Antiviral sheet

Abstract

To provide an antiviral sheet that exhibits favorable mechanical characteristics, prevents detachment of antiviral, deodorizing, and antibacterial ingredients, and demonstrates superior antiviral, deodorizing, and antibacterial effects.SOLUTION: An antiviral sheet having an antiviral activity value (Mv) of at least 2.0 against influenza virus or feline calicivirus in the antiviral test method for textile products specified in JIS L 1922:2016, the antiviral sheet including a metal-containing cellulose-based fiber containing one or more metal ions and / or metal particles selected from the group consisting of Ag, Au, Pt, Pd, Ni, Mn, Fe, Ti, Al, Zn, and Cu.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an antiviral sheet. More specifically, the present invention relates to an antiviral sheet having antiviral and deodorizing functions. This invention relates to an antiviral sheet having antibacterial properties. [Background technology]

[0002] Functional sheets, which are made by adding functional agents to sheet-shaped substrates, are used in a variety of industrial fields. Examples of functions are generally deodorizing, antibacterial, heat-resistant, moisture-resistant, weather-resistant, and solvent-resistant. Examples of applications include packaging materials (paper containers, cardboard boxes, etc.). building materials (wallpaper, decorative paper, flooring paper, etc.), household goods (deodorizing materials, fragrance materials) , industrial supplies (filters, wipers, etc.), medical supplies (masks, etc.), clothing, other paper products ( Render, etc.

[0003] The functional sheets mentioned above are often required to have deodorizing and / or antibacterial properties. For example, the four major odors are ammonia, trimethylamine, hydrogen sulfide, and methyl Effectively and continuously removes odorous components including mercaptans (urine odor, feces odor, putrid odor, etc.) It is necessary to suppress this to

[0004] Various methods have been proposed to impart these deodorizing and antibacterial functions. and 2, one of silicon compounds or aluminum compounds which are components of zeolite. The aqueous solution is impregnated into a hydrophilic polymer substrate such as cellulose fiber, and the basic substance and the other aqueous solution are The mixture was further impregnated with the liquid to support zeolite inside the cellulosic fibers. Inorganic porous crystal-hydrophilic polymer composites have been proposed. It is disclosed that by carrying it, antibacterial and deodorizing effects can be imparted. .

[0005] In addition, Patent Document 3 discloses a method for treating a silicon compound and a basic substance-containing aqueous solution with an aluminum compound. The fiber structure is impregnated with an aqueous solution containing a basic substance and a cellulose-based Silicon compounds and aluminum compounds are reacted inside the fibers to form porous silica-alumina bodies. A cellulosic fiber structure that produces a certain zeolite is disclosed. By introducing metal ions into porous silica alumina, antibacterial and antifungal properties are imparted. It is disclosed that this can be done.

[0006] Patent Document 4 describes silver zeolite, silver zirconium phosphate, silver calcium phosphate, and silver dissolving agent. Antibacterial cellulosic fiber containing one or more silver-based antibacterial agents selected from antibacterial glass Furthermore, a nonwoven fabric using this antibacterial cellulose-based fiber is disclosed. There are.

[0007] Patent Document 5 also describes a paper substrate containing oxidized pulp, in which the carboxylates of the oxidized pulp are The amount of silyl groups is 1.0mmol / g to 2.0mmol / g based on the bone dry weight of oxidized pulp. The paper substrate is disclosed as a base material, and a certain amount of fibers made from a synthetic resin are added to the base material. It is also described that the content is within a range. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 10-120923 [Patent Document 2] Japanese Patent Application Publication No. 11-315492 [Patent Document 3] Japanese Patent Application Laid-Open No. 2008-031591 [Patent Document 4] Japanese Patent Application Publication No. 11-107033 [Patent Document 5] International Publication No. 2014 / 097929 DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0009] However, Patent Documents 1 to 4 disclose a method for manufacturing a fiber-reinforced composite of cellulose fibers and inorganic compounds containing a metal component. Only a simple mixture is described, and it is a mixture of cellulose fiber and inorganic compound containing a metal component. In other words, inorganic compounds containing metal components are not chemically bonded to fibers. Since it does not form a physical or chemical network like other fibers, it is used to manufacture nonwoven fabrics. In this case, the mechanical properties of the base material, such as tensile strength and tear strength, will decrease. However, there is a problem that inorganic compounds such as cellulose acetate may fall off from the substrate.

