JPS6044423B2 - Manufacturing method for textile products treated with antibacterial and antifungal treatment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for treating a knitted fabric or a woven fabric containing elastic polyester urethane yarn with antibacterial and antifungal treatment using a binding agent in combination.

Traditionally, knitted fabrics containing polyester urethane yarn elastic yarns have been prone to staining due to microorganisms, a unique unpleasant moldy odor, and eventually a decrease in the strength of the knitted fabric or fabric.
It is severely damaged and becomes unusable.

For this reason, anti-bacterial and anti-mildew treatments have been applied, but when worn and washed repeatedly, the anti-bacterial and anti-mildew agent falls off, resulting in a decline in its performance. The present inventors conducted research in consideration of the current situation as described above, and as a result, when performing antibacterial and antifungal processing,
By using a fixing agent in combination, it is difficult to elute even after repeated washing, and it is possible to impart antibacterial and antifungal effects to textile products over a long period of time. They found that good effects can also be obtained in terms of color and fastness, and thus completed the present invention. The polyester urethane elastic thread used in the present invention includes, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1|
3-propylene glycol, 2|3-butanediol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, 2,2-dimethyl-1,3
- Alkylene glycols such as propanediol or cycloaliphatic glycols such as 1,4-cyclohexanediol and acids such as succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid. A polymer having a molecular weight of 800 to 4,000 and having a substantially terminal hydroxyl group, or an aliphatic carbonate containing at least two hydroxyl groups, such as 1,4-butanediol, 1 ,6
- polymers with a molecular weight of 800 to 4000 obtained by transesterification of polyhydroxy compounds such as hexanediol, 2,2-dimethyl-1,3-propanediol, 1,8-octanediol with aryl carbonates such as diphenyl carbonate. Molecular weight 800-4 obtained by coalescence or ring-opening polymerization of ε-caprolactone
000 polymers and polyisocyanates such as m- and p-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate, p-xylylene diisocyanate, 4,4''-dimethyl-1, 3-xylylene diisocyanate, 1-alkylphenylene-2
, 4- and 2,6-diisocyanate, 3-(α-isocyanatoethyl) phenyl isocyanate, 2,6
-diethylphenylene-1,4-diisocyanate, diphenylmethane-4,4''-diisocyanate, diphenyl ether-4,4''-diisocyanate, naphthylene-1,5-diisocyanate, 1,6-hexane Methylene diisocyanate, cyclohexylene-4,4''-diisocyanate, and 4,4''-dicyclohexylmethane diisocyanate are reacted in an organic polar solvent with an excess of isocyanate, resulting in a polyfunctional active hydrogen atom. ,water,
Polyhydric alcohol, polyamine, hydrazine, polyhydrazide, polysemicarbazide, hydroxylamine and 1
A high viscosity spinning stock solution is obtained by reacting in stages or in multiple stages.
This can be obtained by conventional dry spinning or wet spinning.

The textile products containing polyester urethane elastic yarn used in the present invention include polyester urethane elastic yarn as a core yarn, and synthetic fibers such as acrylic, polyamide, and polyester fibers, regenerated cellulose, wool, cotton, etc. It is covered with natural fibers such as acrylic, polyamide, and polyester fibers, or is inter-knitted or inter-condensed with natural fibers such as regenerated cellulose, wool, and cotton. The antibacterial and fungicidal agents used in the present invention include 2-(4″-thiazolyl)benzimidazole, 2-methoxycarbonylaminobenzimidazole, 2-(thiocyanatomethylthio)benzothiazole, N-(fluorodichloro Methylthio)-phthalimide, diiodomethyl p-tolylsulfone, N-dimethyl-N''-phenyl-(N''-fluorodichloromethylthio)-sulfamide, N1-trichloromethylthio-4-cyclohexene-1,2-dicarboximide, 2- It is selected from methoxycarbonylamino-5-octylsulfonylbenzimidazole and the like.

The fixing agent used in the present invention is a combination of tannin and tartarite, a chelate of novolax sulfonic acid, or a chelate of formaldehyde condensation of sulfonated dihydroxydiphenyl sulfone (metal compounds include tin, antimony, zinc , barium, aluminum), a formaldehyde condensate of sulfonated dihydroxydiphenyl sulfone, and tartarite, which forms a complex.

The stages of implementing the fixation treatment are: 4 dyeing - fixation treatment - antibacterial and antifungal treatment - heat setting; ◎ dyeing - antibacterial and antifungal treatment - fixation treatment - heat setting; There is a method of simultaneous processing and heat setting, but either method can prevent the antibacterial and fungicidal agent from falling off and maintain the antibacterial and antifungal performance. The present invention will be explained in detail by the following examples.
The present invention is not limited to these examples.

