JPH0643671B2 - Non-uniform dyeing method for cellulosic fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION According to the present invention, an aqueous solution containing an addition-type reactive dye stain-proofing agent and an alkali agent is uniformly applied to cellulose fibers and dried, and then the addition-type reactive dye and other chemicals are added as necessary. The present invention relates to a method for heterogeneous dyeing of cellulosic fibers, which comprises padding an aqueous solution containing it and heat-treating it.

Conventionally, as a means for obtaining a dyed product with a contrast, a cellulose fiber that has been uniformly dyed with an indigo dye or another dye for dyeing a cellulose fiber is used as a final sewing product, and then a washer or the like is used as a physical means. Put a triangular pumice stone in the washing machine and rotate it to peel off a part of the dyed dye to obtain contrast,
Alternatively, as a chemical means, a method in which a similar contrast is obtained by removing a part of the dye dyed with a bleaching agent is carried out.

In addition, a method of obtaining this kind of effect by pretreatment of fibers has also been attempted, and as an example, prepared is a modified cellulose-based fiber at the cotton or yarn stage. Examples include a method of obtaining contrast by dyeing a mixed cotton / knitted or woven or mixed knitted fabric, and using a mixed woven fabric.

However, in the case of the former physical and chemical methods, the effect is obtained by removing the dye. Therefore, when dyeing a dyed product, surface dyeing is required, so the uniformity and effect of patchiness are required. It is pointed out that there are drawbacks such as lack of reproducibility and poor dyeing efficiency for finishing in a short dyeing process, resulting in cost increase.

In addition, the latter method of pretreatment causes cost increase due to modification of cellulose fiber, or it is difficult to balance the inventory of products with different yarn counts or different knitting / fiber making methods, and has poor fastness. There is.

The present inventors have conducted intensive studies on a technique that can be advantageously applied to the reproducibility of processing, dyeing efficiency, processing cost, etc. pointed out in the conventional method, and as a result, found that the present invention can achieve the above.

The present invention will be described in more detail. After uniformly applying an aqueous solution containing a dye and a dyeing agent of an addition-type reactive dye to a cellulosic fiber by a padding method or a coating method and drying, the addition-type reaction dye and if necessary, A dyed product having contrast can be easily obtained with good reproducibility by padding an aqueous solution containing other chemicals and treating with dry heat or wet heat in a dry or undried state.

In the present invention, the addition type reactive dye means the following general formula D-SO ₂ -Y (wherein D is a residue of an organic dye having a sulfonic acid group, Y
Represents a —CH═CH ₂ group or a —CH ₂ CH ₂ OZ group, and Z represents a basic acid residue. ) Are reactive dyes, and many of these dyes are already known.

In the present invention, the anti-staining agent for the addition-type reactive dye may be any known agent that is chemically bonded to the addition-type reaction dye, for example, sodium hydroxymethanesulfonate, a compound of acidic sulfite, piperazine compound, diethylamine, ethylenediamine, diethylenetriamine. , Polycationic compounds such as cationic cocondensates obtained by adding a curing catalyst to a mixed solution of amines such as amino acids, guanyl compounds, aromatic monosulfonamides, cyclic aminotriazines and formaldehyde, or JP-A-53- Examples thereof include compounds described in JP-A 114989 and JP-A-53-114990.

The amount of these chemicals used is in the range of 0.1 to 0.5 times the weight of the dye, and the amount of the reactive dye and the type of the dye-proofing agent may be adjusted as follows by way of example. preferable.

In the present invention, an alkali agent having a pH of 11 or more can be applied as the stain-proofing agent for the addition-type reactive dye or the alkali agent used in combination with the addition-type reactive dye, and examples thereof include alkali metal carbonates, phosphates, silicates, and hydroxides. There is no limitation as a compound such as a substance.

However, alkali metal carbonates and phosphates are advantageous in terms of stability and workability of the padding liquid, and specific examples thereof include sodium bicarbonate, sodium carbonate, and sodium phosphate tribasic. 10-100 in the department
It is used in parts by weight, preferably 20 to 50 parts by weight.

In the padding solution of the present invention, sodium alginate, etherified CMC, high-molecular acrylic acid polymer, vinyl acetate high-molecular compound or the like, which are commonly used as migration inhibitors, may be used alone or in combination.

