JPS6044434B2 - Dyeing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for dyeing cellulose fibers or structures containing the same.

Conventionally, many attempts have been made to dye cellulose fibers favorably using dyes such as disperse dyes that do not inherently have the ability to dye cellulose fibers.

Many of these attempts were made with the development of sublimation transfer printing methods that mainly used disperse dyes. Special Publication No. 47-5173 by method
4, a crosslinking agent, and a swelling agent.
, JP-A-50-38213, JP-A-50-907A, JP-A-50-29552, mainly by fiber processing methods, or by chemically acetylating cellulose fibers that normally have no affinity for disperse dyes. agent, pen. JP-A-50-1877 & JP-A-51-9918 which attempts to impart affinity to disperse dyes by modifying them with chemicals such as sol-forming agents
5 etc. are known. However, although these fiber treatment methods are possible using relatively simple equipment, they lack clarity in color development and have poor color fastness, especially wet fastness. Not good.

On the other hand, conventionally known methods for chemically modifying cellulose involve reaction in an aqueous solution using alkali or reaction in a solvent; The latter has disadvantages such as a long reaction time and unsuitability for actual production.

In order to solve these problems, the inventor developed cellulose fiber structures and mixed structures of cellulose fibers and synthetic fibers.
After alkali treatment, chemical modification treatment is performed in a vapor atmosphere of acid chloride such as p-toluenesulfonyl chloride,
After that, we devised a dyeing method characterized by direct or transfer printing using disperse dyes, oil-soluble dyes, mordant dyes, basic dyes, vat dyes, etc.

Conventionally, methods for chemically modifying cellulose using p-toluenesulfonyl chloride have been described in The Journal of the American Chemical Society, Vol. 72, pp. 670-674 (195:00), Textile Research Journal, No. 32.
Volume 797-804 (1962), Textile Research Journal Volume 3, pages 107-117 (1962)
However, these methods are considered unsuitable for industrial use because they require long modification times and require the use of bulky reagents that are difficult to handle. It's not meant to be.

In contrast, the present invention uses an acid chloride such as P-toluenesulfonyl chloride to improve the dyeability of cellulose fibers with disperse dyes, etc., and uses relatively simple equipment to improve the dyeability of cellulose fibers, including practical aspects and productivity. This is a study of reforming methods. That is, after the cellulose fibers have been treated with an alkaline agent, P
- A method of obtaining a modified fabric by chemically treating an acid chloride such as toluenesulfonyl chloride in a vapor atmosphere is a good process from a practical and production standpoint, and is a process that can be made continuous.

The present invention will be described in detail below.

The modification process includes a method described in literature, in which the alkali cellulose is made into alkali cellulose and then reacted in a P-toluenesulfonyl chloride solution.

These processes are methods in which an alkaline agent is treated and reacted in a P-toluenesulfonyl chloride solution while keeping moisture present. However, in the beginning, the reaction progresses well and modification is performed, but the modification gradually stops.

This is because the alkali agent and water are mixed into the P-toluenesulfonyl chloride solution, and even P-toluenesulfonyl chloride, which does not participate in the reaction, is hydrolyzed, resulting in wasted reagents and was found to be impractical. There is also a reaction in a basic solvent such as pyridine, but this requires a huge amount of equipment cost in terms of production. Therefore, as a result of intensive research, the inventor first dipped the fabric in an alkaline solution, narrowed it down to a certain ratio so that the amount of alkali treated was uniform, and then soaked the fabric in an acid solution such as P-toluenesulfonyl chloride. It has been discovered that chemical modification treatment can be carried out extremely easily by keeping the material in a chloride vapor atmosphere for a certain period of time. As is well known, sulfonic acid chlorides such as P-toluenesulfonyl chloride are usually solid or liquid, and at room temperature, compared to carboxylic acid chlorides such as benzoyl chloride.
It has high stability and is relatively easy to handle. However, P-toluenesulfonyl chloride and the like generally have sublimation properties and are extremely active when heated to temperatures above the boiling point. By simply exposing a fabric containing cellulose fibers for a certain period of time, an esterification reaction (hereinafter referred to as tosylation) between cellulose fibers and acid chloride such as P-toluenesulfonyl chloride occurs, converting cellulose fibers into disperse dye dyeable fibers. Chemical modification treatment can be performed. That is, P
- Acid chlorides such as toluenesulfonyl chloride are relatively stable at room temperature, so the drug has a good shelf life and is easy to handle during preparation, but it becomes highly active only during chemical modification treatment. This means that cellulose fiber fabric can be tosylated very effectively. In the inventor's experiment, a fabric was immersed in an alkaline solution, and the amount of alkali solution was squeezed to a certain level so that the amount of alkali treated was uniform. P- the fabric
The tosylation reaction occurred only when exposed to a vapor atmosphere of acid chloride such as toluenesulfonyl chloride, and almost no reaction occurred in the dry state.

