JP2000256963A - Antimicrobial agent for fiber and antimicrobial textile product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antimicrobial textile product capable of exhibiting excellent antimicrobial effects over the whole pH region without causing discoloration even in the case of a white product or a light-colored product by treating a textile product with an antimicrobial agent for fibers comprising a specific sorbic acid ester. SOLUTION: A textile product comprising synthetic fibers such as a polyester or a nylon and natural fibers, etc., such as cotton or wool is treated with a treating liquid prepared by making an antimicrobial agent for fibers comprising a sorbic acid ester represented by the formula (CH3CH=CHCH=CHCOO)nR (R is an alcohol residue; n is 1-10), e.g. 2-hydroxyethyl sorbate coexist with any of a methylolurea resin, a glyoxal resin, a urethane resin, an acrylic resin, a polyester resin, a polyvinyl alcohol resin, an epoxy resin, an oxazoline-based resin or a silicone-based resin to impart antimicrobial properties thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antibacterial agent for fibers and an antibacterial fiber product. More specifically, the present invention provides
An antibacterial agent for fibers capable of imparting excellent antibacterial properties without causing any health and safety problems to the human body and causing discoloration of textiles, and an antibacterial fiber having excellent antibacterial properties without discoloration About the product.

[0002]

2. Description of the Related Art Hitherto, phenolic compounds, organic copper compounds, organic zinc compounds, silver compounds, quaternary ammonium salt compounds and the like have been used for antibacterial treatment of textile products. However, some of these compounds
There are several problems, such as those that are prone to skin injuries to the human body and those that are prone to discoloration for textiles. Sorbic acid and its salts have very low toxicity and have a broad antibacterial spectrum against aerobic bacteria, yeasts, molds, etc., and are therefore permitted to be used as preservatives and preservatives under the Food Sanitation Law, It is used for meat products, dried seafood products, boiled beans, boiled soybeans, fruit wine, etc. However, sorbic acid and its salts are positive for human skin irritation and skin sensitization, and have low pH.
Although it has high antibacterial activity in the region, it dissociates in the alkaline region and the antibacterial effect is drastically reduced. For this reason, sorbic acid compounds have not been developed for uses other than food additives.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to an antibacterial agent for textiles capable of imparting an excellent antibacterial property without causing a problem in safety and health to human bodies and without causing discoloration in textiles, and discoloration. The object of the present invention is to provide an antibacterial fiber product having no antibacterial property and having excellent antibacterial properties.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, it has been found that sorbic acid ester compounds have an excellent antibacterial action and cause discoloration in textiles. It was found to be harmless to the human body, and based on this finding, the present invention was completed. That is, the present invention provides: (1) an antibacterial agent for fibers, characterized by comprising a sorbic acid ester represented by the general formula [1] as an active ingredient: (CH ₃ CH = CHCH = CHCOO) nR [1] (Where R is an alcohol residue, and n is 1 to
It is 10. ), And, (2) the general formula antimicrobial fiber product characterized by comprising processed by sorbic acid ester represented by _{[1], (CH 3 CH} = CHCH = CHCOO) nR ... [1] ( provided that Wherein R is an alcohol residue and n is 1 to
It is 10. ), Is provided. Further, as a preferred embodiment of the present invention, (3) R is a compound having 1 to 10 carbon atoms.
(4) N-methylol urea resin, glyoxal resin, urethane resin, acrylic resin, polyester resin, PVA resin, epoxy resin, oxazoline resin, The antibacterial agent for fibers according to (1), which contains a silicone resin, (5) the antibacterial fiber product according to (2), wherein R is a monohydroxyalkyl group having 1 to 10 carbon atoms, and (6) In the treatment with sorbic acid ester, N
-The antimicrobial fiber product according to (2), wherein a methylol urea resin, a glyoxal resin, a urethane resin, an acrylic resin, a polyester resin, a PVA resin, an epoxy resin, an oxazoline-based resin or a silicone-based resin coexists. .