If necessary, other agents such as sodium metanitrobenzene sulfonate as a reduction inhibitor, sodium hexametaphosphate as a sequestering agent, sodium ethylenediaminetetraacetate, and urea as a wetting agent can be optionally used.

In the present invention, the cellulose fibers include cotton, viscose staple, viscose human silk, copper acetate human silk, and the like,
These fibers may be used alone or in combination of two or more.

The present invention can be specifically carried out as follows.

That is, a dye-resist solution prepared by adding cotton of cellulose fiber to a dye-addition-type reactive dye-dye, an alkaline agent and, if necessary, a migration inhibitor, a reduction inhibitor, a sequestering agent, and a wetting and dissolving agent. Pad with and dry in the middle.

The temperature at this time is usually in the range of 100 to 150 ° C. for 3 to 5 minutes, for example, by a hot flue dryer.

After the intermediate drying, the reactive dye of the above general formula and an alkaline agent, a migration inhibitor, a reduction inhibitor, a sequestering agent, a wetting and dissolving agent and the like are padded with a dye solution prepared and steaming 100 in a dry or undried state. ~ 150
Treatment at 30 ° C for 30 seconds to 30 minutes or baking,
Fixing treatment is performed at 120 to 150 ° C. for 3 to 5 minutes.

Then, a soaping bath containing a nonionic or anionic detergent is applied at 90 to 95 ° C. for 1 to 5 minutes for finishing.

As described above, the industrial value of the present invention is large because it can obtain a dyed product with contrast by covering the drawbacks which have hitherto been caused by the methods such as pre-treatment and post-treatment and only by the dyeing method.

Next, the present invention will be specifically described with reference to examples. In the sentence,
Parts are parts by weight.

Example 1 6.5 parts of sodium hydroxymethanesulfonate was added to 30 parts of hot water.
After being dissolved in 0 part, 10 parts of sodium metanitrobenzene sulfonate, 3 parts of Clewat N ₂ (EDTA2Na sequestering agent: manufactured by Teikoku Kagaku) and 100 parts of 5% paste of Duck Algin NSPM (sodium alginate: manufactured by Kibun Foods Co., Ltd.) A total of 1000 parts of dye-resist solution is prepared with added water. Immerse the mangle in this stain-proofing agent solution, immerse the cotton twill fabric in it, and use the mangle to uniformly remove the liquid at a pick-up of 60%.
Intermediate drying for 3 minutes.

Separately, 30 parts of Sumifix Brilliant Orange 3R Special (sulfate ethyl sulfone type reactive dye: manufactured by Sumitomo Chemical Co., Ltd.) is dissolved in 300 parts of hot water and cooled, and then 20 parts of sodium bicarbonate and duck algin NSPM (sodium alginate: Kibun) 100 parts of a 5% paste (manufactured by Ward) is added to prepare a dye solution having a total amount of 1000 parts.

Then, the padding cloth is dipped in the dye solution and uniformly drained with a mangle to pick up 60%.

Then, steam treatment is performed for 1 minute at 100 ° C. under saturated steam, followed by washing with water, soaping, and washing.

The dyed cloth thus obtained had an orange contrast.

The same results were obtained with good reproducibility even after repeated staining.

Example 2 20 parts of sodium bicarbonate was dissolved in 300 parts of hot water and cooled, and then 3.6 parts of diethylamine, 10 parts of sodium metanitrobenzenesulfonate, Clewat N ₂ (EDTA2Na sequestering agent: manufactured by Teikoku Kagaku) 3 parts, Snow Algin 100 parts of M (sodium alginate: Fuji Chemical Co., Ltd.) 5% paste is added, and the remaining amount of water is adjusted to 1,000 parts to prepare a dye-proofing agent solution.

A cotton voile fabric is dipped in this dye-resisting agent solution, uniformly drained using a mangle at a pick-up of 60%, and subjected to intermediate drying at 120 ° C. for 3 minutes with a hot flue dryer.

Separately, Sumifix Dark Brown BRS (Sulfatoethylsulfone type reactive dye: Sumitomo Chemical Co., Ltd.) 8
After dissolving 5 parts in 300 parts of hot water and cooling, 100 parts of 5% snow algin M (sodium alginate: Fuji Chemical Co., Ltd.) paste was added, and the remaining amount was diluted with water to immerse the padding cloth in a total of 1000 parts of dye solution. , Use mangle to uniformly remove liquid with a pick up of 60%.