[0010] Furthermore, when the functional sheet is placed in a high humidity environment or gets wet, it becomes antiviral and antiseptic. There is a problem that the odor and antibacterial effects are reduced. Here, when wet, for example, the nonwoven fabric is left in a certain state after drying. It refers to a state in which the mass of a material contains more than 100% water by mass.

[0011] In addition, the paper substrate described in Patent Document 5 does not have sufficient antiviral and deodorizing effects. stomach.

[0012] Therefore, the present invention has good mechanical properties and can suppress the detachment of antiviral, deodorizing, and antibacterial components. At the same time, the antiviral, deodorizing and antibacterial effects are maintained regardless of humidity, even when wet. The purpose is to provide an antiviral sheet. [Means for solving the problem]

[0013] In order to achieve the above object, the antiviral sheet of the present invention is made of Ag, Au, Pt, P One or more metal ions selected from the group consisting of d, Ni, Mn, Fe, Ti, Al, Zn and Cu Metal-containing cellulosic fibers containing metal particles.

[0014] In the metal-containing cellulose fiber, a metal is added to the cellulose fiber having an anionic group. Preferably, the ions are ionically bonded.

[0015] The present invention includes, but is not limited to, the following aspects. (1) JIS L 1922:2016 Antiviral test method for textile products Antiviral activity value (Mv) against influenza virus or feline calicivirus 2.0 or more, and the antiviral sheet is made of Ag, Au, Pt, Pd, Ni, Mn, One or more metal ions selected from the group consisting of Fe, Ti, Al, Zn and Cu and / or gold An antiviral sheet comprising metal-containing cellulosic fibers containing metal particles. (2) In the metal-containing cellulose-based fiber, the metal ions and / or metal particles The antiviral composition according to (1), wherein the content of the compound is 10 to 100 mg / g of the cellulosic fiber. Sex sheet. (3) The metal-containing cellulosic fiber is a cellulosic fiber having an anionic group, and a metal ion is added to the cellulosic fiber. (1) or (2) is a cellulose-based fiber in which Antiviral sheet. (4) The amount of anionic groups in the cellulose fibers having anionic groups is 0.01 to 3.0 mm ol / g. The antiviral sheet according to any one of (1) to (3). (5) The cellulosic fiber having an anionic group is a carboxyl group or a carboxylate group. The antiviral sheet according to (3) or (4), which is an oxidized cellulose fiber having an ester group. Route. (6) The cellulose-based fiber having an anionic group is a carboxyl group having a carboxyalkyl group. The antiviral sheet according to (3), which is made of carboxyalkylated cellulose-based fibers. (7) The cellulose-based fiber having an anionic group is phosphate-esterified to have a phosphate group. The antiviral sheet according to (3), which is made of cellulosic fibers. (8) The cellulosic fiber having an anionic group is a phosphite ester having a phosphite group. The antiviral sheet according to (3), which is made of a cellulose-based fiber. (9) The cellulose-based fiber having an anionic group is a sulfonated cellulose fiber having a sulfate group. The antiviral sheet according to (3), which is made of a polyester fiber. (10) The antiviral sheet contains metal-free cellulose-based fibers. 10. The antiviral sheet according to any one of (10) to (9). (11) Any one of (1) to (10) above, wherein the antiviral sheet contains synthetic fibers. The antiviral sheet described above. (12) The antiviral sheet is a sheet of two or more layers, and at least one layer is The antiviral sheet according to any one of (1) to (11), which contains a metal-containing cellulose fiber. to. (13) The content of metal ions and / or metal particles in the antiviral sheet is 0. 11. The antiviral sheet according to claim 1, wherein the content is 2 to 50% by mass. (14) JIS L 1922:2016 Antiviral test method for textile products , antiviral activity value (Mv) against influenza virus or feline calicivirus It has antiviral properties with a value of 2.0 or more, and contains Ag, Au, Pt, Pd, Ni, Mn, Fe, One or more metal ions and / or metal particles selected from the group consisting of Ti, Al, Zn, and Cu A metal-containing cellulosic fiber containing (15) In the metal-containing cellulose-based fiber, the metal ions and / or metal particles The metal according to (14), wherein the content of the metal is 10 to 100 mg / g of the cellulosic fiber. Contains cellulosic fibers. (16) The metal-containing cellulose fiber is a cellulose fiber having an anionic group. (14) or (15) characterized in that the metal ions are ionically bonded to the cellulose-based fiber. (15) The metal-containing cellulose fiber according to (15). (17) The amount of anionic groups in the cellulose fibers having anionic groups is 0.01 to 3.0 The metal-containing cellulose according to any one of (14) to (16), characterized in that Fiber based. (18) The cellulose-based fiber having an anionic group is a carboxyl group or a carboxy The metal-containing fiber according to (16) or (17), which is an oxidized cellulose-based fiber having a carboxylate group Cellulosic fibers. (19) The cellulose-based fiber having an anionic group is a cellulose-based fiber having a carboxyalkyl group. The metal-containing fiber according to (16) or (17), which is a carboxyalkylated cellulose fiber. Cellulose fiber. (20) The cellulosic fiber having an anionic group is a phosphoric acid ester having a phosphoric acid group. The metal-containing cellulose fiber according to (16) or (17), which is a cellulose-based fiber. (21) The cellulose-based fiber having an anionic group is a phosphite ester having a phosphite group. The metal-containing cellulose fiber according to (16) or (17), which is a methylated cellulose fiber. Wisdom. (22) The cellulose-based fiber having an anionic group is a sulfonated cellulose-based fiber having a sulfate group. The metal-containing cellulose fiber according to (16) or (17), which is a cellulose fiber. [Effects of the Invention]