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the general formula [1]
Is used. _{(CH 3 CH = CHCH = CHCOO} ) nR ... [1] However, in the general formula [1], R is an alcohol residue, n represents 1 to 10. In the present invention, there is no particular limitation on the alcohol that provides the residue represented by R, and examples thereof include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol,
Dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, eicosanol, benzyl alcohol, phenethyl alcohol, allyl alcohol, monohydric alcohol such as cinnamyl alcohol, ethylene glycol, propylene glycol, Dihydric alcohols such as butanediol, pentanediol, neopentyl glycol, hexanediol, octanediol, and decanediol; trihydric alcohols such as glycerin, trimethylolethane and trimethylolpropane; tetrahydric alcohols such as erythritol and pentaerythritol; Examples thereof include hexahydric alcohols such as pentaerythritol and polyhydric alcohols such as a polyvinyl alcohol oligomer. When the alcohol giving the residue represented by R is a divalent or higher alcohol, the compound may be a compound in which all of the hydroxyl groups are esterified with sorbic acid, or a state in which some of the hydroxyl groups are unreacted. May be left as a compound.

In the present invention, the method for producing the sorbic acid ester represented by the general formula [1] is not particularly limited. For example, dehydration esterification of sorbic acid and alcohol, dehydrohalogenation reaction of sorbic halide and alcohol And esterification by transesterification between a lower alcohol ester of sorbic acid and an alcohol. Further, an addition reaction between sorbic acid and a cyclic ether such as an oxirane compound can produce a sorbic acid ester represented by the general formula [1] in which R is a glycol residue. In the sorbic acid ester represented by the general formula [1] used in the present invention, R is preferably a monohydroxyalkyl group having 1 to 10 carbon atoms, and is preferably a 2-hydroxyethylene group or a 2-hydroxypropylene group. Is more preferred. The sorbic acid ester in which R is a 2-hydroxyethylene group or a 2-hydroxypropylene group can be easily produced by an addition reaction of ethylene oxide or propylene oxide to sorbic acid, and has an excellent antibacterial effect. The form of the antibacterial agent for fibers of the present invention is not particularly limited, and for example, can be in a liquid or solid state. There is no particular limitation on the method of bringing the antibacterial agent for fibers of the present invention into a liquid state,
For example, the sorbic acid ester represented by the general formula [1] can be dissolved in various organic solvents to obtain a liquid state,
Alternatively, it can be emulsified or dispersed in water or an organic solvent using a surfactant, an emulsifier, or the like, and the emulsion or dispersion can be used as an antibacterial agent. The organic solvent in which the sorbate represented by the general formula [1] is dissolved or dispersed is not particularly limited, and examples thereof include lower alcohols such as ethanol and propanol, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate and methyl acetate. And the like. When emulsifying or dispersing the sorbic acid ester represented by the general formula [1], there is no particular limitation on the surfactant used, and examples thereof include polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether, and polyoxyalkylene fatty acid ester. , Non-ionic surfactants such as spun, tween, etc.
Polyoxyalkylene alkyl ether sulfonate,
Examples include anionic surfactants such as polyoxyalkylene styrenated phenyl ether sulfonate.

There is no particular limitation on the object to which the antibacterial agent for fibers of the present invention is applied. For example, synthetic fibers such as polyester, nylon and acrylic, natural fibers such as cotton, hemp and wool,
Composite fibers of synthetic fibers and natural fibers can be exemplified. Examples of the form of these fibers include fiber products such as yarn, fabric, knit, woven and non-woven fabric. The method for applying the antibacterial agent for fibers of the present invention is not particularly limited. For example, the antibacterial agent can be applied in a post-processing step such as padding treatment, dipping treatment, dye bath and bath treatment, and coating. The antibacterial agent for fibers of the present invention can impart washing resistance to the antibacterial effect by using a fiber processing resin in combination. As the resin for fiber processing to be used in combination, for example, N
-Methylol urea resin, glyoxal resin, urethane resin, acrylic resin, polyester resin, PVA resin, epoxy resin, oxazoline resin, silicone resin and the like. Since the antibacterial fiber product of the present invention, which has been treated with a sorbic acid ester represented by the general formula [1] in combination with a fiber processing resin, has washing resistance, it can be used for daily use of clothes, towels, bedding and the like. It can be suitably used for applications where washing is repeated. The antibacterial textile product of the present invention treated with the sorbic acid ester represented by the general formula [1] without using a fiber processing resin has no washing resistance, but changes the original texture of the textile product. Since it does not need to be washed, it can be suitably used for applications such as curtains, curtains, furniture coverings, curtains, etc., in which the chances of washing are relatively small. Since the antibacterial agent for textiles of the present invention does not cause discoloration by treating textiles, it can be particularly suitably applied to textiles composed of white or light-colored dyed products. Sorbic acid, which is conventionally recognized as a food additive, shows high antibacterial activity in the low pH range,
In the alkaline region, it becomes dissociated and its antibacterial effect is drastically reduced. Since the sorbic acid ester used in the present invention does not dissociate even in an alkaline region, the antibacterial fiber product of the present invention exhibits an excellent antibacterial effect over all pH ranges. Further, the sorbic acid ester used in the present invention, unlike sorbic acid, has no skin irritation or skin sensitization to humans, and therefore can be used safely.