This is considered to be because the presence of water effectively acts as a catalytic factor in the tosylation reaction. The vapor atmosphere of an acid chloride such as P-toluenesulfonyl chloride as described in the present invention means a certain space filled with the vapor of such a compound and heated to a temperature near or above the boiling point. , refers to a state in which the fiber fabric is sufficiently exposed to the vapor of this compound. The above method is
- There is no waste of acid chlorides such as toluenesulfonyl chloride and alkali agents, and it is practical and can be made continuous, resulting in good productivity.

When the thus obtained modified fabric was dry-transferred using, for example, a commercially available transfer paper using sublimable disperse dyes, the dyeability of the disperse dyes was good, and the dyeability was high and the color fastness was good. I was able to obtain some beautiful prints. Acid chlorides that can be used in this method are compounds having the structure shown below.

(X means H1-HO2, -CH3, or -SO2Cl) Compounds having such a structure include, for example, P-toluenesulfonyl chloride, benzenesulfonyl chloride, 0-nitrobenzenesulfonyl chloride, m
-nitrobenzenesulfonyl chloride, P-nitrobenzenesulfonyl chloride, toluene-3,4disulfonyl chloride, and the like.

Examples of the alkaline agents used in this method include hydroxides or alcoholates of alkali metals or alkaline earth metals such as lithium, sodium, potassium, beryllium, magnesium, calcium, barium, and strontium; metal carbonates or bicarbonates, alkali metal acetates, formates, butyrates, stearates, sulfinates, cyanates,
Salts of strong bases or weak bases and weak acids such as isocyanates and thiocyanates, phosphates of alkali metals, and the like can be used. Moreover, this method can also be used in combination with other conventional methods.

For example, the modified fabric obtained by the above method can be dyed with a resin dyeable with disperse dyes, such as aminoalkyd resin, polyamide,
Treatment with urethane, vinyl chloride, vinyl acetate, polyester, acrylic, acetal, polyvinyl alcohol, vinylidene chloride, vinyl acetal, styrene, precarbonate, epoxy resin, etc., and then dry transfer printing improves density, hue, and depth. etc. can be further improved. In addition, the modified fabric can be dimethylol urea, dimethylol propylene urea, dimethylol dihydroxyethylene urea, dimethylol uron, trimethylol melamine, trimethoxymethyl melamine, hexamethoxymethyl melamine, dimethylol methyl triazone, dimethylol ethyl triazone. , dimethylol hydroxyethyl triazone, dimethylol methyl carbamate, dimethylol ethyl carbamate, dimethylol hydroxyethyl carbamate, N-methylol acrylamide,
A fiber crosslinking agent such as methylolglyoxal monourea, methylolglyoxal diurea, formaldehyde, tetraoxane, glitaraldehyde, diepoxide, divinyl sulfone, 4-methoxy5-dimethyldimethylolpropyleneurea, tetramethylolacetylene diurea, and a crosslinking catalyst such as acetic acid. , organic acids such as maleic acid, ammonium salts such as ammonium chloride, ammonium sulfate, ammonium hydrogen phosphate, amines such as ethanolamine hydrochloride, 2-amino-2methylpropanol hydrochloride, magnesium chloride, zinc nitrate, zinc chloride, magnesium nitrate, By treating with zinc borofluoride, aluminum chloride, magnesium phosphate, etc. and crosslinking with a crosslinking agent, it is possible to improve the texture, and for example, it is possible to freely adjust the finish to a hard finish or a soft finish.