[0016] According to the present invention, it is possible to suppress the detachment of antiviral, deodorizing and antibacterial components, and This results in an antiviral sheet with excellent antiviral properties. DETAILED DESCRIPTION OF THE INVENTION

[0017] The antiviral sheet according to the embodiment of the present invention is compliant with JIS L 1922:2016 Fiber In the antiviral test method for textile products, influenza virus or feline calicivirus An antiviral sheet having an antiviral activity value (Mv) of 2.0 or more against viruses. , Ag, Au, Pt, Pd, Ni, Mn, Fe, Ti, Al, Zn and Cu Metal-containing cellulosic fibers containing one or more metal ions and / or metal particles The antiviral sheet is described in detail below.

[0018] <1. Metal-containing cellulose-based fibers> The metal-containing cellulose fiber of the present invention is a fiber containing Ag, Au, Pt, Pd, Ni, Mn, Fe, One or more metal ions and / or metal particles selected from the group consisting of Ti, Al, Zn, and Cu Also, as will be described later, the metal-containing cellulose fiber The fibers are preferably metal-containing anion-modified cellulose fibers.

[0019] The content of the metal-containing cellulose fiber is preferably 1% by mass or more relative to the sheet. If the content is less than 1% by mass, sufficient antiviral, deodorizing and antibacterial effects are imparted. There are no particular upper limits for the above content, and the desired deodorizing, antibacterial, This can be adjusted appropriately depending on the level of antiviral effect, but it may be 100% by mass.

[0020] <2. Metal-free cellulose-based fibers> The antiviral sheet according to an embodiment of the present invention comprises, in addition to the metal-containing cellulose fiber, A cellulose-based fiber that does not contain metal (hereinafter referred to as "general cellulose-based fiber"), It may be contained depending on the desired functions such as moisture absorption, water absorption, and texture.

[0021] Common cellulosic fibers include, for example, wood pulp; bamboo, cotton, hemp, jute, kenaf, and farmland. Waste, animal (e.g., ascidians), algae, and microbial (e.g., acetobacter) production Examples of suitable pulp include non-wood pulp such as wood pulp, regenerated cellulose, and rayon.

[0022] As the general cellulose fiber, wood pulp is preferable, and one or more types of general cellulosic fibers are used. A mixture of loin-based fibers can be used.

[0023] As described above, the content of the metal-containing cellulose fiber is preferably 1% by mass or more. Therefore, the content of general cellulose fibers in the antiviral sheet is 99% by mass or less. The lower limit of the content of the general cellulosic fiber is not particularly limited. It may not contain cellulose fiber.

[0024] The number average fiber diameter and number average fiber diameter of the metal-containing cellulose fiber and the general cellulose fiber are The average fiber length is not particularly limited, and is determined based on the required mechanical properties such as tensile strength and tear strength. Any value can be used depending on the breathability, texture, etc. Also, the number average fiber diameter Two or more types of fibers having different number average fiber lengths may be mixed in any ratio.