[0008]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Synthesis Example 1 Sorbic acid 20 g (0.18 mol), potassium hydroxide 0.1
After heating a mixture of 05 g and 100 ml of isopropanol to 100 ° C. in an autoclave, 11 g (0.25 mol) of ethylene oxide was added, and the mixture was stirred at 100 ° C. for 5 hours. After the completion of the reaction, isopropanol and unreacted ethylene oxide were removed, and the reaction mixture was further washed with water to obtain 25.6 g of sorbic acid-2-hydroxyethyl ester. The acid value of the obtained sorbic acid-2-hydroxyethyl ester was 0.2 or less. Synthesis Example 2 Sorbic acid 20 g (0.18 mol), potassium hydroxide 0.1
A mixture of 0.5 g of isopropanol and 100 ml of isopropanol was heated to 100 ° C. in an autoclave, and 14.5 g (0.25 mol) of propylene oxide was added thereto.
Stirred at C for 5 hours. After the completion of the reaction, isopropanol and unreacted propylene oxide were removed, and the reaction mixture was further washed with water to obtain 28.3 g of sorbic acid-2-hydroxypropyl ester. The resulting sorbic acid-2-
The acid value of the hydroxypropyl ester was 0.2 or less. Example 1 A treatment bath containing 0.5% by weight of sorbic acid-2-hydroxyethyl ester obtained in Synthesis Example 1 was prepared, and five cotton broad white cloths were dipped / 1 nip at a pickup rate of 59% by weight. After padding under conditions, 105
C. for 3 minutes and cured at 160.degree. C. for 3 minutes. Two of the cotton broad white cloths were washed 10 times according to the manual for pre-treatment of SEK mark products specified by the Textile Product New Function Evaluation Council, and the other three were left unwashed. . Staphylococcus aureus was used as a test bacterium in accordance with the method specified in the Manual for Quantitative Antibacterial Testing of Fiber Products (Unified Test Method) specified by the Textile Products New Function Evaluation Council.
ATCC 6538P) and Klebsiella pneumoniae (Klebsiel)
La pneumoniae ATCC4352), an antibacterial test was performed on the unwashed cloth and the laundry cloth. The unwashed cloth had a viable count after 18 hours for the two bacteria less than the initial inoculum, whereas the laundry cloth had a viable count after 18 hours for the two bacteria for the first inoculation. It was more than the number. For unwashed cloth, colorimeter [Minolta Co., Ltd., CM-370]
0d], the Hunter whiteness was measured. The whiteness is 79
Met. Example 2 An antibacterial test and whiteness were performed in the same manner as in Example 1 except that the sorbic acid-2-hydroxyethyl ester obtained in Synthesis Example 2 was used instead of sorbic acid-2-hydroxyethyl ester. A measurement was made. In the antibacterial test, the unwashed cloth had a viable cell count after 18 hours for the two bacteria less than the initial inoculated cell count, whereas the laundry cloth had a viable cell count after 18 hours for the two cells. Had increased from the initial culture. Whiteness was 80. Example 3 An antibacterial test and whiteness measurement were performed in the same manner as in Example 1 except that sorbic acid-5-hydroxypentyl ester was used instead of sorbic acid-2-hydroxyethyl ester. In the antibacterial test, the unwashed cloth had a viable cell count after 18 hours for the two bacteria less than the initial inoculated cell count, whereas the laundry cloth had a viable cell count after 18 hours for the two cells. Had increased from the initial culture. Whiteness was 80. Example 4 An antibacterial test and whiteness measurement were performed in the same manner as in Example 1 except that sorbic acid-2-hydroxyoctyl ester was used instead of sorbic acid-2-hydroxyethyl ester. In the antibacterial test, the unwashed cloth had a viable cell count after 18 hours for the two bacteria less than the initial inoculated cell count, whereas the laundry cloth had a viable cell count after 18 hours for the two cells. Had increased from the initial culture. Whiteness was 80. Example 5 An antibacterial test and whiteness measurement were performed in the same manner as in Example 1 except that dipentaerythritol pentasorbic acid ester was used instead of sorbic acid-2-hydroxyethyl ester. In the antibacterial test, the unwashed cloth was
The viable count after 18 hours for the two bacteria was less than the initial inoculum, but the laundry cloth had a viable count after 18 hours for the two bacteria that was greater than the initial inoculum. . Whiteness is 80
Met. Comparative Example 1 The same two cotton broad white cloths as those used in Example 1 were washed 10 times in accordance with the SEK mark product pretreatment method manual set by the Textile Product New Function Evaluation Council to form a laundry cloth. The same three cotton broad cloths were prepared as unwashed cloths, and an antibacterial test and whiteness measurement were performed in the same manner as in Example 1. In the antibacterial test, both unwashed cloth and laundry cloth,
The viable cell count after 18 hours for the two bacteria was greater than the initial culture count. Whiteness was 80. Table 1 shows the results of Examples 1 to 5 and Comparative Example 1.

