JPH0313355B2 - - Google Patents

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to a fiber structure that is durable against washing and has both deodorizing and antibacterial effects. (Prior Art) Many conventional deodorizing and antibacterial treatments of fibers have been proposed and put to practical use. There are antibacterial treatments such as JP-A-59-223371, but they do not have a deodorizing effect. In other words, many antibacterial textile products that prevent the growth of fungi that produce bad odors have been proposed, and although their deodorizing effect is recognized in the sense of antibacterial effects, it is difficult to prevent odor from textile products that have not been treated with antibacterial treatment or from the external environment. Antibacterial-treated textile products cannot be expected to be effective in preventing even the transference of bad odors. In addition, although deodorizing processed fiber products have the effect of preventing bad odors from the external environment, they do not have the effect of preventing the growth of microorganisms that produce bad odors and thus have a limited deodorizing effect. A textile product that is resistant to washing and has both the functions of preventing the growth of microorganisms that produce bad odors, cutting off the source of bad odors, and deodorizing by absorbing the transfer of bad odors from the surrounding external environment has not yet been completed. The current situation is that there is no such thing. (Means for Solving the Problems) The present invention provides a mixed deodorizing substance with a weight ratio of ferrous salt and L-ascorbic acid of 50:50 to 90:10, and a solid content of 0.1 to 10% by weight and an antibacterial substance. as solid content
The present invention provides a deodorizing antibacterial fiber structure consisting of a fiber structure in which 0.05 to 4% by weight (all weight percentages are based on the weight of the fiber structure) is fixed together with a synthetic resin. As a solution, it is possible to obtain deodorizing and antibacterial effects that are durable against washing. The ferrous salt used in the present invention includes:
For example, ferrous sulfate, ferrous chloride, ferrous oxalate
Examples include iron, ferrous acetate, ferrous tartrate, and ferrous lactate, but preferred ferrous salts are ferrous sulfate and the ferrous organic acids listed above. Ferrous iron and L-ascorbic acid are used as deodorizing substances in the form of a mixture in a weight ratio of 50:50 to 90:10. As the antibacterial substance used in the present invention, any known antibacterial substance can be used. A preferred example is an organosilicon quaternary ammonium salt.
For example, 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride, which is commercially available as Polon MF50 (trademark: Shin-Etsu Chemical Co., Ltd.), can be used. Alternatively, diphenyl ether compounds can also be used. For example, the commercially available Nitzkan AB
(Nicca Chemical Co., Ltd., solid content 20%) can be applied to fibers at 0.2% to particularly suppress Staphylococcus aureus. 0.1 to 10% by weight of the deodorant substance as a solid content, preferably 0.5 to 6% by weight based on the weight of the fiber structure itself, and 0.05 to 4% by weight of the antibacterial substance as a solid content,
Preferably 0.2 to 2.0% by weight is applied to the fiber structure as a mixed treatment solution with a synthetic resin and fixed.
That is, a treatment liquid, preferably an aqueous treatment liquid, containing a deodorizing substance and an antibacterial substance at a concentration set to provide the above amounts of a deodorizing substance and an antibacterial substance, and also containing a synthetic resin (or its precursor and catalyst) is used. It is applied to the fiber structure by an appropriate method such as dipping, dipping, spraying, etc. The fibrous structure is then dried and optionally heat treated. The synthetic resin applied and fixed to the fiber structure together with the deodorizing substance and the antibacterial substance is preferably an aminoplast resin, a urethane resin, or an acrylic resin. For example, aminoplast resins include trimethylolmelamine, hexamethylolmelamine,
Dimethylol dihydroxyethylene urea, dimethylol ethylene urea, dimethylol dimethoxyethylene urea, dimethylol butylene urea, tetramethylol acetylene diurea, dimethylol propylene urea, dimethylol 5 hydroxypropylene urea, dimethylol triazone, dimethylol uron, Examples include tetramethylolethylenebistriazon. For example, 0.2 to 5.0% by weight of the solid content based on the amount of the fiber structure is applied to the fiber structure together with the catalyst by the padding method, dried at 100 to 130℃, and then fixed by heat treatment at 150℃ for 3 minutes. . As the urethane resin, a polyurethane emulsion is preferably used, and the polyurethane emulsion is, for example, produced in a solvent system as is known in the art, emulsionized with a suitable emulsifier, and the solvent is appropriately recovered. . Examples of specific products include Bondy Tsuk 1610, Bondy Tsuk 1670, and Bondy Tsuk, manufactured by Dainippon Ink Co., Ltd.