The cellulosic fibers applicable to this method include natural cellulose fibers such as cotton, regenerated cellulose fibers such as viscose rayon, and mixtures of these fibers and synthetic fibers such as polyester are also applicable. Of course, thread-like materials other than fabrics are also possible. In addition, dyes that can be used in this method include disperse dyes, oil-soluble dyes, mordant dyes, basic dyes, vat dyes, etc., which may or may not have sublimation properties, and are printed by direct printing or transfer printing. be able to.

In particular, when a sublimable dye is used, a dry transfer printing method is possible. Hereinafter, the present invention will be further explained in detail using the drawings.

That is, FIG. 1 shows a schematic diagram of the reforming apparatus used in the present invention, in which a cellulose fiber structure and a mixed structure of cellulose filter fibers and synthetic fibers, that is, a raw fabric 1, is treated with an alkali via a lead roll R1. The alkaline agent is introduced into the treatment bath 2, and then squeezed with rolls 3 so that the amount of alkaline agent treated is uniform, and then further passed through lead rolls R3 and R4 to P-
After introducing an acid chloride such as toluenesulfonyl chloride into the vapor phase can body 4 and exposing the fabric to the vapor of the acid chloride for a certain period of time, the fabric is released from the can body 4 via lead rolls R5 and R6. After exiting, the fabric is introduced sequentially into a water washing (or hot water) tank 8, a soaping tub 9, and a water washing (or hot water washing) tank via the lead roll R7. A modified fabric (tosylated fabric) 12 is obtained. That is, in the can body 4, 5 indicates a heating heater for heating the acid chloride such as P-toluenesulfonyl chloride in 6 to a temperature near or above its boiling point, and the P heated by this heating heater - Acid chloride 6 such as toluenesulfonyl chloride is vaporized in the can 6'' and a tosylation reaction occurs by exposing the fabric for a certain period of time.Furthermore, the can 4 is provided with a cooling inlet 7 for easy removal of the fabric. It is possible to prevent excess vaporized acid chloride such as P-toluenesulfonyl chloride from leaving the container by cooling it as much as possible. Since the specific gravity of chloride is heavier than air, gas gathers from the bottom of the can and gradually pushes the air out of the can.Furthermore, when the can is filled with gas, the excess will try to escape from the can. By controlling the temperature of the heater 5 and cooling the gas vapor that inevitably tries to escape with the cooler 7, it is possible to minimize the scattering of acid chlorides into the air. The steam that has blown out is exhausted by the exhaust device 13. By adopting such a structure, the structure of the reformer can be extremely simple and the cost of equipment can be reduced. In order to understand this, an explanation will be given using an example. <Example 1> The following experiment was conducted using an apparatus as shown in FIG.

(1) Mercerized polyester/cotton = 65
/35 blended fabric (fabric weight 100 y/d) was immersed in a 1:1 mixed aqueous solution of 8 wt% sodium hydroxide aqueous solution and 8 wt% sodium bicarbonate aqueous solution for 5 seconds, and then the squeezing rate was 100%. It was squeezed with a squeeze roll.

Next, this fabric was allowed to remain in a vapor atmosphere of P-toluenesulfonyl chloride without being dried, and maintained for 5 minutes. (The vapor atmosphere of P-toluenesulfonyl chloride is approximately 1
It was heated to 60°C and filled with steam. ) Furthermore, this fabric was washed with hot water and soaped using Marcel Setsuken.
After washing with water and drying, a chemically modified cloth was obtained. The degree of substitution (DS) of this modified fabric was calculated using the following formula (weight increase method) and was found to be 0.20. [2) Next 60y/d
A transfer paper was obtained by gravure printing on one-sided starch-coated paper using an ink having the composition shown below.

