JPH0577791B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD OF THE INVENTION The present invention relates to a durable creasing agent for woolen textile products. In detail, durable folding of wool fiber products is used for durable fold processing that does not cause discoloration, bad odor, or embrittlement of wool fibers during fold processing of wool fiber products and when worn after processing. Regarding eye finishing agents. Furthermore, durable creases refer to creases that do not disappear even after being immersed in hot water at 70°C for 30 minutes. (Prior Art) Conventionally, in a method for setting wool fiber products that allows the folds or flat shape imparted to the wool fiber products to be permanently set, a function of cleaving disulfide bonds within the wool fibers has been proposed. A setting agent containing a reducing sulfur-containing organic compound is described in Japanese Patent Publication No. 37-3099. This setting agent is a setting agent containing a thiol compound such as ammonium thioglycolate, and the wool fiber product is heated in the presence of this setting agent to cleave the disulfide bonds in the wool fiber, and at the same time fix it in a predetermined shape. The disulfide bonds were recombined and wool fiber products were set. Furthermore, there are products using monoethanolamine bisulfite or monoethanolamine sulfite instead of ammonium thioglycolate. Both of these methods are used in current crease processing. (Problem to be solved by the invention) In the invention described in Japanese Patent Publication No. 37-3099,
Setting agents applied to woolen fiber products contain thiol compounds such as ammonium thioglycolate. In the invention described in Japanese Patent Publication No. 37-3099, in addition to ammonium thioglycolate, mercapto ethanol, thioglycerol, thioacetic acid, thiosalcylic acid, mercapto butyric acid, ethyl mercaptan, thionaphthol, etc. are used as thiol compounds. listed. Although ammonium thioglycolate does act effectively on wool fibers as a setting agent, it has a large effect on dyes and may change the hue of textile products. In addition, it has the property of causing a coloring reaction with metal ions such as iron, and has the disadvantage that it changes color due to the influence of trace amounts of metal in stains on containers and textile products, causing discoloration of textile products. Furthermore, since ammonium thioglycolate is easily oxidized by contact with air, it has the drawback of extremely poor solution stability and poor workability. Additionally, when reducing wool fibers using current durable creasing agents containing monoethanolamine bisulfite or monoethanolamine sulfite, sulfur dioxide gas, hydrogen sulfide, ammonia, etc. are released in small amounts over a long period of time. It has the disadvantage that it spreads over the air and gives off a bad odor. This bad odor disappears temporarily by drying, but the odor comes back when sprayed with water. or,
Since monoethanolamine bisulfite and monoethanolamine sulfite have strong reducing properties, they cause discoloration and embrittlement of wool fibers when disulfide bonds are broken. Furthermore, both monoethanolamine bisulfite and monoethanolamine sulfite generate aminoacrylic acid residues during the reaction, and when this increases, problems such as yellowing of textile products occur. In view of the above issues, the inventors conducted extensive research and found that the amino acid cysteine has excellent reducing properties for wool fibers, and also contains substances that cause discoloration and bad odor.
The present invention was completed based on the knowledge that it is a substance that does not generate any oxidation, and does not cause embrittlement of wool fibers during reduction. An object of the present invention is to provide a durable creasing agent for wool fiber products that does not cause discoloration, bad odor, or embrittlement of wool fibers. (Means and effects for solving the problem) In order to achieve the above object, in the invention according to claim 1, the main component is cysteine or a cysteine derivative that cleaves disulfide bonds in wool fibers in a state where they can be recombined. The gist of this paper is a durable creasing agent for wool fiber products. In the present invention, wool fiber products are not limited to those made only of wool fibers, but also those made by blending, inter-knitting, and twisting wool fibers with other fibers such as mohair fibers, polyester fibers, cellulose fibers, acrylic fibers, etc. It may consist of. Durable creasing agents are based on cysteine or cysteine derivatives that have the function of cleaving disulfide bonds in wool fibers in a recombinable manner. This cysteine includes D-cysteine, L-cysteine,
