JPS6339709B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for chemically modifying cellulose fibers or fibrous structures containing the same. Attempts have been made to dye cellulose fibers well using dyes such as disperse dyes that do not originally have the ability to dye cellulose fibers.
Special Publication 1977-51734, Special Publication 1977-90788, Special Publication 1977-
29552, etc., and methods such as JP-A-50-18778 and JP-A-51-99185, which chemically improve cellulose fibers that normally have no affinity for disperse dyes. method is known. However, although these methods using the above-mentioned fiber treatment agents are possible using relatively simple equipment, they suffer from lack of clarity in color development and poor color fastness, especially wet fastness. On the other hand, conventionally known methods for chemically modifying cellulose fibers have poor workability due to the irritation and odor of the chemicals themselves, and require very expensive equipment investment. In order to solve these problems, the inventors first treated cellulose fibers or a mixed structure of cellulose fibers and synthetic fibers with an alkaline agent and an acid chloride such as P-toluenesulfonyl chloride in any order, and then He invented and applied for a patent for a dyeing method in which chemical modification is performed through steam or dry heat treatment, followed by direct or transfer printing with disperse dyes, oil-soluble dyes, mordant dyes, basic dyes, vat dyes, etc. . Although the above invention provides very good results in chemically modifying textiles, there are several process problems in chemically modifying knitted fabrics and yarn-like fibers. The present invention aims to improve the dyeability of cellulose fiber structures and mixed structures of cellulose fibers and synthetic fibers with disperse dyes, etc., using an acid chloride such as P-toluenesulfonyl chloride using a relatively simple apparatus. This is a highly practical and highly productive chemical modification method that can chemically modify not only woven fabrics, but also knitted and filamentous materials very well. That is, the present invention provides a method for chemically modifying a cellulose fiber structure and a mixed structure of cellulose fibers and synthetic fibers, in which such a structure is previously treated with an alkaline agent and then held in a sealable system. After reducing the pressure in the system appropriately, a compound having the structure shown below (hereinafter referred to as a modifier) is injected into the system in a gaseous state from one side of the fiber structure, and then water vapor is added to the system as well. After the system is evacuated and the pressure is reduced, the modifier is injected into the system in gaseous form from the other side of the fiber structure, and then water vapor is also injected into the system. This method of chemically modifying a cellulose fiber-containing structure is characterized in that one cycle is an operation of holding the cellulose fiber for a certain period of time, and this operation is repeated as necessary.

[Formula] (where, X means H, NO ₂ , CH ₃ SO ₂ Cl) According to this method, cellulose fiber structures and cellulose fibers that have been previously treated with an alkali agent, which are the chemically modified materials, Because the system holding the synthetic fiber mixed structure is once in a reduced pressure state, acid chlorides such as P-toluenesulfonyl chloride, which is used in the next step, easily enter the system in a gaseous state and are chemically reacted. Because it easily penetrates into the inside of the modified material,
The present invention is a chemical modification method that is extremely excellent in terms of economy and productivity, as it allows extremely good chemical modification to be carried out. A more detailed explanation will be given below based on FIG. 1 of the drawings. That is, after a cellulose fiber structure and a mixed structure of cellulose fibers and synthetic fibers are treated with an alkaline agent in advance, they are mounted in a wound state on a drum 8 and the reaction tank 6 is sealed. Next, open valve D, reduce the pressure appropriately with a vacuum pump, and close valve D. Then, open the valve A, and inject the reagent 5, which has been heated and gasified in the oil bath 2, from the reagent tank 4 into the reaction tank 6, and contact it with the fibers that have been treated with the alkali agent from the outside of the drum 8. and close valve A.
Thereafter, valve C is opened to inject steam into the reaction tank 6, valve C is closed and held for a certain period of time, valve D is opened to reduce the pressure at the same time as exhaust, and valve D is closed. Then, open valve B, inject gaseous acid chloride 5 from the reagent tank 3 into 6, bring it into contact with the alkali-treated fibers from the inside of drum 8, close valve B, and open valve C. After water vapor is injected into the reaction tank 6, the valve C is closed and the reaction is maintained for a certain period of time. This operation constitutes one cycle, and by repeating the above operation as necessary, the front and back surfaces of the fiber can be uniformly chemically modified. Therefore, in the method of the present invention, since the modifier permeates in a gaseous state and no tension is applied to the fiber structure, the shape of the cellulose fiber structure and the mixed structure of cellulose fiber and synthetic fiber is similar to that of woven or knitted fabrics. In either case, the front and back sides of the yarn can be improved to be uniform if necessary. In other words, by repeating the above cycle operation as necessary, it is possible to chemically modify cellulose fibers, which originally have no affinity for disperse dyes, to the extent that they can be dyed sufficiently, and on the other hand, it is possible to chemically modify cellulose fibers that have no affinity for disperse dyes, etc. Easy care properties can also be imparted. Furthermore, in the method of the present invention, the modifier is gasified in an independent reagent tank and then injected into the reaction tank 6, where it is first contacted with water and an alkaline agent. It is extremely stable and has excellent economic efficiency and productivity. The modifier has the following structure, specifically p-toluenesulfonyl chloride, O-
Toluenesulfonyl chloride, m-toluenesulfonyl chloride, benzenesulfonyl chloride,
These include o-nitrobenzenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, p-nitrobenzenesulfonyl chloride, toluene-3,4disulfonyl chloride, and the like.