Then, using a high temperature steamer, steam treatment is performed at 120 ° C. for 5 minutes, followed by washing with water, soaping and washing to finish.

The dyed fabric thus obtained had a brown contrast.

The same results were obtained with good reproducibility even after repeated staining.

Example 3 After dissolving 25 parts of sodium bicarbonate in hot water and cooling, 5.9 parts of sodium hydroxymethanesulfonate and Tetron 210
(EDTA2Na sequestering agent: manufactured by Meisei Chemical Co., Ltd.) 3 parts, sodium metanitrobenzene sulfonate 10 parts, duck algin NS
PM (sodium alginate: manufactured by Kibun Foods Co., Ltd.) 5% paste (160 parts) is added, and the remaining amount of water is adjusted to 1000 parts to prepare a dye-proofing agent solution.

A rayon twill woven fabric is dipped in this solution, uniformly drained using a mangle with a pick-up of 60%, and subjected to intermediate drying at 120 ° C. for 5 minutes.

Separately, Sumifix Golden Yellow GG (sulfatoethyl sulfone type reactive dye: Sumitomo Chemical Co., Ltd.)
12 parts, Sumifix Red B Special (sulfate ethyl sulfone type reactive dye: Sumitomo Chemical Co., Ltd.)
After dissolving 2 parts and 19 parts of Sumifix Brilliant Blue R Special (sulfatoethylsulfone type reactive dye: Sumitomo Chemical Co., Ltd.) in 300 parts of hot water and cooling, duck algin NSPM (sodium alginate: manufactured by Kibun Foods Co., Ltd.) ) 160 parts of 5% paste and 100 parts of urea are added to make up a total of 1000 parts of dye solution with water.

Then, the padding cloth is dipped in this dye solution and uniformly drained with a pick-up of 60% using a mangle.
Intermediate drying is performed at 0 ° C. for 3 minutes.

Then, it is baked at 150 ° C. for 4 minutes, washed with water, soaped, and washed to finish.

The dyed cloth thus obtained had an olive color contrast.

The same results were obtained with good reproducibility even after repeated staining.

Example 4 6.5 parts of sodium hydroxymethane sulfonate was added to 30 parts of warm water.
After dissolving in 0 parts, 10 parts of sodium metanitrobenzene sulfonate, 3 parts of Clewat N ₂ (EDTA2Na sequestering agent: manufactured by Teikoku Kagaku), 500 parts of 5% paste of Duck Algin NSPM (sodium alginate: manufactured by Kibun Foods Co., Ltd.) In addition, a total of 1000 parts of dye-proof liquid is prepared with the remaining water.

This liquid is uniformly coated on one surface of the cotton twill fabric using a knife coater so that the adhered amount is 40% of the woven fiber weight, and intermediate drying is performed at 120 ° C. for 3 minutes with a hot flue dryer.

Separately, Sumifix Red B Special (sulfate ethyl sulfone type reactive dye: Sumitomo Chemical Co., Ltd.) 20
After being dissolved in 300 parts of hot water and cooled, 10 parts of sodium metanitrobenzene sulfonate, 25 parts of sodium bicarbonate, 100 parts of 5% paste of Duck Algin NSPM (sodium alginate: manufactured by Kibun Food Co., Ltd.) are added, and the total amount is 1000 with water.
Parts of dye liquor are prepared.

Then, the coating cloth is dipped in the dye solution, and the liquid is uniformly deliquored with a pick-up of 60% using a mangle.
Perform intermediate drying at 120 ° C. for 3 minutes with a hot flue dryer.

Then, a steaming treatment is carried out at 120 ° C. for 5 minutes using a high temperature steamer, followed by washing with water, soaping, and washing with water.

The dyed cloth thus obtained had a red surface with a contrast and a back surface with a uniform red color.

Claims (1)

[Claims] 1. A cellulosic fiber is uniformly applied with an aqueous solution containing an antidye agent for an addition type reactive dye and an alkali agent, and dried, and then padded with an aqueous solution containing the addition type reactive dye and, if necessary, other chemicals. A method for heterogeneous dyeing of cellulose fibers, characterized by heat treatment.