-Cysteine, a mixture thereof, or a racemate thereof. In addition, as cysteine derivatives, N-acyl cysteine such as N-acetyl-L-cysteine, N-caproyl-L-cysteine, N-propionyl-L-cysteine, N-palmitoyl-L-cysteine, or salts thereof ( (sodium salt, potassium salt, ammonium salt, hydrochloride, etc.), organic acid salts (acetate, etc.), and esters (methyl, ethyl, propyl, etc.). A preferred example of the use of the durable creasing agent is one in which the pure content of cysteine or cysteine derivatives listed above on the wool fiber product is 0.1 to 0.8% owf. This is because if the purity of cysteine or cysteine derivative is less than 0.1% owf, sufficient durable folding performance cannot be obtained. Furthermore, if the pure content exceeds 0.8% owf, the amount of unreacted cysteine remaining will increase after the durable crease processing. The above-mentioned durable creasing agent is applied to wool fiber products by conventionally known methods such as coating or spraying, but cysteine or cysteine derivatives applied to wool fiber products are Then, a reaction occurs as shown in the following equation. W-SS-W+T-SH −−−−−→W−SS−T+W−SH W−SS−T+T−SH −−−−−→W−SH+T−SS−T W−SS−W: wool cystine residue , -SS-: disulfide bond, T-SH: cysteine,

[Chemical formula] W-SH: wool cysteine residue, T-SS-T: cystine. As shown in the above formula, cysteine in the durable creasing agent imparted to the wool fiber product reacts with the disulfide bond (-SS-) in the wool fiber,
The disulfide bond (-SS-) is cleaved to generate a cysteine residue, and its thiol group effectively causes the setting to proceed. Additionally, cysteine in the durable creasing agent is a mild reducing compound, so it does not cause odor, discoloration, or embrittlement of wool fibers. Next, an experiment conducted by the present inventors on the exhaustion of cysteine contained in this durable creasing agent into wool fibers will be explained in detail. Experimental Method Exhaustion experiments were conducted under the following six conditions (a) to (f). The immersion bath ratio was 1:4 (for example, 100 ml of immersion liquid and 25 g of wool fiber products), and a certain amount of the remaining bath was taken at each time, and Ellman's reagent (5,5'-dithiobis(2-nitrobenzoic acid)...DTNB ) After color development, absorbance is measured at a maximum absorption wavelength of 412 nm to quantify the amount of remaining cysteine. (a) Immersion liquid: Cysteine 1wt%, Immersion sample: Wool fiber, Immersion temperature: 20℃. Indicated by ● in Figure 1. (b) Immersion liquid: Cysteine 1wt%, Immersion sample: Silk thread Immersion temperature: 20℃. Indicated by a circle in Figure 1. (c) Immersion liquid: Cysteine 1wt%, Immersion sample: Reduced wool fiber, Immersion temperature: 20℃. Indicated by ▲ in Figure 1. (d) Immersion liquid: Monoethanolamine sulfite 5wt
%, soaked sample: wool fiber, soaking temperature: 20℃. It is indicated by an x in Figure 1. (e) Immersion liquid: Cysteine 1wt% + ethylene glycol 1wt%, Immersion sample: Wool fiber, Immersion temperature:
20℃. Indicated by □ mark in Figure 1. (f) Immersion liquid: Cysteine 1wt%, Immersion sample: Wool fiber, Immersion temperature: 50℃. Indicated by △ in Figure 1. The results of this experiment are shown in FIG. As is clear from Figure 1, silk thread is an animal protein fiber, but because it does not have disulfide bonds,
No exhaustion of cysteine was observed. Furthermore, in the reduced wool fiber, most of the disulfide bonds were converted to thiol groups, so almost no exhaustion of cysteine was observed. It was also found that cysteine has a much better exhaustion property for wool fibers than monoethanolamine sulfite. It was also found that by raising the temperature of the cysteine solution, the initial exhaustion rate increased and the exhaustability also improved. From the above results, cysteine has excellent exhaustion properties into wool fibers, and therefore sufficient durable folding performance can be obtained with a low concentration.