[0025] For example, in the case of softwood kraft pulp (NBKP), which is one of the natural cellulose fibers, The number average fiber diameter is about 30 to 60 μm, the number average fiber length is about 2 to 5 mm, and the hardwood bleached kraft In the case of LBKP, the number average fiber diameter is about 10 to 30 μm, and the number average fiber length is about 1 to It is about 2mm.

[0026] The above metal-containing cellulose fibers and general cellulose fibers are both contained in the sheet. In the manufacturing process up to the end of the process, the beating treatment may be carried out one or more times. Beating is a process that applies mechanical shear force to fibers. A portion of the fibers becomes fibrillated or nanofibers, improving mechanical properties such as tensile strength.

[0027] In particular, in the case of metal-containing cellulose fibers, beating treatment removes metal ions and or further enhance the antiviral, deodorizing and antibacterial effects after metal particles are supported. can be done.

[0028] The degree of beating is generally measured by the CSF (Comparative Freeness Factor). The freeness of the fiber base is preferably in the range of 30 to 800 ml.

[0029] If the freeness is lower than 30 ml, the yield in the sheet will be low during the sheet manufacturing process. If the freeness is higher than 800ml, the fibrillation is insufficient and the specific surface area is low. As a result, the exposure of metal ions to the sheet surface is reduced, resulting in deodorizing, antibacterial and antiviral properties. The effectiveness of the product may be reduced.

[0030] The freeness of general cellulose fibers is not particularly limited, and may be within the range of general freeness, e.g. You can freely choose from a range of 5 to 950 ml depending on the quality you require.

[0031] The apparatus used for beating is not particularly limited, and any known apparatus can be used. Examples of equipment include refiners, beaters, PFI mills, kneaders, dispersers, etc. A metal or blade is used to work with pulp fibers around a rotating shaft. By rubbing, as well as high pressure homogenizers, ultra-high pressure homogenizers, nanomizers, Examples of such equipment include a seed mill and a stone mill.

[0032] <3. Production of metal-containing anion-modified cellulose-based fibers> As for the metal-containing cellulose fiber, a cellulose fiber having an anionic group and metal ions is added. Metal-containing anion-modified cellulose fibers in which the anion is ionically bonded are preferred. Examples of the cellulose-based fibers include oxidized cellulose, etherified cellulose (carbo hydroxymethyl cellulose, esterified cellulose (phosphate esterified cellulose, etc.) Examples include:

[0033] The amount of anionic groups in cellulose fibers containing anionic groups is In the case of oxidized cellulose fibers having carboxylate groups, phosphate groups, or sulfonate groups, The above functional groups are collectively referred to as "acid groups."

[0034] 60 ml of 0.5% by mass slurry (aqueous dispersion) of oxidized cellulose fiber sample with acid groups The solution was adjusted to pH 2.5 by adding 0.1M hydrochloric acid, and then 0.05N sodium hydroxide was added. Drop the aqueous solution of ammonium hydroxide and measure the electrical conductivity until the pH reaches 11. From the amount of sodium hydroxide (a) consumed in the neutralization step of a mildly weak acid, Calculate. Amount of anionic groups in oxidized cellulose fibers with acid groups [mmol / g] = a [ml] x 0 .05 / mass of oxidized cellulose fiber with acid groups [g] / x. x: Value corresponding to the valence of the acid group (carboxyl group, carboxylate group, sulfonic acid group: 1 , phosphate group: 2)

[0035] To quantify the amount of anionic groups resulting from carboxyalkylation, the following method is used: Weigh out approximately 2.0 g of carboxyalkylated cellulose fiber (bone dry) and add it to a 300 mL container. 1000 mL of nitric acid and methanol was added to a stoppered Erlenmeyer flask. Add 100 mL of the added solution, shake for 3 hours, and carboxyalkyl cellulose salt (CM Hydrogenated carboxymethyl cellulose (bone dry) was converted into hydrogenated carboxymethyl cellulose. Accurately weigh out 0.5 to 2.0 g and place in a 300 mL Erlenmeyer flask with a stopper. Wet the hydrogenated carboxymethyl cellulose with 15 mL of water, add 100 mL of 0.1 N NaOH, and The mixture was shaken at room temperature for 3 hours. Phenolphthalein was used as an indicator, and the mixture was diluted with 0.1N H2 Excess NaOH was back-titrated with SO4. The degree of carboxyalkyl substitution (DS) was calculated by the following equation: I calculated: A = [(100 × F' - (0.1N H2SO4) (mL) × F) × 0.1] / (hydrogen type Absolute dry mass of carboxyalkylated cellulose (g) DS=0.162×A / (1-0.058×A) A: The amount of 1N NaOH required to neutralize 1 g of hydrogen-type carboxyalkylated cellulose (m L) F': Factor of 0.1N H2SO4 F: Factor of 0.1N NaOH.

