JP3887053B2 - Antibacterial fiber product and its manufacturing method - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a fiber product made of fibers, and relates to a technique for imparting excellent antibacterial property to the fiber product and maintaining the antibacterial property even after many washings.
[0002]
[Prior art]
<Treatment of textile products with disinfectant>
Textile products such as underwear, socks, sports apparel, bedding, and shoes are susceptible to contamination by organic matter and secrets and skin exfoliation discharged from the user's skin. And since these become nutrient sources, it becomes a suitable medium for bacteria to propagate, and as a result, unpleasant odor is generated by the product of the bacteria, and in some cases, it causes skin diseases and food poisoning.
[0003]
In recent years, nosocomial infections due to drug-resistant Staphylococcus aureus frequently occur in medical practice, and food poisoning due to pathogenic E. coli O157 frequently occurs in the food industry, which has become a social problem.
[0004]
From the above viewpoints, clothing used in hospitals, nursing clothes, bedding, curtains, rugs, wallpaper, bandages, towels, towels, and other textile products, headclothes, clothes, aprons, towels, towels used in the food industry, etc. For these textile products, it is desired to develop a technology for applying antibacterial processing effective for this.
[0005]
Conventionally, in order to solve such a problem, a liquid containing various bactericides including cationic bactericides such as benzalkonium chloride and 3- (trimethoxysilyl) propyl octadadecyldimethylammonium chloride is immersed, It is performed to adhere to a textile product by methods such as coating and spraying.
[0006]
As a method for the strong anchoring for textile products fungicides, for example, (i) a method of binding to a portion of the fiber molecules some of bactericidal quaternary ammonium salts via the organic silicone compound, (ii) Attempts have also been made to bond or melt a bactericidal metal compound in the composition of the fiber constituent material to impart antibacterial properties, and (c) to hold other bactericidal compounds with a fixing agent.
[0007]
<Protection of wood and plastics with tebuconazole>
Α- [2- (4-Chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole- (1) -ethanol used in the present invention is a 1H triazole type. It is a kind of compound, and is generally called tebuconazol, and is known to have antibacterial and antifungal activity.
[0008]
For example, JP-A-2-292203 discloses an antibacterial and antifungal composition that combines tebuconazole and propiconazole, and this composition treats plants or their habitats. It is said that it is suitable for the preservation of wood. According to the examples, the composition is used in the form of a hydratable powder, emulsifiable concentrate, powder, extruded granule, coated granule, and suspendable concentrate. In the upper right column to the lower left column of page 2, tebuconazole, its synthesis method, and antibacterial antifungal activity are described in EP-A-0040345 and EP-A-0052424.
[0009]
Japanese Patent Application Laid-Open No. 5-132405 discloses a microbicide comprising an azole-type fungicidal agent such as tebuconazole and an iodopropargyl derivative. There is also a description that it can be used to protect against rotting fungi and wood-discoloring fungi, and that the form of use can be a solution, suspension, emulsion or paste. This publication states that EP-A-0040345 and EP-A-0052424 describe that tebuconazole and propiconazole are used for plant and seed protection.
[0010]
JP-A-5-201806 discloses a microbicide composition comprising an azole derivative (tebuconazole or the like) and a benzimidazole derivative. Similarly, Japanese Patent Application Laid-Open No. 5-201812 discloses a microbicide composition comprising an azole derivative (tebuconazole or the like) and an iodopropargyl derivative. These compositions are used to protect industrial materials, in particular plastics.
[0011]
Japanese Patent Application Laid-Open No. 7-316005 discloses a plant-microbicidal composition comprising a component I such as tebuconazole and a specific component II. This composition is said to be able to suppress or kill microorganisms that develop on plants.
[0012]
JP-A-8-198711 discloses a wood preservative composition containing a wood preservative represented by a triazole derivative (including tebuconazole) and an inorganic acid as essential components. Dosage forms include wettable powders, emulsions, solubilizers, oils, pastes and the like.
[0013]
Japanese Patent Application Laid-Open No. 8-231313 discloses an industrial antibacterial and antifungal composition containing both tebuconazole and 2-benzimidazolylcarbamic acid alkyl ester as active ingredients, and prevents deterioration of materials and deterioration of quality. It is said that maintenance of the overview will be attempted. In the Examples, the antibacterial and antifungal effect of the injection molded plate after the addition of this composition (in the case of 100% tebuconazole) to polypropylene pellets is evaluated.
