HK1089215B - Antibacterial pectocellulose - Google Patents

Description

Antibacterial pectocellulose

Background

The present invention relates to an antibacterial cellulose having an antibacterial agent bonded to a pectic cellulose, particularly a pectic cellulose fiber or a pectic cellulose fiber fabric having an ionic antibacterial agent supported thereon, and a method for producing the same.

Cellulose-based fibers such as cotton fibers, which are representative of natural fibers, have been produced in large quantities on earth, and are valuable fibers possessing recycling properties that have been frequently mentioned recently. In addition, the cotton fiber itself is a comfortable fiber material with moderate hygroscopicity and softness without other improvements. However, in recent years, food poisoning events have occurred with 0 to 157 bacteria, and events caused by various bacteria such as legionella bacteria in 24-hour bathing pools have occurred many times. Further, it has been reported that bacteria, fungi, ticks and the like grow due to increase in humidity and insufficient ventilation accompanying the increase in air tightness of houses. Under such circumstances, the concern for bacteria among consumers is increasing year by year. Various antibacterial processed products have been introduced in the market in response to such a tendency, and more specifically, products in various fields such as fiber products, kitchen products, automobile and toilet products, home electric appliances, and housing equipment are targeted for antibacterial processing.

It is known that antibacterial metals such as silver and copper are used as antibacterial agents in antibacterial processing of cellulosic fiber products such as cotton. Many antibacterial fiber products using silver ions are eluted with silver ions to develop antibacterial properties, and zeolite, clay mineral, glass, and the like are known as carriers for such eluted agents. Further, a method of immersing a cellulose-based fiber product in a mixed solution containing these antibacterial agents and a urethane resin and then drying the same to impart antibacterial properties is known. There is also a method of spraying a mixed liquid containing an antibacterial agent onto fibers using a sprayer. However, these cellulose-based fiber products obtained by conventional antibacterial processing have a problem that the antibacterial agent is released from the fibers after a small number of washing, and as a result, the antibacterial effect is reduced in a short period of time. Further, there have been disclosed a method of imparting antibacterial properties by immersing cellulose fibers in a spinning oil containing a methylol resin and a crosslinking catalyst (patent document 1/japanese patent application laid-open No. 2000-355880), a method of imparting antibacterial properties by binding metal ions such as silver ions and copper ions to cotton fibers as a spacer (patent document 2/japanese patent application laid-open No. 2000-204182), and the like, but none of them satisfies the requirement for the persistence of antibacterial properties.

Therefore, a method for easily, stably and continuously bonding a functional substance such as an antibacterial agent to a fiber is required. Natural fibers, such as cotton fibers, are polysaccharides composed mainly of cellulose and have anionic charges derived from hydroxyl groups of glucose, which is a constituent component of the polysaccharide. However, such charges are very weak and cannot directly bind other inorganic or organic functional substances to the cotton fibers, so research has been conducted to develop a method for directly binding the functional substances to the cotton fibers after the negative charges are chemically enhanced. In addition, a method has been developed in which a functional substance such as an antibacterial agent is adsorbed and formed in a fine-powder ceramic, and then introduced into cotton fibers. In any case, pretreatment by an overstimulated chemical reaction is usually required, and the original properties of the cotton fiber are damaged after the pretreatment, and the treatment cost is high, so that the pretreatment becomes a bottleneck link for endowing the cotton fiber with functionality. Therefore, a method is required in which a functional substance such as an antibacterial agent can be easily and stably incorporated into, for example, cotton fibers.

The object of the present invention is to provide a cellulose having an antibacterial agent incorporated therein, which is derived from a natural cellulose fiber, and an antibacterial pectic cellulose fiber or pectic cellulose fiber fabric having an antibacterial agent supported on pectic cellulose fiber, wherein the antibacterial agent is stably and permanently incorporated in the cellulose, and the antibacterial agent is not easily removed by washing.

Disclosure of The Invention

The present inventors have conducted extensive studies to solve the above problems and as a result, have found that an antibacterial pectocellulose comprising pectin contained in pectocellulose and an inorganic compound antibacterial agent or an organic compound antibacterial agent can be provided by a method comprising treating pectocellulose or pectocellulose fabric with at least one chemical substance selected from the group consisting of acids, bases, salts thereof, chelating agents and pectinolytic enzymes to reduce the pectin content in pectocellulose to 1 to 80% by mass before the treatment, and binding an ionic inorganic compound antibacterial agent or an organic compound antibacterial agent to pectocellulose or pectocellulose fabric.

The present invention is an antibacterial pectocellulose comprising a pectocellulose obtained by incorporating an inorganic antibacterial agent or an organic antibacterial agent into a pectin contained in a pectocellulose.