[Formula] (X means H, -NO ₂ , -CH ₃ , or -SO ₂ Cl) In addition, examples of the alkaline agent used in the present invention include lithium, sodium, potassium, beryllium, magnesium, and calcium. , hydroxides of alkali metals or alkaline earth metals such as barium, strontium, etc. can be used. A more detailed explanation will be given below with reference to Examples. Example 1 (1) 65% polyester, 35% cotton with a basis weight of approximately 100g
A blended knitted fabric consisting of the above was immersed in an aqueous solution containing 10% each of sodium hydroxide and sodium hydrogen carbonate, and the mixture was squeezed to 80% using a mangle to obtain an alkali-treated fabric. The following experiments were carried out using the apparatus shown in FIG. (2) The alkali-treated cloth obtained in (1) was attached to the drum 8, the reaction tank 6 was tightly stoppered, the valve D was opened to reduce the pressure to about 50 mmHg, and then the valve D was closed. (3) Open valve A and inject high concentration gas of p-toluenesulfonyl chloride, which has been gasified from reagent tank 4 previously heated to 100°C, into reaction tank 6.
After about 5 seconds, valve A was closed. (4) Valve C was opened and saturated steam at 100°C was injected into reaction tank 6. When the pressure inside 6 reached 1.2 kg/cm ² , valve C was closed and the reaction vessel was left for 3 minutes. (5) After that, open valve D to exhaust the air, further reduce the pressure to about 50mmHg with a vacuum pump, and then
closed. (6) Next, open valve B and transfer the gasified P-toluenesulfonyl chloride from reagent tank 3 to reaction tank 6.
After about 5 seconds, valve B was closed. (7) Next, open valve C and fill reaction tank 6 with saturated steam at 100°C until the pressure inside the reaction tank is approximately 1.2
When the temperature reached Kg/cm ² , valve C was closed and left for about 5 minutes. (8) Thereafter, valve D was opened to exhaust air, and the pressure was further reduced to approximately 50 mmHg using a vacuum pump. (9) The series of operations (3) to (8) were further repeated five times to obtain a modified fabric. (10) The modified fabric obtained in (9) was thoroughly washed and dried. (11) Next, gravure printing was performed on 60 g/m ² single-sided starch-coated paper using ink having the composition shown below to obtain a transfer paper. <Ink> Sumikalon Red E-FBL (raw powder) (manufactured by Sumitomo Chemical Co., Ltd.) ...10 parts Ethyl cellulose N-7 (manufactured by Hercules) ...9 parts surfactant ...1 part isopropyl alcohol ...40 parts ethanol ... 40 copies (12) Overlap the modified cloth (10) with the transfer paper (11),
When transfer printing was carried out by heating and applying pressure at a temperature of 195° C., a pressure of 300 g/cm ² , and a time of 40 seconds, it was possible to obtain a printed fabric with the same density of red in the polyester and cotton portions. In addition, when measured by the washing fastness (A-2) method based on JIS, it was grade 5, and the printed fabric was fast. Example 2 (1) A 100% cotton broadcloth with a basis weight of approximately 100g was treated with 5% each of sodium hydroxide and sodium hydrogen carbonate.
% dissolved in aqueous solution and by mangling
It was reduced to 80% to obtain an alkali-treated cloth. The following experiments were carried out using the apparatus shown in FIG. (2) The alkali-treated cloth obtained in (1) was attached to the drum 8, the reaction tank 6 was tightly stoppered, and the valve D was opened to reduce the pressure to about 50 mmHg, and then the valve D was closed. (3) Operations (3) to (7) described in Example 1 were performed, and then valve D was opened to exhaust the air, and the sample was taken out, thoroughly washed, and dried. (4) The modified fabric obtained in (3) was immersed in a solution with the following composition, squeezed to 80% with a mangle, then pre-dried at 100℃ in a pin tenter oven, and then
It was cured at 150°C for 3 minutes, thoroughly washed and dried. <Liquid composition> Sumitex Range NS-16 (manufactured by Sumitomo Chemical Co., Ltd.)
...100g Sumitex Range Accelerator x-80 (manufactured by Sumitomo Chemical Co., Ltd.) ...30g Sumitex Softener L ...15g Water ...1 (5) Raw fabric and modified fabric obtained in (3) and The three modified + crosslinked fabrics obtained in (4) were tested for wrinkle resistance (JISL1096.6.22B method) and wrinkles after washing (JISL1096.6.23 tumble drying method). <Results>

[Table] As shown above, easy care properties can be obtained by modification alone, but even higher easy care properties were obtained by further performing general crosslinking treatment.

[Brief explanation of drawings]

The drawings show an embodiment of the present invention, and FIG. 1 is an explanatory diagram thereof. 1...Thermometer, 2...Oil bath, 3, 4...
Reagent (acid chloride) tank, 5... Reagent (acid chloride),
6... Reaction tank, 7... Rolled fiber (cloth or thread), 8... Drum with mesh holes, 9...
Safety valve, 10...Water vapor, 11...Thermometer, 12
...Pressure gauge, 13...Connected to vacuum pump, A,
B, C, D...Valves, and the pipes and reaction tanks between the reagent tanks 3 and 4 and the reaction tank 6 can all be heated and kept warm.

Claims (1)

[Scope of Claims] 1. In a method for chemically modifying cellulose fiber structures and mixed structures of cellulose fibers and synthetic fibers, after pre-treating such structures with an alkaline agent,
The system is kept in a sealable system, the pressure inside the system is appropriately reduced, and a compound having the structure shown below (hereinafter referred to as a modifier) is injected into the system in a gaseous state from one side of the fiber structure. After that, water vapor was similarly injected into the system and maintained for a certain period of time, after which the system was evacuated and the pressure was reduced, and a modifier was further injected in a gaseous state into the system from the other side of the fiber structure. A method for chemically modifying a cellulose fiber-containing structure, characterized in that one cycle is an operation of injecting water vapor into the system and holding it for a certain period of time, and this operation is repeated as necessary. [Formula] (X means H, NO ₂ , CH ₃ SO ₂ Cl)