JPH09315920A - Antibacterial agent and antibacterial fiber material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antibacterial agent capable of suppressing the generation and proliferation of molds and bacteria and free from environmental pollution and obtain an antibacterial fiber material produced by using the agent. SOLUTION: This antibacterial agent is produced by dispersing or dissolving 0.01-40% camellia oil extracted from natural camellia in water together with starch or a starchy liquid mixture produced by mixing starch with an enzyme (cyclodextrin glucanotransferase) and spray-drying the solution or dispersion in the form of fine particles.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial agent which can suppress the generation and reproduction of mold and fungi and does not pollute the environment, and an antibacterial fiber material using the same.

[0002]

2. Description of the Related Art Hitherto, an antibacterial agent (sterilizer) has been used as a fiber material for suppressing the generation or reproduction of mold and fungi or killing them. For example, examples of inorganic antibacterial agents include Zeomic, and examples of organic antibacterial agents include Biosil.

[0003]

However, since the above-mentioned conventional antibacterial agents are poor in water solubility, it is basically impossible to adhere (fix) to hydrophilic fiber materials such as natural fibers. Since the antibacterial agent is not sufficiently fixed even after the immersion treatment for a long time, the antibacterial agent was easily washed off when the fiber material was washed with water.
Therefore, the antibacterial property of the fiber material was hardly maintained or maintained. Although volatile or sublimable antifungal agents are known, their effects are low unless they are in a space having a sufficient sealing property. Furthermore, the antibacterial agent used is required to be nontoxic to the human body or plants and not to adversely affect purified bacteria in wastewater, and has both these properties and the above-mentioned adhesiveness. Such an antibacterial agent has been sought after.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been proposed in view of the above, and the camellia oil extracted from the natural camellia material 0.01 to
The present invention relates to an antibacterial agent characterized in that 40% and a starchy mixture of starch or cyclodextrin glucanotransferase mixed with starch are dispersed or dissolved in water and spray-dried to form fine particles. . The antibacterial agent may contain a water-soluble resin.

The present invention also proposes an antibacterial fiber material characterized in that the above antibacterial agent is dissolved in water, the fibers are impregnated with the antibacterial agent and dried.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The camellia oil used in the present invention is prepared by washing fruits of the camellia (Melamaceae) with water or hot water.
It was obtained by squeezing this oil well and is now marketed separately as oil and fruit. The camellia oil and fruits contain about 90% or more of oleic acid having antibacterial properties.

The above-mentioned camellia oil is converted into starch or starch by cyclodextrin glucanotransferase (B. Mac).
It is dispersed or dissolved in water together with a starchy mixture solution in which a starch-degrading enzyme produced by erans bacteria (hereinafter simply referred to as enzyme) is mixed. If necessary, a water-soluble resin such as methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, etc. may be contained. Incidentally, in the above-mentioned starchy mixture solution obtained by mixing an enzyme with starch, the starch is decomposed into a starchy cyclic oligosaccharide by the action of the enzyme.
A mixed solution containing α-cyclodextrin cyclically bonded to each other, β-cyclodextrin cyclically bonded to 7 cyclics, γ-cyclodextrin cyclically bonded to 8 cyclics, cyclodextrin cyclically bonded to 6 or less cyclically, and the like. There is. The temperature at which the camellia oil is dispersed or dissolved in water together with the starch or the starchy mixture may be set appropriately within the range of -10 to 120 ° C. The same applies when a water-soluble resin is added. In addition, camellia oil is 0.0
1% to 40% is added, but if it is less than 0.01%, the antibacterial effect is not sufficient, and if you try to manufacture it at a rate of less than 0.01%, the rate will be accurately measured for small lot production. Difficult to produce variations in quality. Also, 40
%, There is no further improvement in the antibacterial effect, and the oil content is too high to cause embossing, which is economically unfavorable.

The above-mentioned solution is made into a fine granular powder by a known spray drying method, and the drying temperature is-
It may be set appropriately in the range of 20 to 160 ° C. Incidentally, when camellia oil is used, camellia oil is not completely dissolved in water and a part of the oil is in a state of floating on the liquid surface, but in this case as well, spray drying while thoroughly stirring, A fine-grained antimicrobial agent is created.

Since the antibacterial agent thus prepared is water-soluble and is a natural material, it is harmless to humans and plants, and when it is disposed of in water and sewers, it purifies bacteria in wastewater. Etc. will not be affected.

In order to fix the antibacterial agent to the fiber material, the antibacterial agent is dissolved in water at a rate of 0.01 to 30%, and this solution is applied to the fiber material, sprayed, or Is immersed in the above solution for 2 seconds to 30 minutes, and then -20 to 1
It may be dried appropriately in the range of 60 ° C. This fiber material is
It may be a filamentous fibrous material or a knitted or woven textile product,
In addition, as the material, protein fibers such as cotton, hemp, silk (silk) and wool are preferable, but acrylic fibers and the like can also be applied.