1640 (all trademarks), Izerax S4040N (trademark) manufactured by Hodogaya Chemical Co., Ltd., Evaphanol NS-2, Evaphanol S manufactured by NICCA Chemical Co., Ltd.
-5, Evaphanol KH (all trademarks), and the like. For example, by padding 0.2 to 15.0% by weight of the solid content based on the weight of the fiber structure, or by adding kerosene to increase the viscosity from 2000 to 10000.
It is adjusted to centipoise and applied to the fiber structure by the coating method, and after drying at 100° to 130°C,
Heat treated at ℃ for 3 minutes. Acrylic resins include methyl acrylate,
Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-
Ethylhexyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, methoxypolyethylene glycol acrylate, 2-hydroxyethyl acrylate, 2-
Hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 1,4-
Examples include emulsions of butylene glycol monoacrylate alone or copolymers, or mixed emulsions of these homopolymers. By padding method,
Or add kerosene to adjust the viscosity to 2000 to 10000 centipoise and apply it to the fiber structure by a coating method, dry at 100° to 130°C, then 150°C,
It is fixed by heat treatment for 3 minutes. In addition, epoxy-modified silicone oil emulsion, such as Deutsuku Silicone Softner A-900 (trademark) manufactured by Dainippon Ink Co., Ltd., or amino-modified silicone oil emulsion, such as Dainippon Ink Co., Ltd., may be used to adjust the texture of the fiber structure. Deitsuku Silicone Softner 200 (trademark) manufactured by Nippon Ink Co., Ltd. can be applied in an amount of 0.2 to 0.8% by weight as a solid content based on the weight of the fiber structure. If necessary, a strong alkaline salt of a weak acid such as sodium formate, sodium ascorbate, or sodium acetate may be added as a buffer to adjust the pH of the treatment solution to 6.5 to 7.5. (Example) The present invention will be explained in detail in the following examples. Regarding (1) deodorizing effect in the examples, one sample (deodorizing cloth 20 cm x 25 cm) was placed in a 350 ml airtight container, and 0.3% trimethylamine Add 1 ml or 0.5 ml of 1.4% ammonia, seal, leave for 1 hour, then turn off headspace gas 1.
ml, conduct gas chromatography analysis, and conduct a blank test (1 ml of 03% trimethylamine without adding deodorizing cloth).
or 0.5 ml of 1.4% ammonia) to determine the removal rate. (2) The antibacterial effect was expressed as the bacterial reduction rate measured by the shake flask method. (3) Laundry items
After washing 10 times using the JISL0217-103 method, each of the above tests was conducted. Example 1 5.0 g of ferrous sulfate was added as a deodorizing substance to a satin fabric of 100% cotton, 40th grit, 130 g/ ^m2 , which was desizing, scouring, bleaching, mercerizing, and printing using conventional methods.
and Polon manufactured by Shin-Etsu Chemical Co., Ltd., containing 3.1 g of L-ascorbic acid/40% solid content of 3-(trimethoxydilyl)propyldimethyloctadecyl ammonium chloride as an antibacterial substance.
MF50 (trademark) 16.7g/, urethane emulsion resin made by Dainippon Ink Co., Ltd. Bonditsu 1610 (trademark, solid content 40% content) 20g/, Dainippon Ink Co., Ltd. amino-modified silicone oil emulsion, Daitsuku Silicone Softener 200 (trademark, containing 40% solids) 10g/mixture with 10g/epoxy-modified silicone oil emulsion Date Silicone Softener A-900 (trademark, containing 40% solids) manufactured by Dainippon Ink Co., Ltd. After padding the aqueous solution at a squeezing rate of 60%, drying at 100℃,
After heat treatment at 150°C for 3 minutes, 0.3% by weight of ferrous sulfate and L-ascorbic acid were added to the weight of the fiber structure.