The binding state includes chemical binding, and ionic inorganic compound antibacterial agent or organic compound antibacterial agent is bound to an active group having an ionic binding ability in pectin contained in the pectocellulose by an ionic bond. The above-mentioned pectic cellulose is not particularly limited, and japanese paper containing paper mulberry (Edgeworthia) and triloba (paper mulberry), cotton, hemp, rayon, kenaf, and pectic cellulose derived from a material selected from these raw materials can be used.

Further, the present invention relates to

(1) And treating the pectic cellulose fiber or pectic cellulose fiber fabric with at least one chemical substance selected from the group consisting of acids, bases, salts thereof, chelating agents and pectinolytic enzymes to reduce the pectin content in the pectic cellulose fiber to 1 to 80% by mass before the treatment, wherein the treated pectic cellulose fiber or pectic cellulose fiber fabric is loaded with an ionic inorganic compound antibacterial agent or an organic compound antibacterial agent to obtain an antibacterial pectic cellulose fiber or antibacterial pectic cellulose fiber fabric.

(2) And (1) the pectocellulose fiber or pectocellulose fiber fabric, wherein the pectocellulose fiber or pectocellulose fiber fabric is made of cotton or hemp

(3) The pectic cellulose fiber or pectic cellulose fiber fabric according to item (1) or (2), wherein the acid is an inorganic acid such as phosphoric acid or sulfuric acid, or an organic acid such as acetic acid, and the base is a base such as sodium hydroxide, potassium hydroxide or calcium hydroxide, the salt is a salt of the acid with the base, and the chelating agent is ethylenediaminetetraacetic acid, nitrilotriacetic acid or the like.

(4) The pectocellulose fiber or cellulose fiber fabric according to any one of (1) to (3), wherein the inorganic antibacterial agent is silver, copper, titanium or a compound containing any of these metals, and the organic antibacterial agent is quaternary ammonium, chitin, chitosan or the like.

(5) A process for producing an antibacterial pectocellulose fiber or an antibacterial pectocellulose fiber fabric, which comprises treating a pectocellulose fiber or a pectocellulose fiber fabric with at least one chemical substance selected from the group consisting of an acid, an alkali, a salt thereof, a chelating agent and a pectinolytic enzyme to reduce the pectin content in the pectocellulose fiber to 1 to 80% by mass before the treatment, and loading an ionic inorganic compound antibacterial agent or an organic compound antibacterial agent on the treated pectocellulose fiber or pectocellulose fiber fabric to form the antibacterial pectocellulose or antibacterial pectocellulose fabric.

(6) And a fibrous product comprising the pectin cellulose fiber of any one of (1) to (4).

Best Mode for Carrying Out The Invention

Hereinafter, the best mode for carrying out the present invention will be described.

The present invention relates to an antibacterial pectocellulose comprising pectocellulose wherein an inorganic antibacterial agent or an organic antibacterial agent is incorporated in the pectin contained in the pectocellulose. The inorganic antibacterial agent is preferably silver, copper or titanium or a metal compound containing these metals, and the organic antibacterial agent is preferably quaternary ammonium, chitin or chitosan.

As an embodiment of the present invention, an antibacterial pectic cellulose fiber composed of the aforementioned antibacterial pectic cellulose can be provided, but an antibacterial composite cellulose can be provided regardless of the form of "fiber".

Therefore, the present embodiment can provide the antibacterial pectocellulose itself or various fiber products containing the antibacterial pectocellulose fiber, and can also provide a fiber product containing the antibacterial pectocellulose fiber alone or mixed or compounded with other fibers.

Specifically, the pectin cellulose fiber or the pectin cellulose fiber fabric is treated with at least one chemical substance selected from the group consisting of acids, bases, salts thereof, chelating agents and pectin decomposing enzymes to reduce the pectin content in the pectin cellulose fiber to 1 to 80% by mass before the treatment, and the treated pectin cellulose fiber or the pectin cellulose fiber fabric is loaded with an ionic inorganic compound antibacterial agent or an organic compound antibacterial agent to form an antibacterial pectin cellulose fiber or an antibacterial pectin cellulose fiber fabric.

The method for quantifying pectin according to the present invention is carried out as follows. The pectin cellulose fiber or the pectin cellulose fiber fabric was heat-treated in 0.1M sodium hydroxide solution at 90 ℃ for 60 minutes, and the amount of galacturonic acid in the solution was determined by the carbazole sulfuric acid method, and this was used as the pectin content. More specifically, 0.125mL of the test solution treated with sodium hydroxide was mixed with 0.125mL of a 0.2 mass% carbazole solution (ethanol solution), and a 1.5mL31.5n sulfuric acid solution was added thereto, followed by cooling and thoroughly mixing. Then, this mixed solution was heated at 75 ℃ for 20 minutes, left to cool to room temperature, and the absorbance was measured at a wavelength of 570nm with a spectrophotometer. And preparing a standard curve according to the measurement of the known quantity of galacturonic acid, reading the content of galacturonic acid in the measured liquid according to the measured absorbance in the standard curve, and calculating the content of pectin in the pectin cellulose fiber by using the read data.