In addition, by increasing the temperature of the cysteine solution,
It was confirmed that the initial exhaustion rate of cysteine can be accelerated. When the durable creasing agent is absorbed into the wool fibers, the reaction shown in the above equation occurs, but if a surfactant, wetting agent, swelling agent, etc. By adding the agent, the exhaustability to wool fibers can be further improved, and sufficient durable folding performance can be obtained at a low concentration. Next, durable creasing agents according to claims 2 to 4 to which the above additives are added will be explained. The invention according to claim 2 provides durability of wool fiber products characterized by containing an anionic or nonionic surfactant together with cysteine or a cysteine derivative that cleaves disulfide bonds in wool fibers in a state in which they can be recombined. Its gist is a targeted crease finishing agent. Since cysteine or a cysteine derivative is the same as the invention described in claim 1, the explanation will be omitted, and the surfactant added to the durable creasing agent will be explained. Surfactants improve the penetration of the durable creasing agent into wool fibers. This also reduces the amount of cysteine or cysteine derivatives remaining on the surface of the wool fiber product. Examples of nonionic surfactants include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, etc. Examples of anionic surfactants include neocol type, such as dialkyl sulfosuccinate ester sodium salt, etc. preferable. The invention as claimed in claim 3 improves the durability of a wool fiber product, which contains a wetting agent such as an alcohol or a glycol in addition to cysteine or a cysteine derivative that cleaves disulfide bonds in wool fibers in a state where they can be recombined. Its gist is a targeted crease finishing agent. Since cysteine or a cysteine derivative is the same as the invention described in claim 1, the explanation will be omitted, and the wetting agent added to the durable creasing agent will be explained. The wetting agent has the function of retaining moisture on the wool fiber surface and improving the absorption of the durable creasing agent into the wool fiber.By adding this wetting agent, the wool fiber The durable folding performance of the product can be further improved. Preferred examples of the wetting agent include alcohols such as ethanol, propanol and butanol, and glycols such as ethylene glycol, propylene glycol, ethyl ethylene glycol, 2-propanediol and 3-butanediol. The invention according to claim 4 provides a durable wool fiber product characterized by containing a swelling agent such as water-soluble amines together with cysteine or a cysteine derivative that cleaves disulfide bonds in wool fibers in a state where they can be recombined. Its gist is a crease finishing agent. Since cysteine or a cysteine derivative is the same as the invention described in claim 1, the explanation will be omitted, and the swelling agent added to the durable creasing agent will be explained. Swelling agents have the effect of opening up the molecules of wool fibers, improve the absorption of the durable creasing agent into the wool fibers, and improve the durable creasing performance of wool fiber products. can be increased. As the swelling agent, water-soluble amines such as mono-ethanolamine, di-ethanolamine, and tri-ethanolamine are preferred. The three types of additives of claims 2 to 4 mentioned above are not limited to those added singly to the durable crease finishing agent containing cysteine or cysteine derivatives, but may be added in combination of multiple types. That's fine. The method of using the above-described durable creasing agent for wool fiber products will now be described. First, the above-mentioned durable creasing agent is applied to the wool fiber product, and then the wool fiber product is steamed using a press, an autoclave, or other steaming device while being held at a predetermined crease. As the steaming conditions, a temperature of 90 to 120°C for 1 to 10 minutes is preferable. Thereafter, the wool fiber product is air-dried or forced-dried to complete the durable crease treatment of the wool fiber product. Incidentally, in order to improve the abrasion strength of the wool fiber product during the above-mentioned durable crease processing, a resin may be used in combination. As the resin, cationic polyamide epichlorohydrin, polyurethane resin, fluorine water- and oil-repellent resin, etc. are preferable. In addition, if thiol groups remain in the wool fibers after the above-mentioned durable folding treatment of the wool fiber product, a problem arises in that the folds of the wool fiber product return to their original state. In order to prevent this problem, after steaming, the wool fiber product may be subjected to oxidation treatment by applying an oxidizing agent such as hydrogen peroxide or potassium bromate. When this oxidizing agent is applied to wool fiber products by spraying or coating, the thiol groups remaining within the wool fibers or on the surface of the wool fiber products are converted to disulfide bonds. As a result, the disulfide bonds in the wool fibers are not cleaved again. (Examples) Hereinafter, the durable creasing agent for wool fiber products according to claims 1 to 4 of the present invention will be described in more detail according to examples. Example 1 1.5wt% L-cysteine as a surfactant
A durable creasing agent was prepared by adding 1.2 wt% polyoxide ethylene nonylphenyl ether (EO=8 moles). Apply this durable creasing agent to both sides of the fabric (top dyed pure wool serge, anti-dyed pure wool serge) using a hand spray gun using compressed air at 2.0 kg/cm ² in an amount of 40% owf of the fabric weight. Spray and steam for 30 seconds using a steam press, then bake for 30 seconds and bake for 10 seconds. The steam pressure at this time is 4.5Kg/cm ² and steam is injected from the top and bottom of the iron simultaneously. Then let it dry naturally. A fold durability test is performed on the durable folded fabric as described above. Fold durability test: A total of four pieces of fabric are cut out from two places above and below two folds made on the fabric, that is, 1 cm in the length direction of the fold and 2 cm in width from the fold. Five folded pine needle-like threads are then loosened from each piece of fabric. These are 0.1wt