A deodorizing and antibacterial cotton satin fabric was obtained to which 0.186% by weight (total 0.44% by weight), 0.4% by weight of antibacterial substance, 0.48% by weight of urethane resin, 0.24% by weight of amino-modified silicone oil, and 0.24% by weight of epoxy-modified oil were added. The odor removal rate and antibacterial effect of trimethylamine and ammonia after processing of the obtained fabric after 1 hour and the odor removal rate and antibacterial effect after 10 washings were evaluated first.
Shown in the table. Example 2 7.0 g of ferrous lactate was added as a deodorizing substance to a gear bagine made of 65% polyester, 35% cotton, and 40 grit fabric weight 250 g/m ² that had been desized, scoured, bleached, mercerized, and dyed using conventionally known methods. L-ascorbic acid 4.0
Contained 25 g of Poron MF50 (containing 40% solid content) manufactured by Shin-Etsu Chemical Co., Ltd. as an antibacterial substance and 20 g of Boncoat R-3020 (40% solid content) manufactured by Dainippon Ink Co., Ltd. as an acrylic ester. After making a coating liquid whose viscosity was increased to 3000 centipoise with kerosene, it was coated with a knife coater so that the coating amount was 40% by weight based on the weight of the gearbagin fabric, dried at 100℃, and coated at 150℃. After heat treatment for 3 minutes, 0.28% of ferrous lactate was added as a deodorizing substance to the weight of gearbagin fabric.
wt% and L-ascorbic acid 0.16 wt% (total
A deodorizing and antibacterial gear bagin fabric was obtained, to which 0.44% by weight), 0.4% by weight of antibacterial substances, and 0.32% by weight of acrylic ester were added. Table 1 shows the odor removal rate and antibacterial effect of trimethylamine and ammonia after processing the obtained fabric after 1 hour. Example 3 8 g of ferrous acetate and 2 g of L-ascorbic acid were added as deodorizing substances to a 100% rayon, 30-count plain fabric with a basis weight of 195 g/m ² that had been desized, scoured, bleached, and dyed using a commonly known method. , a mixed solution containing 25 g of Polon MF50 manufactured by Shin-Etsu Chemical Co., Ltd. as an antibacterial substance, 20 g of Betsukamine LKS (containing 40% solid content) manufactured by Dainippon Ink Co., Ltd. and 10 g of Catalyst G manufactured by Dainippon Ink Co., Ltd. as glyoxal resin was squeezed to a squeezing rate of 60.
% padding, drying at 100°C, heat treatment at 150°C for 3 minutes, and adding 0.48% by weight of ferrous acetate and L- as deodorizing substances to the weight of the rayon plain woven fabric.
Ascorbic acid 0.12% by weight (total 0.60% by weight),
0.6% by weight of antibacterial substances, glyoxal resin
A deodorant and antibacterial rayon plain fabric containing 0.48% by weight was obtained. The odor removal rate and antibacterial effect of trimethylamine and ammonia after processing of the obtained fabric after 1 hour and the odor removal rate and antibacterial effect after 10 washings were evaluated first.
Shown in the table. Comparative Example 1 The same printed cotton used in Example 1
100% 40-count satin fabric with a basis weight of 130 g/m ² and 5.0 g of ferrous sulfate and 3.1 g of L-ascorbic acid as deodorizing substances and Poron MF50 (contains 40% solids) manufactured by Shin-Etsu Chemical as an antibacterial substance. After padding 16.7g/mixed aqueous solution at a squeezing rate of 60%, drying at 100℃ and heat treatment at 150℃ for 3 minutes, 0.3% by weight of ferrous sulfate was added as a deodorizing substance to the weight of the cotton sateen fabric. L-ascorbic acid 0.186% by weight (total
A deodorizing and antibacterial satin fabric was obtained to which 0.486% by weight) and 0.4% by weight of antibacterial substances were added. The odor removal rate and antibacterial effect of trimethylamine and ammonia after processing of the obtained fabric after 1 hour and the odor removal rate and antibacterial effect after 10 washes were the first.