The pectic cellulose fiber in the present invention is a natural fiber containing pectin, and the pectic cellulose is a cellulose containing pectin. It is important that the cellulose or the fiber contains pectin. Examples of the pectic cellulose fibers include cellulose fibers such as cotton, hemp and rayon, and preferably cotton. In addition, as described above, Japanese paper and kenaf containing paper mulberry and twigs can be used. Or using these starting material forms separately. Or a mixture obtained by mixing at least two of them is used. The pectin cellulose fiber is naturally used, and the content of pectin in cotton is usually 7 to 8 mass% and the content of pectin in hemp is usually about 10 to 11 mass% depending on the kind and the place of production.

The acid used in the present invention may be an organic acid or an inorganic acid. The inorganic acid is not particularly limited, and examples thereof include phosphoric acid, sulfuric acid, nitric acid, sulfonic acid, hydrochloric acid, boric acid and the like, and phosphoric acid and sulfuric acid are preferred. The organic acid is not particularly limited, and examples thereof include acetic acid, butyric acid, carboxylic acid, lactic acid, formic acid, oxalic acid, tartaric acid, citric acid, malic acid, sulfamic acid, pyruvic acid and the like, and acetic acid and citric acid are preferred.

The base is not particularly limited, and sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, adenine and the like are exemplified, and sodium hydroxide, potassium hydroxide and calcium hydroxide are preferred.

The salt may be any of the above acids and bases, and preferably sodium sulfate, potassium sulfate, or dipotassium hydrogen phosphate.

The chelating agent is not particularly limited, and specific examples thereof include ethylenediaminetetraacetic acid or a salt thereof, nitrilotriacetic acid or a salt thereof, citric acid or a salt thereof, etidronic acid, L-aspartic acid diacetic acid, L-glutamic acid diacetic acid, sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate, etc., preferably ethylenediaminetetraacetic acid or a salt thereof, nitrilotriacetic acid or a salt thereof, and sodium hexametaphosphate.

As the pectinolytic enzyme of the present invention, protopectinase is preferably used. Protopectinase is a generic term for enzymes having an activity of liberating insoluble protopectin present in plant tissues into water-soluble pectin. In the present invention, as the pectinolytic enzyme, a microorganism containing or producing the enzyme or a treated product thereof can be used. Commercially available products may also be used. Specific examples of the microorganism capable of producing a pectinolytic enzyme used in the present invention include the following microorganisms.

1. Examples of the yeast microorganism include the following. Trichosporon virens belonging to the genus Trichosporon, Engomyces geotrichum and Neurospora linderae belonging to the genus Neurospora; endophytic fungus Endomycopsis veralis, which is a microorganism belonging to the genus Endomyces; saccharomyces microorganisms such as Saccharomyces cerevisiae, Saccharomyces delbrueckii, and Saccharomyces cerevisiae; schizosaccharomyces octasporum, which is a microorganism of the genus Schizosaccharomyces; pichia Orientalis, Pichia polymorpha, Pichia farinosa as a microorganism of the genus Pichia; hansenula Tusella, Hansenula parvum as microorganisms of Hansenula; debaryomyces hansenii, Debaryomyces castellii, as a microorganism of the genus Debaryomyces; hansenula pseudomondii and Hansenula polymorpha as microorganisms of the Hansenula pseudomondii genus; torulopsis toruloides and Torulopsis pinelliae as microorganisms of the genus Torulopsis; candida krusei, Candida globosa, and Candida machiensis as Candida microorganisms; and Kluyveromyces fragilis, Kluyveromyces lactis, Kluyveromyces marxianus, Kluyveromyces drosophilus, and the like and variants of these microorganisms, such as Trichosporon furilans SNO-3 ATCC42397, Candida krusei IFO 0013, Candida globosa IFO 1353, Candida machiensis AKU4587, Debaryomyces hansenii IFO 0794, Debaryomyces castellii IFO 1359, Engomyces geotrichum IFO 9541, Neurospora lindanensis AKU 4206, Farner Bostonia sordida IFO 0115, Hansenula cinerea IFO 1012, Hansenula terrestris IFO 1411411411417, Hansenula pseudostellerii IFO 0117, Hansenula parvisceruloides IFO 0975, Kluyveromyces IFO 0288, Kluyveromyces lactis IFO, Kluyveromyces maruyveromyces IFO 7, Kluyveromyces lactis yeast IFO 1090, Pichia pastoris IFO 4251, Pichia farinosa 4251, and Pichia farinosa, Grape juice yeast IFO 0565, Bayer yeast IFO1047, Delbert yeast IFO 0285, fermentation yeast IFO 0422, Schizosaccharomyces pombe IFO 0353, Torulopsis toruloides IFO 0648, Torulopsis pinicola IFO 0741, Neurospora capsulata IFO 0672, and Endomycopsis vernalis AKU 4210;

2. examples of the microorganism of the genus Bacillus include the following. Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus cereus, Bacillus circulans, Bacillus coagulans, Bacillus firmus, Bacillus licheniformis, Bacillus pumilus, Bacillus macerans, and the like and variants of these strains, such as Bacillus subtilis IFO 3108, 3134, 3336, 3513, 12112, 12113, 12210, 13719, 13721, 14117 and 14140, Bacillus amyloliquefaciens IFO 14141, Bacillus cereus IFO 3002 and 3132, Bacillus circulans IFO 13632, Bacillus coagulans IFO 12583, Bacillus firmus IFO 3330, Bacillus licheniformis IFO 14206, Bacillus pumilus IFO 12087, and Bacillus macerans IFO 3490.