The fiber material thus prepared has antibacterial properties, and most of the antibacterial agent is not washed off and remains adhered and remains in the fiber material even after washing for several tens of times, and the antibacterial effect is continuously maintained for a long period of time. It became something to do. Although the detailed reason for this is unknown, since the antibacterial agent is water-soluble, it penetrates into the inside of the fiber, and the surface-active emulsifying action of the starch or starchy mixture contained in the antibacterial agent is also present. However, it is presumed that the adhesiveness after drying firmly adheres to the surface of the fiber material. It is also presumed that it was denatured by heat and other factors and became insoluble in water.

In addition, when the antibacterial agent is dissolved in the dye solution in the dyeing step, the antibacterial fiber material can fix the antibacterial agent together with the dyeing process. In addition, it has extremely high practical value.

[0013]

EXAMPLES Examples of the present invention will be shown below.

[Example 1] Production of antibacterial agent; camellia oil {Tsubaki pure oil solution, Tsubaki Motoshima Co., Ltd.} 10
0 cc and starch {Dixiace, Shimizu Port Refinery Co., Ltd.} 1
And 000 g were dispersed and dissolved in 10000 cc of water and stirred sufficiently. This solution (dispersion) is made into fine particles by a spray dryer {powder manufacturing machine, Shimizu Minato Sugar Co., Ltd.} 9
After drying at 0 ° C., 1001 g of antibacterial agent was obtained.

Production of antibacterial fiber material: 7.5 g of the antibacterial agent obtained above was dissolved in 1500 cc of warm water for 5 minutes, and this solution was mixed with animal fiber (wool cloth), vegetable fiber (flat cloth), 1000g of rayon (fukin) each
Was impregnated for 5 minutes and dried at 80 ° C. for 30 minutes to adhere the antibacterial agent to the fiber surface.

Antibacterial effect test of antibacterial fiber material: antibacterial fiber material (wool cloth, flat cloth,
Fukin, etc. are processed and evaluated by the Japan Chemical Fiber Testing Association for antibacterial and deodorant products Manual Shake Flask Method (Test Bacteria: Klebsiella pneumoniae ATCC 435
2. Shaking conditions: List action 330 rpm x 1 hour,
The sterilization rate was measured with a test piece mass: 0.75 g). The results are shown in Table 1. The measurement results of unprocessed products are also shown.

[0017]

[Table 1]

Safety test of antibacterial fiber material; gauze cloth treated with 0.1% aqueous solution of the antibacterial agent obtained above,
Regarding towel cloth, knit cloth, and flat cloth, Ministry of Health and Welfare No. 3
The amount of free formaldehyde (content of formalin for baby products) was tested in accordance with the test method for baby products among the test methods specified in No. 4 (1974). The results are shown in Table 2.

[0019]

[Table 2]

[Example 2] Production of antibacterial agent; camellia oil {Tsubaki pure oil liquid, Tsubaki Motoshima Co., Ltd.} 15
0 cc and starch {Dixiace, Shimizu Port Refinery Co., Ltd.} 5
50 g and cyclodextrin glucanotransferase 550 g were dispersed and dissolved in 10000 cc of water, and stirred sufficiently. This solution (dispersion) was made into fine particles with a spray dryer {powder manufacturing machine, Shimizu Minato Sugar Co., Ltd.} and dried at 90 ° C. to obtain 1123 g of the antibacterial agent.

Production of antibacterial fiber material: 7.5 g of the antibacterial agent obtained above was dissolved in 1500 cc of warm water for 5 minutes, and this solution was mixed with animal fiber (wool cloth), vegetable fiber (flat cloth), 1000g of rayon (fukin) each
Was impregnated for 5 minutes and dried at 80 ° C. for 30 minutes to adhere the antibacterial agent to the fiber surface.

Antibacterial effect test of antibacterial fiber material; antibacterial fiber material (wool cloth, flat cloth,
Fukin, etc. are processed and evaluated by the Japan Chemical Fiber Testing Association for antibacterial and deodorant products Manual Shake Flask Method (Test Bacteria: Klebsiella pneumoniae ATCC 435
2. Shaking conditions: List action 330 rpm x 1 hour,
The sterilization rate was measured with a test piece mass: 0.75 g). The results are shown in Table 3. The measurement results of unprocessed products are also shown.

[0023]

[Table 3]

[Example 3] Production of antibacterial agent; camellia oil {Tsubaki pure oil solution, Tsubaki Motoshima Co., Ltd.} 15
0 cc and starch {Dixiace, Shimizu Port Refinery Co., Ltd.} 1
000 g and polyvinyl alcohol 20 g were added to water 10
It was dispersed and dissolved in 000 cc and stirred sufficiently. This solution (dispersion liquid) is made into fine particles with a spray dryer {powder manufacturing machine, Shimizu Minato Sugar Co., Ltd.} and dried at 90 ° C.
20 g of antibacterial agent was obtained.

Production of antibacterial fiber material: 7.5 g of the antibacterial agent obtained above was dissolved in 1500 cc of warm water for 5 minutes, and this solution was mixed with animal fiber (wool cloth), vegetable fiber (flat cloth), 1000g of rayon (fukin) each
Was impregnated for 5 minutes and dried at 80 ° C. for 30 minutes to adhere the antibacterial agent to the fiber surface.