Example 1 A two-way tricot knitted fabric knitted using 4cm polyester urethane yarn and 50d nylon yarn was dyed with acid dye.
H3-5, 6 powder dyeing with 2% 0wf1100'C, tannin 3%0wf1 acetic acid 1.8%0wf1 bath ratio 1:40 at 50℃, 3C@ treatment, drain, then tartarite 1.5 %0W
f1 acetic acid 0.9%0Wf1 bath ratio 1:40 at 50℃, 30
After the separation, it was washed with water.

After applying 1% 0 wf of 2-(4″-thiazolyl)-benzimidazole to this knitted fabric using the Bud method, it was squeezed uniformly with a mangle and heat-set using a regular heat setter (
Let this sample be A). On the other hand, a knitted fabric dyed and washed in the same manner was heated to a formaldehyde condensate of sulfonated dihydroxydiphenyl sulfone (FK8O8 manufactured by Fuji Chemical Co., Ltd.) in a bath ratio of 3% 0Wf1 at a temperature of 9.
After 6 dust treatments at 5°C, it was washed with water.

Next, 1% 0wf of 2-(4″-thiazolyl)-benzimidazole was applied by the Bud method (this sample is designated as B).The washing durability of Sample A and Sample B is shown below.2-( The remaining amount of 4''-thiazolyl)-benzimidazole was determined by a method.

Washing method Sample A and sample B were collected separately, and
lunder-Tester (YamaguchiSc
ienceInd. C.O. ) for 5 minutes at New Beads (manufactured by Kao Soap) at a temperature of 4 CfC and a bath ratio of 1:30, and then rinsed with water for 1 minute.

This 5-minute washing and the subsequent 1-powder washing are considered to be one wash. Analysis method The knitted fabric after washing was air-dried, extracted with acetone, and analyzed by gas chromatography for the amount of 2-(4''-thiazolyl)-benzimidazole attached.

Gas chromatography analysis conditions were Shimadzu 0-7AFI.
D1 column 5% SE-30/Simalite W1 glass column 177! ．． , He7Oml/min, Hl, O. 6k9/
d1 air 0.5kg/Crll injection temperature 3
Inject 1 μe at 00°C and column temperature of 260'C, prepare a calibration curve, and quantify. Table 1 shows the results of gas chromatography analysis regarding the washing durability of Sample A and Sample B.

Example 2 The two-way tricot knitted fabric used in Example 1 was dyed under the same conditions and then fixed under the following conditions (a), (b), (c), and (d).

(a) Tannin 3% 0Wf1 acetic acid 1.8% 0Wf1 bath ratio 1:40 at 50°C, 3 powder treatment, draining, then tartarite 1.5% 0Wf1 acetic acid 0.9% 0Wf1 bath Ratio 1:40
Treat with 3 powders at 50°C and wash with water.

(b) Chelate of formaldehyde condensate of sulfonated dihydroxydiphenyl sulfone (Nihon Senka Hi-Fix GM) 3% 0Wf1 at 95°C in bath ratio 1:40
6. Treat with dust and wash with water.

(C) Formaldehyde condensate of sulfonated dihydroxydiphenyl sulfone (Fuji Chemical Co., Ltd. FK8
O8) 3% 0Wf1 bath ratio 1:40 at 95°C for 60 minutes, drained, then tartarite 1.5% 0Wf1 acetic acid 0.
Treat with 9% 0Wf1 bath ratio 1:40 for 50'Cl3O minutes and wash with water. (d) Formaldehyde condensate of sulfonated dihydroxydiphenyl sulfone (Fuji Chemical Co., Ltd. FK8O8) 3% 0Wf1 at 95°C in a bath ratio of 1:40
, 6. Treat with dust and wash with water.

Next, antibacterial and fungicidal agents 1 to 8 were applied using the Bud method.

12-(4″-thiazolyl)benzimidazole, 22
-methoxycarbonylaminobenzimidazole, 3
2-(thiocyanatomethylthio)benzothiazole,
4N-(fluorodichloromethylthio)-phthalimide, 5diiodomethyl p-tolylsulfone, 6N-dimethyl-N''-phenyl-(N''-fluorodichloromethylthio)-sulfamide, 7N-trichloromethylthio 4-cyclohexene-1,2-di Carboximide,
82-Methoxycarbonylamino-5-octylsulfonylbenzimidazole.