[0036] The amount of anionic groups in the cellulose-based fiber is preferably 0.01 to 3.0 mmol / g. If the amount of acid groups is less than 0.01 mmol / g, the metal ion-supporting step described below may be carried out. In this case, the amount of metal ions present on the surface of cellulose-based fibers is insufficient, and deodorizing, antibacterial, On the other hand, if the amount of acid groups exceeds 3.0 mmol / g, the antiviral function may be impaired. During the polymerization reaction, cellulose tends to be cleaved as a side reaction, resulting in a decrease in yield.

[0037] The metal-containing anion-modified cellulose fiber is obtained by modifying a general cellulose fiber as follows: The anion-modified groups were introduced into the glucose units on the surface by chemical modification. It can be produced by supporting metal ions and / or metal particles.

[0038] Hereinafter, an anion-modified group will be introduced into the glucose unit on the surface of the cellulose-based fiber. and subsequent methods for loading metal ions and / or metal particles, respectively. This will be explained.

[0039] <3-1. Oxidized Cellulose> Cellulose has three hydroxyl groups per glucose unit, allowing it to be easily synthesized by a variety of chemical reactions. It is possible to perform a modification treatment. Oxidized cellulose is a material that can be modified by denaturing cellulose in the process described below. A modification in which a carboxyl group or a carboxylate group is introduced into at least a part of the carbon fiber To have sex.

[0040] Here, the carboxyl group refers to a group represented by -COOH, and the carboxylate group refers to a group represented by -COOH. The counter ion of the carboxylate group is not particularly limited. Carboxyl groups and carboxylate groups are also collectively referred to as "acid groups."

[0041] The method of modifying the cell after modification to introduce a carboxyl group or a carboxylate group is as follows: There are no particular limitations on the cellulose fiber as long as it contains a carboxyl group or a carboxylate group. These will be explained in detail below.

[0042] (3-1-1. Oxidation of cellulosic fibers) In the present invention, the method for oxidizing cellulosic fibers is not particularly limited, and known methods can be used. Examples include N-oxyl compounds, bromides, iodides, and A method for the preparation of cellulose derivatives in water using an oxidizing agent in the presence of a substance selected from the group consisting of a mixture of According to this method, the glucopyranose on the cellulose surface is oxidized. The primary hydroxyl group at C6 of the ring is selectively oxidized to give aldehyde, carboxyl, and carboxyl groups. The concentration of the cellulose raw material during the reaction is particularly Although not limited thereto, it is preferably 5 mass % or less.

[0043] N-oxyl compounds are compounds that can generate nitroxy radicals. Examples of the oxyl radical include 2,2,6,6-tetramethylpiperidine 1-oxyl (T N-oxyl compounds include compounds that promote the target oxidation reaction. Any compound can be used as long as it is a compound.

[0044] The amount of N-oxyl compound used is not particularly limited as long as it is a catalytic amount capable of oxidizing cellulosic fibers. For example, the amount is preferably 0.01 mmol or more per 1 g of bone dry cellulose. The upper limit is preferably 10 mmol or less, and more preferably 1 mm 100 mmol or less is more preferable, and 0.5 mmol or less is even more preferable. The amount of the mixture used is preferably 0.01 to 10 mmol per 1 g of bone dry cellulose. It is more preferably 0.01 to 1 mmol, and even more preferably 0.02 to 0.5 mmol.

[0045] Bromides are compounds containing bromine, such as aluminum bromide, which can dissociate and become ionized in water. Potassium metals, such as sodium bromide, are examples. Iodides are compounds containing iodine. The amount of bromide or iodide used is, for example, alkali metal iodide. The total amount of bromide and iodide is selected within the range that can promote the oxidation reaction. The amount is preferably 0.1 mmol or more, more preferably 0.5 mmol or more, relative to cellulose. The upper limit is preferably 100 mmol or less, more preferably 10 mmol or less, and Therefore, the total amount of bromide and iodide is 1000 ppm or less per 1 g of bone-dry cellulose. Preferably, the amount is 0.1 to 100 mmol, more preferably 0.1 to 10 mmol, 0.5 to 5 mmol is more preferable.

