chloroacetamide and 0.45 g of hydroquinone monomethyl ether in 177 g of water is added. However, the graft polymer content
446 g of 4.2% gel are obtained. The viscosity of this gel measured at 25°C was 96750 mPas.

Production Example 5 The same procedure as in Production Example 4 was carried out except that instead of the adduct used in Production Example 4, an adduct obtained by adding 53 moles of propylene oxide to 1 mole of trimethylolpropane was used. 446 g of gel with a graft polymer content of 4.2% was obtained. The viscosity of this gel measured at 25°C was 19500 mPas.

Production example 6 17.24 g of acrylamide, 4.31 adduct of 70 moles of propylene oxide added to 1 mole of glycerin
A solution of 0.035 g of potassium peroxydisulfate and 0.035 g of potassium peroxydisulfate in 200 g of water is heated to 50° C. with stirring under a nitrogen atmosphere and maintained at this temperature for 4 hours. Subsequently, this solution, in which the viscosity increases further, is heated to 55° C. for 5 hours. water to the resulting gel
A solution of 0.4 g of chloroacetamide and 0.4 g of hydroquinone monomethyl ether in 291 g is added.
513 g of gel with a polymer content of 4.2% are thus obtained.
The viscosity of this gel measured at 25°C was 25750 mPas.

Production Example 7 In 200 g of water, 15.1 g of acrylamide, 70 moles of an adduct of 70 moles of propylene oxide added to 1 mole of glycerin, and potassium peroxydisulfate.
0.025 g of the mixture was stirred under nitrogen atmosphere.
Heat to 50°C and hold at this temperature for 3 hours. This solution, which further increases in viscosity, is then diluted with 5
Heat to 55 °C for an hour. Add water 291 to the resulting gel
A solution of 0.4 g of chloroacetamide and 0.4 g of hydroquinone monomethyl ether in g is added.
512 g of gel with a polymer content of 4.2% are obtained. 25℃
The viscosity of this gel measured at 16300 mPas.

Production Example 8 In 150 g of water, 13 g of acrylamide, 8.7 g of an adduct of 70 moles of propylene oxide added to 1 mole of glycerin, and potassium peroxydisulfate.
0.015 g of the mixture was stirred under nitrogen atmosphere.
Heat to 50°C and hold at this temperature for 4 hours. The solution, whose viscosity increases further, is then heated to 65°C for 2 hours and then to 60°C for a further 3 hours.
The resulting gel contains 94% of chloroacetamide in 347g of water.
g and 0.4 g of hydroquinone monomethyl ether. Gel 519 with 4.2% polymer content
g is obtained. The viscosity of this gel measured at 25°C is
It was 15582 mPas.

Application Examples Example 1 Untreated cotton knitted fabric with a bulk density of 165 g/m ² at 25°C.
The dye liquor was impregnated to 107% pick-up (based on dry substrate weight). The dye solution used contained the following components (amount per dye solution): 50 g of dye of the following formula (101) Pentadecane-1-sulfonic acid sodium salt and
C ₉ -C ₁₁ -Lubricant consisting of an adduct of 4 moles of ethylene oxide added to moles of primary alcohol (weight ratio 3:1) 2.5 g Graft polymer produced in Production Example 2 10 ml Sodium hydroxide solution (30%) 10ml Sodium silicate solution with silicate content 26.3-27.7%
75ml.

The immersion time at this time was 0.86 seconds and the roller pressure was 1.5 bar/cm ² .

After impregnation, the fabric is rolled up and
It was left at 25°C for 6 hours. The fabric was then rinsed and laundered for 20 minutes at boiling temperature using a non-ionic detergent (0.5 g/adduct of 9 moles of ethylene oxide to 1 mole of nonylphenol) in a bath ratio of 1:40. . After that, I rinsed it again and dried it.

This gave a deep and vivid red dyeing, which had an excellent level appearance.