[0014]
[Problems to be solved by the invention]
The method for adhering a liquid containing a bactericidal agent such as benzalkonium chloride and 3- (trimethoxysilyl) propyl okdadecyldimethylammonium chloride to a textile product by dipping, coating, spraying, etc. is described above. Even if a method such as (i) to (c) is taken, the disinfectant decomposes without being able to withstand the heating during the processing operation, and the carrying amount is reduced, the processing step is complicated and expensive, washing with water, Dropping off due to external influences such as washing, etc., the duration of efficacy is short, the texture of the textile product after antibacterial treatment changes, yellowing over time, harmful when the product is discarded or incinerated There were various disadvantages such as generation of substances.
[0015]
On the other hand, triazole derivatives such as tebuconazole are used for protecting plants (wood, etc.) and plastics, but are only for improving the preservation of plants and plastics themselves.
[0016]
The present invention has good operability during processing of fiber products made from fibers, the processed products have excellent antibacterial properties, and the antibacterial properties are maintained even after many washings, Therefore, it is an object of the present invention to provide an antibacterial fiber product that is less likely to cause yellowing and texture change of the fiber product and has high safety, and a method for producing the same.
[0017]
[Means for Solving the Problems]
The antibacterial fiber product of the present invention has α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2 on the fiber surface of a fiber product made from the fiber. , 4-triazole- (1) -ethanol (generic name: tebuconazole) is carried without using a binder resin in combination .
[0018]
The method for producing an antibacterial fiber product of the present invention is obtained by bringing a fiber product made from fibers into contact with a treatment liquid emulsified, suspended or dissolved in a medium without using a binder resin together with a binder resin , and then drying. Alternatively, it is characterized by imparting antibacterial properties to the fiber product by drying and curing .
[0019]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
[0020]
Tebuconazole has been used mainly as a microbicide (bactericidal fungicide) for plants (especially for wood preservation) as described in the section of the prior art. It is a triazole compound having the structure shown.
[0021]
[Chemical 1]
[0022]
Tebuconazole has an LD ₅₀ of 4000 mg / kg (rat male, oral administration), has extremely low toxicity, and is not irritating to the skin or eyes, so it can be used with confidence even when used in products that come into direct contact with the human body. it can. It also has excellent heat resistance, weather resistance, and hydrolysis resistance.
[0023]
The antibacterial fiber product of the present invention is obtained by supporting tebuconazole on the fiber surface of a fiber product made from the fiber .
[0024]
Textile products include natural fibers such as cotton, linen, silk, and wool, regenerated or semi-synthetic fibers such as rayon and acetate, acrylic, polyester, polyvinyl alcohol, polyamide, polyvinyl chloride, and polyvinylidene chloride. And products made from synthetic fibers such as polyolefins. Products refer to yarns, woven fabrics, non-woven fabrics, knitted fabrics, cloths, flocked fabrics, cotton-like products, or products obtained by further cutting, sewing, secondary processing, and the like.
[0025]
Among these fibers, natural fibers having reactive functional groups, regenerated or semi-synthetic fibers, or some synthetic fibers such as acrylic are preferred because of their high affinity with tebuconazole. However, even in the case of fibers such as polyester and polyamide, the affinity may be relatively good depending on the physical properties such as the surface state and density of the fibers .
[0026]
The antibacterial fiber product of the present invention is obtained by bringing a fiber product made from fibers into contact with a treatment liquid obtained by emulsifying, suspending or dissolving tebuconazole in a medium without using a binder resin. It is manufactured by performing curing, and thereby, antibacterial properties can be imparted to the textile product.
[0027]
Tebuconazole is a compound that is hardly soluble in water, and is used for the treatment of textiles in the form of a solution in which it is emulsified or suspended or dissolved in a solvent.
[0028]
The emulsion is obtained by emulsifying a solvent solution of tebuconazole in water with the help of an emulsifier. As the emulsifier, for example, various surfactants such as polyoxyethylene nonylphenyl ether sulfonate soda, polyoxyethylene nonylphenyl ether EO (ethylene oxide) adduct, hydrogenated castor oil EO adduct are used. Examples of the solvent include alcohols (such as isopropanol), glycols (such as butyl diglycol), dimethyl sulfoxide, dimethylformamide, petroleum, alkylbenzene, spindle oil, monochloronaphthalene, vegetable oil (such as castor oil), and the like. The emulsified liquid is prepared, for example, by emulsifying an emulsified stock solution composed of 5 to 20% by weight of tebuconazole, 5 to 30% by weight of an emulsifier, and 90 to 50% by weight of a solvent in water.