[0046] The oxidizing agent is not particularly limited, but examples thereof include halogen, hypohalous acid, halo acid, perchloric acid, and the like. Examples include halogen acids, their salts, halogen oxides, and peroxides. Hypohalous acid or its salt is preferred because it has a low environmental load. is more preferred, and sodium hypochlorite is even more preferred.

[0047] The amount of oxidizing agent used is preferably 0.1 mmol or more per 1 g of bone-dry cellulose. More preferably, it is 1 mmol or more, and even more preferably, it is 3 mmol or more. The upper limit is 500 mmol. 1 or less is preferable, 50 mmol or less is more preferable, and 25 mmol or less is even more preferable. .

[0048] When using an N-oxyl compound, the amount of oxidizing agent used is The amount of the oxidizing agent is preferably 1 mol or more, and the upper limit is preferably 40 mol. is preferably 1 to 40 mol per 1 mol of the N-oxyl compound.

[0049] The conditions for the oxidation reaction, such as pH and temperature, are not particularly limited, and are generally relatively mild. The reaction temperature is preferably 4°C or higher, and more preferably 15°C or higher. The upper limit is preferably 40°C or less, and more preferably 30°C or less. The temperature is preferably 40°C, but may be about 15 to 30°C, ie, room temperature.

[0050] The pH of the reaction solution is preferably 8 or higher, more preferably 10 or higher. The upper limit is preferably 12 or lower. Therefore, the pH of the reaction solution is preferably 8 to 12, more preferably 11 or less. The preferred range is about 10 to 11.

[0051] Normally, carboxyl groups are generated in the cellulose as the oxidation reaction proceeds. Therefore, in order to efficiently proceed with the oxidation reaction, the pH of the Add an alkaline solution such as an aqueous sodium chloride solution to maintain the pH of the reaction solution within the above range. The reaction medium for oxidation is preferably one that is easy to handle and unlikely to cause side reactions. For these reasons, water is preferred.

[0052] The reaction time for oxidation can be appropriately set according to the degree of progress of oxidation. The upper limit is usually 6 hours or less, preferably 4 hours or less. The reaction time for oxidation is usually 0.5 to 6 hours, for example, about 0.5 to 4 hours.

[0053] The oxidation may be carried out in two or more stages. For example, after the first stage reaction is completed, filtration is carried out. The oxidized cellulose obtained by separation can be oxidized again under the same or different reaction conditions. This allows for efficient oxidation without being inhibited by the salt produced as a by-product in the first reaction. It is possible. Another example of an oxidation method is a method of oxidation by ozone treatment. Therefore, at least the hydroxyl groups at positions 2 and 6 of the glucopyranose ring constituting cellulose are oxidized. As the cellulose is converted into cellulose, the cellulose chains are degraded.

[0054] Ozone treatment is usually carried out by contacting cellulose raw materials with a gas containing ozone. The ozone concentration in the gas is 50 g / m 3 The upper limit is preferably 250. g / m 3 Preferably, it is 220 g / m or less. 3 It is more preferable that: The ozone concentration in the gas is 50 to 250 g / m 3 It is preferable that the ratio is 50 to 22 0g / m 3 It is more preferable that:

[0055] The amount of ozone added is 0.1 parts by mass or more relative to 100% by mass of the solid content of the cellulose raw material. The upper limit is usually 30% by mass or less. Therefore, the amount of ozone added is 0.1% by mass relative to 100% by mass of the solid content of the cellulose raw material. It is preferably up to 30% by mass, and more preferably 5 to 30% by mass.

[0056] The ozone treatment temperature is usually 0°C or higher, preferably 20°C or higher. Therefore, the ozone treatment temperature is preferably 0 to 50°C, and more preferably 20 to 50°C. More preferably, it is 50°C.

[0057] The ozone treatment time is usually 1 minute or more, preferably 30 minutes or more. Therefore, the ozone treatment time is usually about 1 to 360 minutes, and 30 Approximately 360 minutes is preferable.