3. Examples of the filamentous microorganism include the following. Galactomyces reussiiL, Aspergillus oryzae, Aspergillus sojae, Rhizopus oryzae, Trametes sanguineus, Trametes alba, Trametes cubensis, Trametes cinnabarinus, Trametes versicolor, Trametes herbarum, Trametes angustifolia, and the like and variants of these strains, for example, Galactomyces reussiiLIAM 129, Trametes sanguineus IFO 6490, 6491, Trametes orientalis IFO 6483, 6484, Trametes alba IFO 6434, 6510, Trametes cubensis IFO 9285, Trametes versicolor IFO 4946, Trametes herbarum IFO6264, Trametes angustifolia IFO 9286, Aspergillus oryzae IFO 4277, Aspergillus sojae IFO 4200, and Rhizopus oryzae IFO 4734.

Among the above-mentioned pectinolytic enzyme-producing bacteria, Kluyveromyces marxianus (IFO 0277), Kluyveromyces fragilis (IFO 0288), Trichosporon furilans SNO-3(ATCC 42397), Galactoomyces reussil (IAM 129), Bacillus subtilis (IFO 3134), or Thrombus sanguineus (IFO 6490) is preferable.

The enzyme used in the present invention is obtained by culturing the above-mentioned microorganism in a conventional manner. Such culture conditions are not always consistent depending on the microorganism used, and suitable conditions are selected to maximize the enzyme production as much as possible. The medium used for the culture is not particularly limited, and any medium to which various nutrients for ordinary culture are added can be used. The medium may be supplemented with starch, peptone, casein hydrolysate, yeast extract, glucose, or, as the case may be, inorganic salts such as phosphate, magnesium salt, and potassium salt. In addition, nutrient sources such as wheat bran and soybean powder can also be added.

In these media, the conditions for culturing the microorganism are appropriately selected so that the production amount of the target enzyme is maximized, and the culture is usually carried out at about 20 to 37 ℃ for about 10 to 50 hours. The culture may be performed by shaking, standing, aeration-agitation or mass culture.

In the culture solution obtained as described above, the pectocellulose fiber or pectocellulose fiber fabric may be directly subjected to a soaking treatment, and preferably an enzyme solution obtained by removing all or part of solid components such as cells by centrifugation, filtration, dialysis, or the like using the culture solution. Further, an enzyme solution obtained by purifying such an enzyme solution by a conventional method such as column chromatography or the like and diluting the enzyme solution to an appropriate concentration can be used. In addition, a substance which promotes the decomposition of pectin, such as an inorganic salt or a surfactant, may be added to the enzyme solution.

Pectin cellulose fibers contain so-called impurities such as wax, pectin, and protein in addition to cellulose, and this hinders the hydrophilicity of pectin cellulose fibers. Therefore, the method of refining is a method in which, for example, pectin cellulose fibers or pectin cellulose fiber cloth are immersed in a mixture of a refining aid containing a surfactant as a main component together with an alkali, and the resultant is treated at a high temperature (about 90 ℃ or higher) to completely remove impurities contained in the pectin cellulose fibers.

The present invention is characterized in that, focusing on that most of pectin, which is an impurity contained in pectic cellulose fibers, is an acidic polysaccharide and has high reactivity, pectin contained in pectic cellulose fibers is not completely removed, but pectic cellulose fibers or pectic cellulose fiber cloth are treated with at least one chemical substance selected from the group consisting of acids, bases, salts thereof, chelating agents and pectinolytic enzymes under the condition that the hydrophilicity of pectic cellulose fibers is not impaired, so that the content of pectin in pectic cellulose fibers is reduced to 1 to 80 mass% before the treatment, and active groups having an ion-binding ability are generated in pectin.