The washing method and the analysis of the antibacterial and antifungal agent were conducted according to the method described in Example 1. The residual rate of the antibacterial and antifungal agent after washing 5 (2) is shown in Table 2 below. Example 3 The washing durability of the antibacterial and antifungal agent for the two-way tricot knitted fabric in Example 1 was as described in Example 1, but the residual amount of the antibacterial and antifungal agent was In order to see the effect on mold performance, the following tests were conducted.

A test was conducted in accordance with JIS-Z-2911 to examine antibacterial and antifungal properties.

The test method was to dissolve agar medium in 50 y/e of water, adjust the pH to 5.5, sterilize it, and then dissolve it in 90 y/e of water.
Pour into a φ sterilized jar and allow to solidify. On top of this medium, each test knitted fabric was pasted on a stainless steel frame to prevent the sample from directly touching the medium. Aspergillus niger suspended in physiological saline (
Spray ATCC6275) using a sprayer, place in a constant temperature and humidity machine, and culture at a temperature of 30° C. and a humidity of 90%. Observe the number of days that defects appear on the knitted fabric. The results are shown in Table 3, and the antibacterial and antifungal performance of the fixing treatment using tannin-tartarite was good.

In addition, the fading fastness, which is the original purpose of the fixing treatment, was measured by the following method.

Light fastness: Tested according to JIS-0842, sample A and sample B were each 6.5C77! ×11c! The specimen was irradiated with carbon arc light (fade meter) for 2 hours, and the discoloration of the test piece was evaluated on a gray scale of grades 1 to 5 (grade 5 good → grade 1 bad).

Wet friction fastness was determined according to JIS-0849, and each knitted fabric was approximately 22c! n×3c! n, using a friction tester to test the white cotton cloth for friction in a 100% wet state between test pieces WO at 30 rpm per minute.
Go back and forth 10 times and judge the degree of coloring on a scale of 1 to 5 (5
Grade good → Grade 1 bad).

The fastness to fading is as shown in Table 4, and the fastness of the fixed knitted fabric was good.

Example 4 After dyeing the two-way tricot given in Example 1 and washing with water, 1.0% 0 wf of 2-(4″-thiazolyl)benzimidazole was applied using a bud method, and after drying with a heat setter, tannin was applied. 3%0Wf1 Acetic acid 1.8%0Wf
After 5 (sub) and 3 treatments at a bath ratio of 1:40, the liquid was drained, and then treated with 50'Cl3 powder at a bath ratio of 1:40. After washing with water, it was set in a heat setter (this is referred to as sample C).

Next, after dyeing the two-way tricot knitted fabric, tannin 3%0wf12-(4″-thiazolyl)benzimidazole 1.0%0Wf1acetic acid 1.8%0Wf1Bath ratio 1:
5 (generations) at 40, after processing 3 powders, drain the liquid, then add 0 tartarite
．． 9%0Wf1 acetic acid 0.9%0wf, bath ratio 1:40 5
A three-powder fixation process was performed at 0°C, and then set in a heat setter (this is referred to as sample D).

In order to examine the washing durability of these fabrics, the residual rate of 2-(4-thiazolyl)benzimidazole was analyzed using the analytical method used in Example 1. The results are shown in Table 5, and the effect was observed no matter how the fixing agent tannin-tartar and the antibacterial and antifungal agent were used in combination.

Claims (1)

[Claims] 1 When performing antibacterial and antifungal treatment on knitted fabrics or textiles containing polyester urethane elastic yarns, 2-(4'-thiazolyl)benzimidazole, 2-methoxycarbonylamino-benzimidazole, 2-(thiocyanatomethylthio)benzothiazole , N-(fluorodichloromethylthio)-phthalimide, jodomethyl p-tolylsulfone, N-dimethyl-N'-phenyl-(N'-fluorodichloromethylthio)-sulfamide, N-trichloromethylthio-4-cyclohexene-1,2 -dicarboximide, 2-methoxycarbonylamino-5-
An antibacterial and fungicidal agent selected from octylsulfonylbenzimidazole, a combination of tannin and tartarite, a combination of sulfonated dihydroxydiphenylsulfone formalin resin and tartarite, and a chelate of sulfonated dihydroxydiphenylsulfone formalin resin ( Antibacterial treatment characterized by using a combination of fixing agents selected from metals (tin, antimony, zinc, barium, aluminum) and novolax sulfonic acid chelates (metals: tin, antimony, zinc, barium, aluminum) A method for producing anti-mildew textile products.