% of penetrant in water at 25°C for 2 minutes, the fold angle (opening angle) of the thread in the water was measured from above using a protractor. Then, the average opening angle of a total of 20 threads was determined. Note that the smaller the opening angle, the better the durability of the fold, and it must be within 90°. As a result, the top dyed pure hair surge was 64°, and the anti-dyed pure hair surge was 66°. Example 2 1.5 wt% L-cysteine and 0.1 wt% polyoxide ethylene nonyl phenyl ether (EO=
8 mol) as a wetting agent, 0.5 wt% or
8 kinds of durable crease processing by adding 0.1wt% glycerin, 0.5wt% or 1.0wt% ethylene glycol, 0.5wt% or 1.0wt% diethylene glycol, 0.5wt% or 1.0wt% propylene glycol, respectively. A drug was prepared. Using these durable folding agents, the fabric was subjected to durable folding under the same processing conditions as in Example 1, and the durability test of the folds of the fabric was conducted, as shown in Table 1. I got good results. Table 1 Opening angle Durable creasing agent Anti-dye Top dyeing 0.5wt% 80° 75° Glycerin 1.0wt% 79° 66° Glycerin 0.5wt% 78° 67° Ethylene glycol 1.0wt% 71° 64° Ethylene glycol 0.5wt% 79゜ 78゜Diethylene glycol 1.0wt% 76゜ 76゜Diethylene glycol 0.5wt% 75゜ 72゜Propylene glycol 1.0wt% 73゜ 68゜Propylene glycol Example 3 2.0wt% L-cysteine hydrochloride, 0.1wt% of polyoxide ethylene nonyl phenyl ether (EO = 8 mol) as a swelling agent, 0.6 wt%
Two types of durable creasing agents were prepared by adding 1.2 wt% of monoethanolamine to each. Using these durable folding agents, the fabric was subjected to durable folding under the same processing conditions as in Example 1, and the durability test of the folds of the fabric was conducted, as shown in Table 2. I got good results. Table 2 Opening angle Durable creasing agent Anti-dye Top dyeing 0.6wt% 84° 83° Monoethanolamine 1.2wt% 77° 74° Monoethanolamine Example 4 1.5wt% of L-cysteine was added with surfactant A durable creasing agent was prepared by adding 0.1 wt% polyoxide ethylene nonyl phenyl ether (EO=8 mol) as an agent. Using this durable creasing agent, a woven fabric was subjected to durable creasing under the same processing conditions as in Example 1, and a durability test of the folds of the woven fabric was conducted. As a result, the opening angle of top dyed pure hair serge is
The opening angle of the anti-dyed pure hair serge was 78° and 82°. Comparative example 5wt% monoethanolamine sulfite and
Using a folding agent containing 1.5wt% polyoxide ethylene nonyl phenyl ether (EO = 8 mol), the fabric was subjected to durable folding under the same processing conditions as in Example 1, and the folds of the fabric were A durability test was conducted. As a result, the opening angle of top dyed pure hair serge is
The opening angle of the anti-dyed pure hair serge was 69° and 74°. From the above Examples 1 to 4 and comparative examples, the durable crease finishing agent according to the present invention has the same or more creases as compared to the conventionally used crease finishing agent. It has become clear that it has durability. (Effects of the Invention) By adopting the above configuration, in the durable creasing agent for wool fiber products of the invention as claimed in claim 1, when this is applied to wool fiber products, cysteine is mild. Since it is a reducing compound, it does not cause bad odor, discoloration, or brittleness and yellowing of wool fibers. Furthermore, the cysteine contained in this durable creasing agent has a very excellent ability to be absorbed into wool fibers, and sufficient durable creasing performance can be obtained with a low concentration. Furthermore, by increasing the temperature of the solution, the initial exhaustion rate of cysteine can be accelerated.
The processing efficiency of durable crease processing can be improved. In the invention as set forth in claim 2, since the durable creasing agent contains a surfactant, its permeability into wool fibers is improved and higher durable creasing performance can be obtained. In the invention according to claim 3, since the durable creasing agent contains a wetting agent, moisture is retained on the surface of the wool fiber, and the absorption property of the wool fiber is improved. Highly durable crease performance is obtained. According to the invention described in claim 4, since the durable creasing agent contains a swelling agent, the gaps between the molecules of the wool fiber are opened, and the exhaustability of the wool fiber is improved, and the swelling agent is improved. Highly durable crease performance is obtained.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the exhaustion of cysteine contained in a durable creasing agent into wool fibers.

Claims (1)

[Scope of Claims] 1. A durable creasing agent for wool fiber products, characterized in that the main component is cysteine or a cysteine derivative that cleaves disulfide bonds in wool fibers in a state that allows them to be recombined. 2. Durable folding of the wool fiber product according to claim 1, characterized in that it contains an anionic or nonionic surfactant together with cysteine or a cysteine derivative that cleaves disulfide bonds in wool fibers in a state where they can be recombined. Eye finishing agent. 3. Durability of the wool fiber product according to claim 1 or 2, which contains a wetting agent such as alcohols or glycols together with cysteine or a cysteine derivative that cleaves disulfide bonds in wool fibers in a state where they can be recombined. Target crease processing agent. 4. The wool fiber product according to claim 1, 2 or 3, which contains a swelling agent such as water-soluble amines together with cysteine or a cysteine derivative that cleaves disulfide bonds in wool fibers in a state where they can be recombined. Durable creasing agent.