The pectic cellulose fibers or pectic cellulose fiber fabrics are treated with at least one chemical substance selected from the group consisting of acids, bases, salts thereof, chelating agents and pectinolytic enzymes, and then washed with distilled water or an acid as required. And then dried to obtain a treated pectic cellulose fiber or pectic cellulose fiber fabric (pectic cellulose fiber or pectic cellulose fiber fabric having an active group having an ion-binding ability). As the treatment conditions for the treatment with any of an acid, a base, a salt thereof and a chelating agent, the concentration of these compounds is usually about 0.01 to 100mM, preferably about 0.1 to 50mM, the treatment temperature is usually about 5 to 40 ℃ and preferably about 15 to 25 ℃ and the treatment time is usually about 0.1 to 5 hours, preferably about 1 to 2 hours, for convenience of the treatment. When the pectocellulose fiber or pectocellulose fiber fabric is treated with the pectinolytic enzyme, the pectocellulose fiber or pectocellulose fiber fabric may be treated by directly immersing in the culture solution of the pectinolytic enzyme obtained above, and preferably a pectinolytic enzyme solution obtained by removing all or a part of the solid components such as cells from the culture solution of the pectinolytic enzyme by a method such as centrifugation, filtration, or dialysis. Alternatively, a pectinolytic enzyme solution obtained by diluting a pectinolytic enzyme obtained by refining by a conventional method such as column chromatography to an appropriate concentration may be used. The pectin-degrading enzyme solution may contain a substance for promoting pectin degradation, the above salt (preferably an inorganic salt), for example, a cationic surfactant, an anionic surfactant or a nonionic surfactant. The concentration of the pectinolytic enzyme added is usually about 1 to 5000 units/mL (aqueous solution), preferably about 1000 to 3000 units/mL (aqueous solution). Wherein the 1 unit of pectinolytic enzyme is defined as an amount of enzyme that decomposes the white layer in lemon peel and releases pectin equivalent to 1. mu. mol of galacturonic acid in 1 hour. The treatment conditions for treating the pectocellulose fibers or the pectocellulose fiber cloth with the pectinolytic enzyme are usually about 0.5 to 24 hours, preferably about 2 to 10 hours, the pH of the aqueous solution of the pectinolytic enzyme is usually about 5 to 10, and the soaking treatment temperature is usually about 30 to 55 ℃, preferably about 30 to 40 ℃. For the adjustment of pH, a buffer such as a phosphate buffer solution can be used as an aqueous solution.

The pectocellulose fiber or pectocellulose fiber fabric (pectocellulose fiber or pectocellulose fiber fabric having an active group having an ion-binding ability) treated by the above method is loaded with an antibacterial agent. The antibacterial agent may be either an inorganic antibacterial agent or an organic antibacterial agent.

Specific examples of the inorganic antibacterial agent include silver bromide or iodine complex salts, metal ions such as silver, copper, zinc, platinum, nickel, cobalt, chromium, and titanium, and metal compounds such as oxides and hydroxides of these metals. Preferably silver. These inorganic antibacterial agents may be used alone in 1 kind, or in combination of plural kinds.

Examples of the organic antibacterial agent include quaternary ammonium, thiabendazole, and バイアジン, and polycations such as chitin and chitosan. Quaternary ammonium and chitosan are preferred. These organic antibacterial agents may be used alone in 1 kind, or in combination of plural kinds.

When the pectic cellulose fiber or pectic cellulose fiber fabric is treated with the antibacterial agent, the concentration of the antibacterial agent is usually 0.1 to 100mM, preferably about 1 to 30mM, the treatment temperature is usually 5 to 40 ℃, preferably about 15 to 25 ℃, and the treatment time is usually 0.1 to 5 hours, preferably about 1 to 2 hours.

The method for producing a fabric using the antibacterial pectic cellulose fibers carrying an antibacterial agent in the present invention is not particularly limited, and a known method may be used. The antibacterial pectin cellulose fiber carrying the antibacterial agent can be woven into a fabric by, for example, plain weaving, satin weaving, twill weaving, wale weaving, leno weaving, basket weaving, or the like. The antibacterial pectocellulose fiber carrying the antibacterial agent can be woven into a fabric by, for example, plain weaving, rib weaving, or cross weaving, straight weaving such as single bar warp flat weaving or single bar warp flat weaving, or lace weaving. Further, a fabric is produced using pectocellulose fibers not carrying an antibacterial agent, and the antibacterial agent can be carried on the fabric by the present invention. In this case, the method for producing the fabric is not particularly limited, and a known method may be used. Examples of the fabric include the above.

The pectin cellulose fibers and pectin cellulose fabrics carrying an antibacterial agent of the present invention obtained by the above-mentioned method can be used for various fiber products. In addition, the pectin cellulose of the present invention can be provided as an antibacterial cellulose material.

As the fiber product of the present invention, clothing, for example; household sundries such as handkerchiefs, women's ornaments, ribbons, towels, rags, wipes (leather shoes, beds, glasses, etc.) or curtains; bed clothes such as blankets, quilt covers, bed sheets, pillow covers, cushions or cushions; furniture and indoor articles such as carpets, curtains and wallpaper; medical materials such as gauze, mask, and cap; recreational articles such as materials for handicraft suit tailor and the like. The fiber product of the present invention may be composed of only the pectocellulose fiber fabric carrying the antibacterial agent of the present invention, or may be used only in a part of the fiber product. The fiber product of the present invention may be composed of only the antimicrobial agent-carrying pectin cellulose fiber of the present invention.