Antibacterial effect test of antibacterial fiber material; antibacterial fiber material (wool cloth, flat cloth,
Fukin, etc. are processed and evaluated by the Japan Chemical Fiber Testing Association for antibacterial and deodorant products Manual Shake Flask Method (Test Bacteria: Klebsiella pneumoniae ATCC 435
2. Shaking conditions: List action 330 rpm x 1 hour,
The sterilization rate was measured with a test piece mass: 0.75 g). The results are shown in Table 3.

[Example 4] Production of antibacterial agent; camellia oil {Tsubaki pure oil liquid, Tsubaki Motoshima Co., Ltd.} 15
0 cc and starch {Dixiace, Shimizu Port Refinery Co., Ltd.} 1
000 g, cyclodextrin glucanotransferase 10 g, and polyvinyl alcohol 10 g,
It was dispersed and dissolved in 10000 cc of water and stirred sufficiently.
This solution (dispersion) is made into fine granules by a spray dryer {powder manufacturing machine, Shimizu Minato Sugar Co., Ltd.} and dried at 90 ° C.,
1028 g of antibacterial agent was obtained.

Production of antibacterial fiber material: 7.5 g of the antibacterial agent obtained above was dissolved in 1500 cc of warm water for 5 minutes, and animal fiber (wool cloth), vegetable fiber (flat cloth), 1000g of rayon (fukin) each
Was impregnated for 5 minutes and dried at 80 ° C. for 30 minutes to adhere the antibacterial agent to the fiber surface.

Antibacterial effect test of antibacterial fiber material; antibacterial fiber material (wool cloth, flat cloth,
Fukin, etc. are processed and evaluated by the Japan Chemical Fiber Testing Association for antibacterial and deodorant products Manual Shake Flask Method (Test Bacteria: Klebsiella pneumoniae ATCC 435
2. Shaking conditions: List action 330 rpm x 1 hour,
The sterilization rate was measured with a test piece mass: 0.75 g). The results are shown in Table 3.

[Example 5] Production of antibacterial agent: An antibacterial agent was produced in the same manner as in Example 1.

Manufacture of antibacterial fiber material: 0.375 g of the antibacterial agent obtained above was dissolved in 1500 cc of warm water for 5 minutes, and animal fiber (wool cloth), vegetable fiber (flat cloth), 100 each of rayon (fukin)
0 g was impregnated for 5 minutes and dried at 80 ° C. for 30 minutes to adhere the antibacterial agent to the fiber surface.

Antibacterial effect test of antibacterial fiber material; antibacterial fiber material (wool cloth, flat cloth,
Fukin, etc. are processed and evaluated by the Japan Chemical Fiber Testing Association for antibacterial and deodorant products Manual Shake Flask Method (Test Bacteria: Klebsiella pneumoniae ATCC 435
2. Shaking conditions: List action 330 rpm x 1 hour,
The sterilization rate was measured with a test piece mass: 0.75 g). The results are shown in Table 3.

[0033]

As described above, since the antibacterial agent of the present invention uses camellia oil extracted from natural camellia wood as a raw material, it is possible to suppress the generation and reproduction of mold and fungi, or to kill them. Even when it is disposed of in water and sewage, it does not affect the purification bacteria in the wastewater and does not pollute the environment.

Further, since the antibacterial agent is water-soluble, it has high permeability when it is fixed to the fiber material, and the antibacterial agent reaches and adheres to the inside of the fibrin. Due to the action of the starch or starch cyclic oligosaccharide contained in the antibacterial agent or the water-soluble resin, the sufficiently dried fibrous material does not wash away the antibacterial agent even after washing with water for several tens of times, and Therefore, the antibacterial effect can be maintained and continued.

Further, when the fiber material having the above-mentioned antibacterial property is prepared, for example, an antibacterial agent may be added to the dyeing solution and the immersion treatment may be carried out. Since the process added to the conventional treatment process is substantially eliminated, it has an extremely high practical value in industrial production.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location // (A01N 65/00 63:00) (72) Inventor Manabu Maki Machi Yachiyodai-nishi, Yachiyo-shi, Chiba 10-32-3 (72) Inventor Rika Mimaki Yachiyodainishi, Yachiyo-shi, Chiba 10-32-3

Claims (3)

[Claims] 1. Camellia oil extracted from natural camellia oil 0.01 to
An antibacterial agent characterized in that 40% and a starchy mixture of starch or cyclodextrin glucanotransferase mixed with starch are dispersed or dissolved in water and spray-dried to form fine particles. 2. Camellia oil 0.01 to extracted from natural camellia wood
40%, starch or a starchy mixture of cyclodextrin glucanotransferase mixed with starch, and a water-soluble resin are dispersed or dissolved in water and spray-dried to form fine particles. Agent. 3. An antibacterial fiber material obtained by dissolving the antibacterial agent according to claim 1 or 2 in water, impregnating the solution with water, and drying.