Shown in the table. Comparative Example 2 The same printed cotton used in Example 1
After padding a mixed aqueous solution of 5.0 g of ferrous sulfate and 3.1 g of L-ascorbic acid as a deodorizing and antibacterial substance on a 100% 40-count satin fabric with a basis weight of 130 g/m ² at a squeezing rate of 60%, it was heated to 100°C. 0.3% by weight of ferrous sulfate and 0.186% by weight of L-ascorbic acid based on the weight of the cotton satin fabric.
A deodorizing and antibacterial satin fabric conforming to the Daicel Chemical Pamphlet was obtained. The odor removal rate and antibacterial effect of trimethylamine and ammonia after processing of the obtained fabric after 1 hour and the odor removal rate and antibacterial effect after 10 washes were the first.
Shown in the table.

[Table] Comparative Example 3 The same printed cotton as that used in Example 3
A 100% 40-count satin fabric with a basis weight of 130 g/m ² was coated with 5 g of ferrous sulfate and 3.1 g of L-ascorbic acid as deodorizing substances, and Poron MF50 manufactured by Shin-Etsu Chemical (containing 40% solid content) as an antibacterial substance. ) After padding 16.7g/mixed aqueous solution at a squeezing rate of 60%, it was heated to 100℃.
It was dried. In addition, Boncoat manufactured by Dainippon Ink Co., Ltd.
A coating liquid containing 20 g of R3020 (solid content 40%) thickened to 5000 centipoise with kerosene was applied to the fabric at a coating rate of 40% by weight.
Coating was performed using a knife coater, dried at 100°C, and heat treated at 150°C for 3 minutes. Table 2 shows the odor removal rate and antibacterial effect of the resulting product after processing and after washing 10 times.

[Table] (Effects of the invention) The higher the odor removal rate, the better the deodorizing effect, and the higher the bacteria reduction rate, the better the antibacterial effect. As can be seen from Table 1, the product of the present invention exhibits excellent durability in both deodorizing and antibacterial effects even after 10 washes. When ferrous sulfate and L-ascorbic acid are used in the conventional manner, there is no washing resistance of the deodorizing and antibacterial effect. Compared to conventional deodorizing or antibacterial effects alone, the present invention uses a durable antibacterial substance that has both the effect of preventing the generation of bad odors and further protecting textile structures from bad odor contamination from the external environment. Moreover, each effect has washing durability, which is an important characteristic desired by the textile industry.

Claims (1)

[Claims] 1. The weight ratio of ferrous salt and L-ascorbic acid is
50:50~90:10 mixed deodorizing substance as solid content
0.1~10% by weight and antibacterial substances as solid content 0.05~
A deodorizing antibacterial fiber structure comprising a fiber structure in which 4% by weight (all weight% is based on the weight of the fiber structure) is fixed together with a synthetic resin. 2. The deodorant antibacterial according to claim 1, wherein the ferrous salt is ferrous sulfate, ferrous chloride, ferrous oxalate, ferrous acetate, ferrous tartrate, or ferrous lactate. Textile structures. 3. The deodorant antibacterial fiber structure according to any one of claims 1 to 2, wherein the antibacterial substance is an organosilicon quaternary ammonium salt or a diphenyl ether compound. 4. The fibrous structure according to any one of claims 1 to 3, wherein the synthetic resin is an aminoplast resin, an acrylic resin, or a urethane resin. 5. The fiber structure according to any one of claims 1 to 4, wherein the fiber structure is a knitted fabric, a woven fabric, or a nonwoven fabric containing natural fibers, synthetic fibers, or regenerated fibers.