Example 2 25 on untreated cotton knitted fabric (bulk density 165 g/m ² )
The dye liquor was impregnated to 110% pick-up (based on dry substrate weight) at . The dye solution used contained the following components (the amount is 1 dye solution).
Per): 50g of dye of the following formula (102) Lubricant used in Example 1 2.5g Graft polymer prepared in Production Example 2 10ml Sodium hydroxide solution (30%) 92ml Sodium silicate solution 100ml This impregnated cotton fabric was wound into a roll and heated at 25°C. was left for 18 hours. Thereafter, the dyed product was finished in the same manner as in Example 1.

This gave a deep, vivid red dyeing, and the dyed cotton fabric was distinguished by good penetration of the dye and a very level appearance.

Example 3 An untreated cotton knitted fabric (bulk density 165 g/m ² ) was impregnated with a dye liquor to a pick-up of 109% (based on dry substrate weight) at a temperature of 40°C. Each dye liquor contained the following components: 20 g of Direct Dye Direct Red 80C.I.No. 35780 5 g of the lubricant described in Example 1 20 g of the graft polymer prepared in Preparation Example 2 Urea 100g In this impregnation process, the soaking time is 0.86 seconds and the roller pressure is 1.5 bar/ ^cm2 . After impregnation,
The fabric was left at 25°C for 16 hours. The dyeings were then rinsed with hot (40° C.) and cold water, post-treated in the usual way with cationic auxiliaries to improve wet fastness, rinsed once more and dried.

This resulted in a dyed cotton fabric with a deep red color, which gave it an evenly dyed appearance. This example showed a 30% improvement in dyeing yield compared to the case of dyeing using a conventional dyeing method.

Example 4 Bleached cotton velvet (350g/m ² )
95% pick-up at 25°C (based on dry substrate weight)
It was impregnated with the dye solution until the end. Each dye liquor contained the following amounts of components:

Dye of formula (101) 40g Alkylbenzenesulfonate such as dodecylbenzenesulfonate (sodium salt) 23
1 _g Urea ₁₀₀ g Preparation Example 2 Graft polymer prepared by: 20 g Sodium carbonate (anhydrous) 20 g m-nitrobenzenesulfonic acid (sodium salt) 2 g The soaking time during impregnation is 0.86 seconds and the roller pressure is 2 bar/cm ² . After this, the fabric to be dyed
Steamed at 102°C for 3 minutes. Then rinse and
and non-ionic detergent (0.5 adduct of 9 moles of ethylene oxide added to 1 mole of nonylphenol).
g/) at a bath ratio of 1:40 for 20 minutes at boiling temperature. Rinse again and dry.

A deep, vivid red dyeing was obtained which had a level appearance.

Example 5 Bleached cotton velvet (350g/m ² )
The dye liquor was impregnated to 90% pick-up (based on dry substrate weight) at 40°C. Each dye liquor contained the following components: 20 g of dye of the following formula (103) 1 g of the wetting agent described in Example 4 100 g of urea 20 g of the graft polymer prepared in Preparation Example 2 The through-liquid speed during this impregnation is 2 m/min and the roller pressure is 2 bar/cm ² . The fabric was then steamed at 102°C for 3 minutes. The fabric was subsequently rinsed with hot (40° C.) and cold water and post-treated with a cationic fixative to improve wet fastness.

As a result, a dark brown dyed product having good color fastness and giving a level appearance was obtained.

Example 6 Untreated cotton knitted fabric (bulk density 165 g/m ² )
The dye liquor was impregnated to 104% pick-up (based on dry substrate weight) at 25°C. Each dye solution used contained the following components: 20 g of dye of the following formula (104) Sodium sulfate 50g Graft polymer produced in Production Example 1 20g m-nitrobenzenesulfonic acid sodium salt
5g Pentadecane-1-sulfonic acid sodium salt 43
%, _C9 - _C11 -fatty alcohol polyglycol ether 14%, and 2-ethylhexanol 5%
2.5 g of aqueous wetting agent containing % Sodium carbonate 20 g The article was then steamed at 102° C. for 90 seconds. This was followed by rinsing, soaping as described in Example 1, rinsing again and drying. The deep blue dyeing thus obtained was distinguished by good penetration of the dye and a very level appearance.

Similar excellent dyed products were obtained when the same amount of the graft polymer produced in Production Example 3 was used in place of the graft polymer produced in Production Example 1.