[0009]

[Table 1]

As can be seen from Table 1, the unwashed cloths of Examples 1 to 5 treated with the antibacterial agent for fibers of the present invention show good antibacterial properties and have not been subjected to the antibacterial treatment. The whiteness equivalent to that of the cotton broad white cloth of Comparative Example 1 is maintained. However, after 10 washes, the antibacterial properties are lost. Example 6 0.5% by weight of sorbic acid-2-hydroxyethyl ester obtained in Synthesis Example 1 and a glyoxal resin [Sumitomo Chemical
A processing bath containing 1.0% by weight of Sumitex Resin NS-19] and 0.4% by weight of a catalyst for glyoxal resin [Sumitomo Chemical Co., Ltd., Sumitex Accelerator X-80] was prepared. 5 pieces of cotton broad white cloth 1 dip /
After padding under the conditions of 1 nip and a pickup rate of 59% by weight, dried at 105 ° C. for 3 minutes,
Cure at 0 ° C. for 3 minutes. Two of the cotton broad white cloths were washed 10 times according to the manual for pre-treatment of SEK mark products specified by the Textile Product New Function Evaluation Council, and the other three were left unwashed. . According to the method specified in the Manual for Quantitative Antibacterial Testing of Fiber Products (Unified Test Method) specified by the Textile Products New Function Evaluation Council,
Staphylococcus aureus (Staphyloco)
ccus aureus ATCC 6538P) and Klebsiella pneumoniae A
Using TCC4352), an antibacterial test was carried out on an unwashed cloth and a washed cloth. In both the unwashed cloth and the laundry cloth, the viable cell count after 18 hours was less than the initial multiplied cell count for the two bacteria. About unwashed cloth, colorimeter [Minolta Co., Ltd., CM-
Hunter whiteness was measured using 3700d]. The whiteness was 79. Example 7 An antibacterial test and whiteness were performed in the same manner as in Example 6 except that the sorbic acid-2-hydroxypropyl ester obtained in Synthesis Example 2 was used instead of sorbic acid-2-hydroxyethyl ester. A measurement was made. In the antibacterial test, the viable cell count after 18 hours was less than the initial cell count of the two bacteria in both the unwashed cloth and the laundry cloth. Whiteness is 8
It was 0. Example 8 An antibacterial test and whiteness measurement were performed in the same manner as in Example 6 except that sorbic acid-5-hydroxypentyl ester was used instead of sorbic acid-2-hydroxyethyl ester. In the antibacterial test, the viable cell count after 18 hours was less than the initial cell count of the two bacteria in both the unwashed cloth and the laundry cloth. Whiteness was 80. Example 9 An antibacterial test and whiteness measurement were performed in the same manner as in Example 6 except that sorbic acid-2-hydroxyoctyl ester was used instead of sorbic acid-2-hydroxyethyl ester. In the antibacterial test, the viable cell count after 18 hours was less than the initial cell count of the two bacteria in both the unwashed cloth and the laundry cloth. Whiteness was 80. Example 10 An antibacterial test and whiteness measurement were performed in the same manner as in Example 6, except that dipentaerythritol pentasorbic acid ester was used instead of sorbic acid-2-hydroxyethyl ester. In the antibacterial test, the viable cell count after 18 hours was less than the initial cell count of the two bacteria in both the unwashed cloth and the laundry cloth. Whiteness was 80. Comparative Example 2 Glioxal resin [Sumitomo Chemical Co., Ltd., Sumitex Resin NS-19] 1.0% by weight and catalyst for glyoxal resin [Sumitomo Chemical Co., Ltd., Sumitex Accelerator X]
-80] A treatment bath containing 0.4% by weight was prepared, and padding was performed on five cotton broad white cloths under the conditions of 1 dip / 1 nip and a pickup rate of 59% by weight, and then 105
C. for 3 minutes and cured at 160.degree. C. for 3 minutes. Two of the cotton broad white cloths were washed 10 times in accordance with the SEK mark product pretreatment method manual set by the Textile Product New Function Evaluation Council, and the other three sheets were left as unwashed cloths. An antibacterial test and whiteness measurement were performed in the same manner as in Example 6. In the antibacterial test, the viable cell count after 18 hours for the two types of bacteria in both the unwashed cloth and the laundry cloth was larger than the initial number of cultured cells. Whiteness was 80. Comparative Example 3 Instead of sorbic acid-2-hydroxyethyl ester, sorbic acid of a food additive grade was used,
An antibacterial test and whiteness measurement were performed in the same manner as in Example 6. In the antibacterial test, the unwashed cloth had a viable count after 18 hours for the two bacteria less than the initial infested count. Laundry cloth showed that the viable count after 18 hours for Staphylococcus aureus was less than the initial inoculum, but the viable count after 18 hours for Klebsiella pneumoniae was greater than the initial inoculum . The whiteness was 79. Comparative Example 4 An antibacterial test and whiteness measurement were performed in the same manner as in Example 6 except that benzalkonium chloride was used instead of sorbic acid-2-hydroxyethyl ester. In the antibacterial test, the unwashed cloth had a viable count after 18 hours for the two bacteria less than the initial infested count. Laundry cloth showed that the viable count after 18 hours for Klebsiella pneumoniae was greater than the initial count, but the viable count at 18 hours for Staphylococcus aureus was less than the initial count. . The whiteness was 77. Table 2 shows the results of Examples 6 to 10 and Comparative Examples 2 to 4.