Examples

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto

[ example 1 ]

Unrefined cotton cloth for bathrobes (cotton origin: Pakistan, using cotton thread count: 20 (same length and width), weave pattern: plain weave, sample size: width 8 cm. times.length 8cm, mass: 0.68g) was treated in a pectinolytic enzyme aqueous solution (this treatment is called bioscouring). That is, the above-mentioned sample was soaked in a solution containing 3000 units/mL (aqueous solution) of a pectinolytic enzyme and a surfactant (ウオミン TE, manufactured by imperial dentistry corporation) in an amount of 0.1 mass% for 2 hours at room temperature (hereinafter, such a treated product is referred to as bioscouring cloth).

The bio-scouring cloth was sufficiently washed with water and then dried (hereinafter, this cloth is referred to as a bio-chemical cloth). This ionized cloth was put into 50mL of distilled water, and after stirring, the pH of the distilled water was measured to be 5.2. The ionized cloth was taken out from the distilled water and placed in a glass vessel, and reacted at room temperature for 1 hour while stirring with adding a silver nitrate solution to a final concentration of 10 mM. The ionized cloth thus treated with the silver nitrate solution (hereinafter referred to as silver-treated cloth) was taken out from the solution, sufficiently wrung out to remove the solution, and sufficiently washed with distilled water. The difference between the pH of the washing water formed from this distilled water and the pH (5.2) measured above was determined as pH-logH⁺The amount of silver ions bound to the cloth was calculated, and as a result, about 6 millimoles of silver ions were bound to the silver treated cloth of the present invention. The content of pectin in the cotton fibers of the bio-refined cloth was measured by the above-mentioned pectin quantitative method, and as a result, the content of pectin was 3.4 mass% with respect to the cotton fibers.

As a control, the unrefined cotton bathrobe cloth (cotton origin: Pakistan, using cotton count: 20 (same length and breadth), weave pattern: plain weave, sample size: width: 8 cm. times. length: 8cm, mass: 0.68g) was prepared by heat-treating in 1N sodium hydroxide solution at 90 ℃ for 1 hour to prepare a cloth (hereinafter referred to as chemically refined cloth). The chemical scouring cloth was treated in the same manner as the silver nitrate solution applied to the biological scouring cloth (referred to as a control silver treated cloth). As in the case of the silver-treated cloth of the present invention, from the results of calculating the amount of silver ions in the control silver-treated cloth, it was not confirmed that silver ions were bound in the control silver-treated cloth. The pectin content in the cotton fibers of the chemically refined cloth was measured by the above-described pectin quantitative method, and was 0 mass% with respect to the cotton fibers.

The binding amounts of silver ions in the silver-treated cloth of the present invention and the control silver-treated cloth were measured by a fluorescence X-ray measuring apparatus (manufactured by shimadzu corporation), and were 6.5 mmol and 1 mmol or less, respectively.

In order to evaluate the antibacterial properties of the silver-treated cloths of the present invention and the control silver-treated cloth, the following method was used. That is, 5mL of each of two culture media to which Pseudomonas aeruginosa was added (culture media containing 2 mass% glucose, 0.5 mass% peptone, and 0.5 mass% yeast extract (hereinafter referred to as GYP medium)), each of the silver-treated cloths of the present invention and control silver-treated cloth samples (each sample size: 2.5 cm. times.2.5 cm, and each sample mass: 0.08g) prepared as described above were put, and Pseudomonas aeruginosa was cultured (as culture conditions, temperature: 30 ℃ C., culture time: 24 hours), after each culture was completed, 1mL of each culture solution was withdrawn, diluted 5-fold with distilled water, and the absorbance (at 660 nm) was measured, using the absorbance value of each as the antibacterial index, the absorbance measurement results of the silver-treated cloths of the present invention and control silver-treated cloths are shown in Table 1, and when the silver-treated cloth of the present invention was added to the culture media, the growth of Pseudomonas aeruginosa could not be confirmed by the very small absorbance values, confirming that the silver-treated fabric of the present invention has antibacterial properties. In addition, the control silver-treated cloth has high absorbance, and the proliferation of pseudomonas aeruginosa can be seen, so that the antibacterial effect is not seen, thereby proving the advantages of the silver-treated cloth of the invention.

Next, in order to evaluate the stability of antibacterial properties, the change in antibacterial properties of the silver-treated fabric of the present invention after repeated water washing was observed. That is, the silver-treated cloth of the present invention is put into the culture medium for Pseudomonas aeruginosa as described above, and after the culture under the above culture conditions, the silver-treated cloth of the present invention is taken out, washed in 100mL of distilled water for 1 hour, and then put into a newly prepared culture medium for Pseudomonas aeruginosa, and after the culture under the above culture conditions, the absorbance of the culture solution is measured again in the same manner as described above. This series of operations was repeated 5 times. The results are shown in Table 2. As is clear from table 2, the antibacterial property of the silver-treated fabric of the present invention was stable without decreasing as shown by the absorbance values after 5 times of water washing.