Example 7 Untreated cotton knitted fabric was dyed with an aqueous dye solution heated to 30°C.
It was impregnated to 104% pick-up (based on dry substrate weight). The dye solution used contained the following amounts of components per unit: 50 g of dye of formula (102) 20 g of the graft polymer prepared in Production Example 4 5 g of the wetting agent used in Example 6 Sodium hydroxide solution (30 g) %) 92ml sodium silicate solution 100ml The impregnated fabric was steamed at 102°C for 90 seconds, rinsed, washed at high temperature and rinsed again. This gave a deep red dyeing with a very well leveled appearance.

Similar good results were obtained when the same amount of the graft polymer prepared in Preparation Example 5 was used in place of the graft polymer prepared in Preparation Method 4.

Example 8 Untreated cotton knitted fabric with a bulk density of 165 g/ ^m2
The dye liquor was impregnated to 128% pick-up (based on dry substrate weight) at 250°C. Each dye liquor contained the following components: 50 g of dye of formula (101), sodium pentadecane-1-sulfonate;
C ₉ -C ₁₁ -Lubricant consisting of an adduct of 1 mol of primary alcohol and 4 mol of ethylene oxide (weight ratio: 3:1) 2.5 g Graft polymer prepared in Production Example 2 10 ml Sodium hydroxide solution ( 30%) 10ml 75ml sodium silicate solution with 26.3-27.7% silicate content.

Immersion time is 0.86 seconds, roller pressure is 1.5 bar/
^cm2 . The fabric is then rolled up, wrapped in a plastic sheet, and then
It was treated with 2450MHz microwave for 3 minutes. next,
The dyed material was washed with a nonionic detergent (nonylphenol 1
Adduct of 9 moles of ethylene oxide added to mole
1:40 bath ratio using 0.5g/20 at boiling temperature
Soaped for a minute. This was followed by another rinse and drying.

This gives a deep, vivid red dyeing with good leveling.

Similarly excellent dyed products were obtained when the same amounts of the graft polymers produced in Production Examples 1 and 3 to 8 were used in place of the graft polymer produced in Production Example 2.

Example 9 Untreated glued cotton fabric (208g/
m ² ) was impregnated with dye liquor at 25° C. to a pick-up of 119% (based on dry substrate weight). Each dye liquor contained the following components: 35 g of dye of the following formula (105) Dye of formula (104) 15g Wetting agent used in Example 1 5g Graft polymer prepared in Production Example 2 20g Urea 200g Sodium bicarbonate 15g m-nitrobenzenesulfonic acid sodium salt
5g.

After this the fabric was dried at 100°C and then treated for 40 seconds at 180°C for dye fixation. Subsequently, finishing treatment was carried out in the same manner as in Example 1.

This gave a green dyeing with good penetration of the dye and a level appearance.

Similar excellent dyed products were obtained when the same amount of the graft polymer produced in Production Example 7 was used in place of the graft polymer produced in Production Example 2.

Example 10 An untreated cotton knitted fabric (165 g/m ² ) was impregnated with dye liquor to a pick-up of 67% at a temperature of 25°C. Each dye liquor used contained the following components: 1 g dye of formula (104) 5 g wetting agent used in Example 1 15 ml sodium hydroxide solution (30%) Silicate content 26.3-27.7 75 ml of sodium silicate solution with a roller pressure of 2 bar/m ² . The fabric was then wound up into a roll and left at 25°C for 6 hours. Next, without intermediate drying, the dyed fabric is dyed again in Patsuda with the following dye solution at 12.5%.
The pick-up was impregnated. This dye solution is 1
Each contains the following amounts of ingredients: 5 g of the above wetting agent 20 g of the graft polymer prepared in Preparation Example 2 50 ml of sodium hydroxide solution (30%) Magnesium salt of diethylenetriaminepentaacetic acid
10 g aqueous hydrogen peroxide solution (35%) 50 ml Roller pressure was 2 bar/m ² . The fabric was re-rolled and left at 25°C for 15 hours. Afterwards, rinse the fabric and
Then, finishing treatment was carried out in the usual manner. This gives a bright blue contact dyeing with an excellent bleaching effect. In the case of this wet-in-wet method (Nass-in-wet method), by adding the graft polymer produced in Production Example 2, the processing solution pick-up necessary for the bleaching process can be achieved without intermediate drying. It became possible to achieve this.