[0011]

[Table 2]

As can be seen from Table 2, the cotton broad white cloths of Examples 6 to 10 treated with the antibacterial agent for fibers of the present invention show good antibacterial properties in both unwashed cloth and laundry cloth.
In addition, the whiteness is equivalent to that of the cotton broad white cloth of Comparative Example 2 not subjected to the antibacterial treatment. The results are shown in Examples 1 to
Compared with the result of 5, after adding glyoxal resin and a catalyst for glyoxal resin to the treatment bath, padding, curing after drying, after repeating the washing 10 times,
It can be seen that the antibacterial property is maintained. In Comparative Example 3 in which sorbic acid was used as a drug, the laundry showed good antibacterial properties against Staphylococcus aureus, but was impaired in antibacterial properties against Klebsiella pneumoniae. The cotton broad white cloth of Comparative Example 4 using benzalkonium chloride as a drug
Although the whiteness is low, and the laundry shows good antibacterial properties against Staphylococcus aureus, the antibacterial properties against Klebsiella pneumoniae are impaired.

[0013]

Industrial Applicability The antibacterial agent for fibers of the present invention can provide excellent antibacterial properties without causing any problem in safety and hygiene for human bodies and without causing discoloration of fiber products. Further, the antibacterial fiber product of the present invention does not discolor even if it is a white or light-colored product, and exhibits an excellent antibacterial effect over the entire pH range.

Continuation of the front page (72) Inventor Kimihiro Makino 4-23-1, Bunkyo, Fukui-shi, Fukui Prefecture F-term in Nichika Chemical Co., Ltd. 4H011 AA02 BB06 BC19 DA10 DD07 DE17 DF03 DG02 DG05 DH08 4L033 AB01 AC10 AC15 BA19

Claims (2)

[Claims] 1. An antibacterial agent for fibers comprising a sorbic acid ester represented by the general formula [1] as an active ingredient. _{(CH 3 CH = CHCH = CHCOO} ) nR ... [1] ( In the formula, R is an alcohol residue, n represents 1
It is 10. ) 2. An antibacterial fiber product treated with a sorbate ester represented by the general formula [1]. _{(CH 3 CH = CHCH = CHCOO} ) nR ... [1] ( In the formula, R is an alcohol residue, n represents 1
It is 10. )