[0029]
A suspension is obtained by suspending tebuconazole in water with the aid of a dispersing agent. At this time, a thickener may be added, or an antifoaming agent or an antifreezing agent may be added. As the dispersant, for example, various surfactants such as nonylphenol EO phosphate soda salt, styrenated phenol EO phosphate soda salt, lignin sulfonate and naphthalene sulfonate are used. As the thickener, polyacrylic acid soda, xanthan gum and the like are used. The suspension is, for example, tebuconazole 5 to 50% by weight, dispersant 1 to 10% by weight, thickener 0 to 1% by weight, antifreezing agent 0 to 5% by weight, antifoaming agent 0 to 1% by weight, remaining It is prepared by diluting a suspension stock solution having a composition consisting of water with water.
[0030]
The solvent solution is obtained by dissolving tebuconazole in a solvent. As the solvent, those described above in the description of the emulsion are used. The concentration of tebuconazole in the solution is set to 0.1 to 30% by weight, for example.
[0031]
Add plasticizer, softener, fluorescent agent, heat stabilizer, UV absorber, weather resistance improver, lubricant, dye / pigment, antistatic agent, reinforcing agent, flame retardant, etc., as necessary. You can also In addition to tebuconazole, other bioactive substances such as insecticides, pest repellents, moth repellents, fungicides, fungicides, etc. are used in combination to enhance the effect, expand the antibacterial spectrum, and expand the application range. You can also
[0032]
The contact between the textile product and the treatment liquid is performed by dipping, coating, spraying, or the like. Industrially, a method of dipping a fiber product in room temperature or a heated treatment solution for a certain period of time and then squeezing and drying (or drying and curing) is employed.
[0033]
The amount of tebuconazole attached is suitably 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the weight of the fiber product. If the amount of tebuconazole attached is too small, the antibacterial effect will be insufficient, while if it is too much, the antibacterial effect will not be improved beyond a certain limit, and the properties of the fiber product may be deteriorated. Also disadvantaged.
[0034]
<Action>
According to the present invention, the required amount of tebuconazole can be reliably supported not only on natural fibers but also on regenerated or semi-synthetic fibers, and even fiber products made of synthetic fibers or blended fibers thereof. Antibacterial textile products after treatment are highly safe and have excellent antibacterial activity against various bacteria including drug-resistant Staphylococcus aureus and pathogenic Escherichia coli, and the antibacterial properties are easily impaired by washing. Absent. If the conditions are selected , antibacterial activity is maintained even after many washings. In addition, the antibacterial fiber product of the present invention does not easily cause yellowing or texture change despite the antibacterial treatment, has no odor, and does not impair the original properties of the material fiber.
[0035]
【Example】
Next, the present invention will be described in detail with reference to examples. “CPTE” is tebuconazole. Hereinafter, “%” refers to weight%.
[0036]
<Test method>
The following method was adopted as a test method.
・ Laundry method: JIS L0217-103 method and JIS L1042: F-2 method + bleach added.
-Antibacterial test: About Staphylococcus aureus FDA 209P and methicillin resistant Staphylococcus aureus (MRSA) and Escherichia coli IFO 3301) Viable counts of unprocessed and processed samples were measured. For the evaluation of the effect, the evaluation index log B / C> 2 was set to be effective (O) for the sake of simplicity, and no other effect was set (X). However, B is the number of viable cells after 18 hours of cultivation of the unprocessed sample, and C is the number of viable cells after 18 hours of cultivation of the processed sample.
[0037]
Example 1
An emulsified liquid was prepared by emulsifying an emulsified stock solution of the following formulation in water so that the pure content of CPTE was 0.01% and 0.06%, respectively. After immersing cotton cloth in this emulsified liquid, it was squeezed so that a liquid equivalent to the weight of the cotton cloth adhered, and dried with hot air at 130 ° C. for 3 minutes to prepare a sample. Further, this sample was washed 10 times by the JIS L0217-103 method and used as a sample after washing. The results are shown in Table 1. MRSA and E. coli were used for the antibacterial test.
[0038]
<Emulsification stock formulation>
20% CPTE
・ 10% sodium polyoxyethylene nonylphenyl ether sulfonate (emulsifier)
・ 10% hydrogenated castor oil EO (ethylene oxide) adduct (emulsifier)
・ 20% castor oil (solvent)
・ 40% butyl diglycol (diethylene glycol monobutyl ether) (solvent)
[0039]
On the other hand, as a comparative control drug, parachlorometaxylenol (abbreviated as PCMX) and quaternary ammonium silicone antibacterial agent 3- (trimethoxysilyl) propyl octadadecyldimethylammonium chloride (abbreviated as Si-QAC) The sample and the sample after washing were prepared in the same manner as described above. The results are also shown in Table 1.