Claims (1)

[Claims] 1. A method for dyeing a textile product made entirely or partially of cellulose fibers with a direct dye or a reactive dye, in which the cellulose material is dyed with, in addition to the dye,
Patching with an aqueous dye liquor containing a graft polymer obtained from an adduct of an alkylene oxide to at least trihydric aliphatic alcohol having 3 to 10 carbon atoms and acrylamide or methacrylamide; A method characterized by fixing the dye by heat treatment or a room-temperature patching method. 2. The patch dye liquor contains a graft polymer produced from an adduct obtained by adding 4 to 100 moles of propylene oxide to a tri- to hexahydric alcohol having 3 to 6 carbon atoms, and acrylamide or methacrylamide. A method according to claim 1, characterized in that: 3. The graft polymer is characterized in that it contains 2.5 to 50% by weight of the adduct as defined above and 50 to 97.5% by weight of grafted acrylamide or methacrylamide, based on the total graft polymer. A method according to claim 1 or 2. 4. The graft polymer contains 2.5 to 20% by weight of adducts and 80 to 80% by weight based on the total graft polymer.
97.5% by weight of grafted acrylamide. 5. Any one of claims 1 to 4, characterized in that the patch dye liquor contains a graft polymer of acrylamide and an adduct obtained by adding 40 to 80 moles of propylene oxide to 1 mole of glycine. Method described in Crab. 6. The graft polymer contains 4 to 10% by weight of an adduct obtained by adding 40 to 80 mol of propylene oxide to 1 mol of glycine and 90 to 96% by weight of acrylamide, based on the total graft polymer. The method according to claim 5, characterized in that: 7 The patch dyeing liquid is in the form of a 3 to 10% aqueous solution,
7. Process according to any one of claims 1 to 6, characterized in that it contains 5 to 40 g/preferably 8 to 20 g/of graft polymer. 8. The method according to any one of claims 1 to 7, which comprises dyeing with a reactive dye. 9. The method according to any one of claims 1 to 8, characterized in that fixation of the dye is carried out using microwaves. 10. The method according to any one of claims 1 to 8, characterized in that the dye is fixed by a thermosol method. 11. The method according to any one of claims 1 to 8, characterized in that the dye is fixed by steaming. 12 Claims 1 to 8 characterized in that the dye is fixed by a patch batch method at room temperature.
The method described in any of the paragraphs. 13. The method according to any one of claims 1 to 12, characterized in that the patch dye liquor further contains an alkali-resistant wetting agent in addition to the graft polymer. 14. The wetting agent comprises (A) an alkyl sulfonate whose alkyl moiety has from 8 to 20 carbon atoms, and (B) 1 mole or alkyl moiety of a fatty alcohol or fatty acid having from 8 to 22 carbon atoms. 2 to 1 mole of ethylene oxide to 1 mole of alkylphenol having a total of 4 to 12 carbon atoms
14. The method according to claim 13, characterized in that it contains an adduct of 40 mol. 15. Component (B) of the wetting agent is an adduct of 2 to 10 moles of ethylene oxide to 1 mole of fatty alcohol having 8 to 12 carbon atoms. the method of. 16 The patch dye liquor contains, in addition to the dye, an aqueous preparation, and the aqueous preparation contains at least the following components: 1 to 10% by weight of the graft polymer, the alkyl portion of which contains 8 to 20 carbon atoms; 8 to 25% by weight of alkyl sulfonates having atoms in 1 mole of fatty alcohols or fatty acids having 8 to 22 carbon atoms or in 1 mole of alkylphenols having 4 to 12 carbon atoms in the alkyl part thereof Ethylene oxide 2 to
Process according to claim 1, characterized in that it contains from 3 to 10% by weight of adduct containing 40 moles and from 65 to 88% by weight of water.