[ Table 1 ]

	Absorbance at 660nm
		Silver processing cloth (invention)	0.069
Contrast silver treated cloth	2.905

Absorbance at 660nm was measured with a spectrophotometer, and the degree of proliferation of pseudomonas aeruginosa was determined (the same applies hereinafter).

[ Table 2 ] Effect of Water washing on antibacterial Properties of silver-treated cloth

Number of washes	Absorbance at 660nm
		0	0.069
1	0.064
		2	0.068
3	0.061
		4	0.069
5	0.064

[ example 2 ]

An unfinished bathrobe fabric (cotton origin: pakistan, using cotton count: 20 (in the same length and width), weave pattern: plain weave, sample size: width 8cm × length 8cm, mass: 0.68g) similar to example 1 was soaked in 0.1 mass% of 0.5M sodium hexametaphosphate solution to which a surfactant (ウオミン TE, imperial corporation was made) was added, stirred at all times, and heat-treated at 80 ℃ for 1 hour. The resultant was thoroughly washed with water and dried, and then treated with silver nitrate in the same manner as in example 1. The amount of silver ions in the silver nitrate-treated sample was calculated by the pH difference method in the same manner as in example 1, and as a result, 7 mmol of silver ions were bound. The pectin content of the cotton fibers of the cotton fabric treated in the 0.5M sodium hexametaphosphate solution was measured by the above pectin quantitative method, and was 6.4 mass% based on the cotton fibers.

[ example 3 ]

An unfinished bathrobe fabric (cotton origin: pakistan, using cotton count: 20 (in the same length and width), weave pattern: plain weave, sample size: width 8cm × length 8cm, mass: 0.68g) similar to example 1 was soaked in 0.1 mass% of 0.02M dipotassium hydrogenphosphate solution to which a surfactant (ウオミン TE, manufactured by imperial corporation) was added, stirred at all times, and heat-treated at 80 ℃ for 1 hour. The resultant was thoroughly washed with water and dried, and then treated with silver nitrate in the same manner as in example 1. The amount of silver ions in the silver nitrate-treated sample was calculated by the pH difference method in the same manner as in example 1, and as a result, 10 mmol of silver ions were bound. The pectin content of the cotton fibers of the cotton fabric treated with the solution of 0.02M dipotassium hydrogen phosphate was measured by the above pectin quantitative method, and was 5.9% by mass based on the cotton fibers.

[ example 4 ]

0.6g of the silver nitrate-treated sample, which was the same as in example 3, was repeatedly washed with 100mL of distilled water while stirring, and the antibacterial stability was evaluated in the same manner as in example 1, and the antibacterial activity was not confirmed to be reduced at least 5 times by washing (Table 3).

[ Table 3 ] Effect of Water washing on antibacterial Properties

Number of washes	Absorbance at 660nm
		0	0.071
1	0.066
		2	0.067
3	0.061
		4	0.070
5	0.060

[ example 5 ]

As in example 3, 0.6g of the silver nitrate-treated sample was not washed with distilled water for 1 hour, but was repeatedly washed with 100mL of 0.1 mass% soap lye (weakly alkaline, 28% of pure soap contained) in 0.1 mass% of a 0.1 mass% lithargite preparation プアベ - ス feeder at 80 ℃. The stability of antibacterial activity was evaluated in the same manner as in example 4, and the antibacterial activity was not confirmed to be reduced at least 5 times after washing (Table 4).

[ Table 4 ] Effect of washing on antibacterial Properties

Number of washes	Absorbance at 660nm
		Control (before silver treatment)	2.812
0	0.108
		1	0.134
2	0.122
		3	0.110
4	0.133
		5	0.125

[ example 6 ]

The cotton knit fabric was treated with copper sulfate in the same manner as in example 1 except that copper sulfate was used in place of silver nitrate and a cotton knit fabric (20 cotton threads, knitting form: plain needle, sample size: length × width: 8cm × 8cm) was used in place of unrefined cotton bathrobe cloth, and the amount of copper ions was calculated by the same pH difference method as described in example 1 to confirm that the cotton knit fabric contained 10 mmol of copper ions. The content of pectin in the cotton fibers of the cotton fabric bioscoured in the same manner as in example 1 was measured by the pectin quantitative method, and as a result, the pectin content was 3.1% by mass based on the cotton fibers.

[ example 7 ]

Chitosan (chitosan 10B, フナコシ corporation) was used in place of copper sulfate, and the same treatment as in example 6 was performed. It was confirmed that 5 mmol of glucosamine was bound to the cotton fabric (chitosan was measured by エルソン - モルガン method). The content of pectin in the cotton fibers of the cotton fabric bioscoured in the same manner as in example 1 was measured by the pectin quantitative method, and as a result, the content of pectin was 3.2% by mass based on the cotton fibers.