Ink〉 Sumikalon Red E-FBL (powder) (manufactured by Sumitomo Chemical Co., Ltd.) 1 Ethylcellulose N-7 (manufactured by Hercules Co., Ltd.) 9〃 Surfactant 1〃 Isopropyl alcohol 40'' Ethanol 40〃 (3), (1) When the transfer paper (2) was placed on top of the modified cloth, and transfer printing was performed by heating and pressurizing at a temperature of 195°C and a pressure of 300 fI/Cl) for a time of 10 seconds, the polyester and cotton parts were the same red color. It was possible to obtain a printed fabric with a density of .

In addition, when measured by the washing fastness (A-2) method based on JIS, it was grade 5, and the printed fabric was fast.

(The degree of substitution is the average value of hydroxyl groups substituted by tosyl groups among the three hydroxyl groups present in one glucose unit of cellulose).

, 162.08 is the molecular weight of one glucose unit, and 1 is the atomic weight of hydrogen. <Example 2> (1) A modified fabric was obtained as in Example-1.

Next, the modified fabric was immersed in a solution of the following formulation (a), then squeezed to a squeezing rate of 80%, pre-dried at 100°C for 2 minutes, and then baked at 150°C for 3 minutes. (a) Prescription Sumitex Resin NS-16 (Sumitomo Chemical) (glyoxal crosslinking agent) 1 Sumitex Resin AMH3OOO
(Sumitomo Chemical) (Acrylic Acid Ester Emulsion) Sumitex Accelerator X-80 (Sumitomo Chemical) 1
(80% water) (2) Next, transfer paper was prepared as in (Example-1).

(3) When the modified fabric (1) and the transfer paper (2) were superimposed and transferred under the conditions of temperature 195°C and pressure 300 da/C7lI) for a time of 70 seconds, the polyester part When we measured the washing fastness, we were able to obtain a printed fabric with the same red density, coloring, and depth on the cotton part.
The printed fabric was rated grade 5 according to method (A-2) and was strong.
When the color density of the transfer printed fabrics treated with resin and those without resin treatment was measured using a Macbeth reflection densitometer, the former was 1.32 and the latter was 1.27, indicating an increase in density.

<Example 3> A similar test was conducted using a mixed solution of O-toluenesulfonyl chloride/P-toluenesulfonyl chloride 73/23 instead of P-toluenesulfonyl chloride in Example-1. Good results similar to 1 were obtained.

However, in this case, the degree of substitution D. S. was 0.18. BRIEF DESCRIPTION OF THE DRAWINGS The drawings show one embodiment of the present invention.
The figure shows a schematic diagram of a modification device used in the dyeing method of the present invention.

1... Raw fabric, 2... Alkaline treatment bath, 3... Squeezing roll, 4... Acid chloride vapor such as P-toluenesulfonyl chloride Phase can body, 5
... Heater, 6 ... Chemical modifier (acid chloride such as P-toluenesulfonyl chloride), 7
...Cooler, 8...Washing (or hot water) bathtub, 9...Soaping bathtub, 10...
Water washing (or hot water washing) bathtub, 11... Drying dryer, 12... Chemically modified cloth, 13... Exhaust duct, Rl, R2, R3, R4, R5, R6 ,R7・
...Lead roll.

Claims (1)

[Claims] 1. In a method for chemically modifying cellulose fiber structures and mixed structures of cellulose fibers and synthetic fibers, such structures are treated with an alkali agent in advance and then exposed to a vapor atmosphere of p-toluenesulfonyl chloride or o-toluenesulfonyl chloride. A dyeing method characterized by carrying out chemical modification in the dye, followed by direct dyeing or transfer printing with disperse dyes, oil-soluble dyes, mordant dyes, basic dyes, vat dyes, etc.