[0040]
[Table 1]

Drugs and adhesion Laundry MRSA E. coli Of processed cloth
Quantity (wt%) Number of inoculations Number of collections Number of inoculations Number of collections Yellowing
Unprocessed cloth 0 1 x 10 ⁶ 1 x 10 ⁸ 2 × 10 ⁶ 1 x 10 ⁸ None
CPTE 0 1 × 10 ⁶ <10 ² 2 × 10 ⁶ <10 ² None
0.01 Ten 1 x 10 ⁶ 1 x 10 ³ 2 × 10 ⁶ 2 × 10 ⁴ None
CPTE 0 1 × 10 ⁶ <10 ² 2 × 10 ⁶ <10 ² None
0.06 Ten 1 x 10 ⁶ <10 ² 2 × 10 ⁶ 3 × 10 ² None
PCMX 0 1 × 10 ⁶ 1 × 10 ⁴ 2 × 10 ⁶ 4 × 10 ⁴ None
0.06 Ten 1 x 10 ⁶ > 10 ⁷ 2 × 10 ⁶ > 10 ⁷ None
Si-QAC 0 1 × 10 ⁶ 1 × 10 ⁵ 2 × 10 ⁶ 5 × 10 ⁵ Large
0.06 Ten 1 x 10 ⁶ > 10 ⁶ 2 × 10 ⁶ > 10 ^{7 a} little present [0041]
As is clear from Table 1, the sample treated with the emulsion containing CPTE maintained good antibacterial properties even after 10 washes. In addition, when the comparative control drugs “PCMX” and “Si-QAC” were used, no antibacterial effect was observed after 10 washes. When “Si-QAC” was used, yellowing was also observed.
[0042]
Example 2
Based on the emulsion stock solution formulation of Example 1, an emulsion having a pure CPTE content of 1.0% was prepared. Further, a solvent formulation solution having a formulation of 1% CPTE (raw material) and 99% butyl diglycol (solvent) was prepared. A sample was prepared using a 100% polyester cloth in the same manner as in Example 1, and an antibacterial test for Staphylococcus aureus FDA 209P was performed. The results are shown in Table 2.
[0043]
[Table 2]

Emulsified solvent solvent solution
Drugs and adhesion Laundry S. aureus FDA 209P S. aureus FDA 209P
Quantity (wt%) Number of inoculations Number of collections Number of inoculations Number of collections
Unprocessed cloth 0 6 x 10 ⁵ 2 × 10 ⁸ 2 × 10 ⁶ 2 × 10 ⁸
CPTE 0 6 × 10 ⁵ <10 ² 2 × 10 ⁶ <10 ²
1.0 Ten 6 x 10 ⁵ 2 × 10 ⁵ 2 × 10 ⁶ 1 x 10 ⁵
PCMX 0 6 × 10 ⁵ > 10 ⁷ 2 × 10 ⁶ > 10 ⁷
1.0 Ten 6 x 10 ⁵ > 10 ⁷ 2 × 10 ⁶ > 10 ⁷
Si-QAC 0 6 × 10 ⁵ > 10 ⁷ 2 × 10 ⁶ > 10 ⁷
1.0 Ten 6 x 10 ⁵ > 10 ⁷ 2 × 10 ⁶ > 10 ⁷
[0044]
As is clear from Table 2, the sample treated with the emulsion containing CPTE was washed 10 times even without binder resin even if it was made of 100% polyester fiber, which is difficult to adhere, with 1.0% CPTE attached. The antibacterial property was maintained afterwards. On the other hand, when using a comparative drug,
Antibacterial properties could not be maintained before and after washing.
[0045]
【The invention's effect】
As described in the section of action, according to the present invention, the necessary amount of tebuconazole is required not only for natural fibers but also for regenerated or semi-synthetic fibers, and even for fiber products made of synthetic fibers or blended fibers thereof. It can be reliably supported. Antibacterial textile products after treatment are highly safe and have excellent antibacterial activity against various bacteria including drug-resistant Staphylococcus aureus and pathogenic Escherichia coli, and the antibacterial properties are easily impaired by washing. Absent. If the conditions are selected , antibacterial activity is maintained even after many washings. In addition, the antibacterial fiber product of the present invention does not easily cause yellowing or texture change despite the antibacterial treatment, has no odor, and does not impair the original properties of the material fiber.

Claims (2)

Α- [2- (4-Chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole- (1)-is formed on the fiber surface of the fiber product made from the fiber. Antibacterial fiber product that supports ethanol (generic name: tebuconazole) without using binder resin . α- [2- (4-Chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole- (1) -ethanol (generic name: tebuconazole) in combination with binder resin The fiber product made from the fiber is brought into contact with the treatment liquid emulsified, suspended or dissolved in the medium without drying, and then the fiber product is given antibacterial properties by drying or drying and curing. A method for producing an antibacterial fiber product characterized by the above.