[ example 8 ]

The same procedure as in example 3 was repeated except that 1g of 20 cotton threads (pakistan cotton) was used instead of the cotton bathrobe cloth. The amount of silver ions was calculated by the same pH difference method as described in example 1, and it was confirmed that 6 mmol of silver ions were bonded to 20 cotton threads. The content of pectin in the cotton threads treated with 0.02M dipotassium hydrogen phosphate solution as in example 3 was measured by the above pectin measuring method, and the pectin content was 6.0 mass% with respect to the cotton threads.

Possibility of industrial utilization

According to the invention, as described above, the antibacterial agent is firmly supported on the pectic cellulose fiber, and the antibacterial agent is stably and permanently bonded to the pectic cellulose fiber and is not easily separated from the pectic cellulose fiber by washing.

Therefore, the cellulose fiber can be used as an antibacterial pectic cellulose fiber and an antibacterial pectic cellulose fiber fabric, and therefore, the cellulose fiber can be applied to various fiber products, such as clothes; household sundries such as handkerchiefs, women's ornaments, ribbons, towels, rags, wipes (leather shoes, beds, glasses, etc.) or curtains; bed clothes such as blankets, bed sheets, bedspreads, pillow covers, cushions or cushions; furniture and indoor articles such as carpets, curtains and wallpaper; medical materials such as gauze, mask or cap; recreational articles such as materials for handicraft suit tailor and the like. In addition, it can be used as an antibacterial cellulose fiber itself.

Claims (13)

1. An antibacterial pectocellulose characterized by containing a pectocellulose, wherein an inorganic compound antibacterial agent or an organic compound antibacterial agent is incorporated in pectin contained in the pectocellulose as an impurity.

2. The antibacterial pectocellulose of claim 1, wherein an ionic inorganic compound antibacterial agent or an organic compound antibacterial agent is bonded to the active group having an ionic bonding ability in the pectin contained in the pectocellulose via an ionic bond.

3. The antibacterial pectocellulose of claim 1, wherein the inorganic antibacterial agent is silver, copper or titanium or a metal compound containing these metals, and the organic antibacterial agent is quaternary ammonium, chitin or chitosan.

4. The antibacterial pectocellulose according to claim 1, wherein the pectocellulose comprises Japanese paper containing Broussonetia papyrifera and trilobe, cotton, hemp, rayon, kenaf, and a material selected from these raw materials.

5. An antibacterial pectocellulose fiber, characterized in that it comprises the antibacterial pectocellulose of claim 1.

6. A fibrous product comprising the antibacterial pectic cellulose fiber according to claim 5.

7. The fiber product according to claim 6, wherein the fiber product comprises the antibacterial pectic cellulose fiber alone or in combination or composite with other fibers.

8. An antibacterial pectocellulose fiber or pectocellulose fiber fabric, characterized in that the pectocellulose fiber or pectocellulose fiber fabric is treated with at least one chemical substance selected from the group consisting of acids, alkalis, salts thereof, chelating agents and pectinolytic enzymes to reduce the content of pectin contained in the impurities in the pectocellulose fiber to 1 to 80% by mass before the treatment, and an ionic inorganic compound antibacterial agent or an organic compound antibacterial agent is supported on the treated pectocellulose fiber or pectocellulose fiber fabric.

9. The pectic cellulose fiber or pectic cellulose fiber fabric according to claim 8, wherein the pectic cellulose fiber or pectic cellulose fiber fabric is made of cotton or hemp.

10. The pectic cellulose fiber or pectic cellulose fiber fabric according to claim 8, wherein the acid is phosphoric acid, sulfuric acid, or acetic acid, the base is sodium hydroxide, potassium hydroxide, or calcium hydroxide, the salt is a salt of the acid with the base, and the chelating agent is ethylenediaminetetraacetic acid or nitrilotriacetic acid.

11. The pectic cellulose fiber or pectic cellulose fiber fabric according to claim 8, wherein the inorganic antibacterial agent is silver, copper or titanium or a metal compound containing these metals, and the organic antibacterial agent is quaternary ammonium, chitin or chitosan.

12. A process for producing an antibacterial pectocellulose fiber or pectocellulose fiber fabric, characterized by treating a pectocellulose fiber or pectocellulose fiber fabric with at least one chemical substance selected from the group consisting of acids, alkalis, salts thereof, chelating agents and pectinolytic enzymes to reduce the content of pectin contained in impurities in the pectocellulose fiber to 1 to 80% by mass before the treatment, and loading an ionic inorganic compound antibacterial agent or an organic compound antibacterial agent on the treated pectocellulose fiber or pectocellulose fiber fabric to obtain the antibacterial pectocellulose fiber or pectocellulose fiber fabric.

13. A fibrous product comprising the pectic cellulose fiber of claim 8.