[0058] If the ozone treatment conditions are within the above range, the cellulose may be excessively oxidized and decomposed. This can prevent the above-mentioned problems, resulting in a good yield of oxidized cellulose.

[0059] The resultant product obtained after the ozone treatment may be further subjected to a post-oxidation treatment using an oxidizing agent. The oxidizing agent used in the additional oxidation treatment is not particularly limited, but examples thereof include chlorine dioxide, sodium chlorite, etc. Chlorine compounds such as thorium; oxygen, hydrogen peroxide, persulfuric acid, peracetic acid, etc. For example, the oxidizing agent may be dissolved in water or a polar organic solvent such as alcohol. One method is to dissolve the cellulose in an oxidizing agent solution to prepare an oxidizing agent solution, and then immerse the cellulose raw material in the oxidizing agent solution. can be.

[0060] Carboxyl groups, carboxylate groups, and aldehydes contained in oxidized cellulose fibers The amount of the group can be adjusted by controlling the oxidation conditions such as the amount of oxidizing agent added and the reaction time. This can be done.

[0061] (3-1-2. Etherification of cellulosic fibers) As for etherification, in order to introduce metal ions into the cellulosic fibers in the subsequent process, Any method can be used as long as the functional group after the reaction contains a carboxyl group or a carboxylate group. Any of these methods may be used, and known methods can be used. For example, carboxymethyl ( Etherification, carboxyethyl (etherification), carboxypropyl (etherification), Carboxyalkyl etherification such as carboxybutyl (ether) and carboxyphenyl Among these, carboxymethylation is one example. The method is described below.

[0062] The method of carboxymethylation is not particularly limited, and known methods can be used. For example, there is a method in which cellulose raw materials as bottom raw materials are mercerized and then etherified. A common solvent is used for the carboxymethylation reaction. Examples of the solvent include water, Alcohols (e.g., lower alcohols) and mixed solvents thereof. Lower alcohols Examples of suitable solvents include methanol, ethanol, N-propyl alcohol, and isopropyl alcohol. Examples include ethanol, N-butanol, isobutanol, and tertiary butanol.

[0063] The mixing ratio of the lower alcohol in the mixed solvent is usually 60% by mass or more or 95% by mass or more. The amount of the solvent is preferably 60 to 95 mass % relative to the cellulose raw material. The amount is usually 3 times by mass. The upper limit is not particularly limited, but is 20 times by mass. The amount is preferably 3 to 20 times by mass.

[0064] Mercerization is usually carried out by mixing the cellulose raw material with a mercerizing agent. Examples of the hydroxide include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. The amount of the mercerizing agent used is preferably 0.5 times or more by mole per anhydrous glucose residue of the starting material. The amount is preferably 1.0 mole or more, and more preferably 1.5 moles or more. The upper limit is usually 20 times or less by mole, preferably 10 times or less by mole, and more preferably 5 times or less by mole. Therefore, the amount is preferably 0.5 to 20 times by mole, and more preferably 1.0 to 10 times by mole. 1.5 to 5 times the molar amount is more preferred.

[0065] The reaction temperature for mercerization is usually 0°C or higher, preferably 10°C or higher. The reaction temperature is usually 70°C or lower, preferably 60°C or lower. Therefore, the reaction temperature is usually 0 to 70°C. The temperature is preferably 10 to 60° C. The reaction time is usually 15 minutes or more, preferably 30 minutes or more. The upper limit is usually 8 hours or less, preferably 7 hours or less. Therefore, the upper limit is usually 15 minutes to The time is 8 hours, preferably 30 minutes to 7 hours.

[0066] The etherification reaction is usually carried out by adding a carboxymethylating agent to the reaction system after mercerization. An example of a carboxymethylating agent is sodium monochloroacetate. The amount of carboxymethylating agent added is usually 0.05 times the glucose residue of the cellulose raw material. The molar amount is preferably 0.5 times or more, more preferably 0.8 times or more. The upper limit is usually 10.0 times or less by mole, preferably 5 times or less by mole, and more preferably 3 times or less by mole. Therefore, it is preferably 0.05 to 10.0 times by mole, and more preferably The molar amount is preferably 0.5 to 5, and more preferably 0.8 to 3 times.

[0067] The reaction temperature is usually 30°C or higher, preferably 40°C or higher, and the upper limit is usually 90°C or lower, preferably Therefore, the reaction temperature is usually 30 to 90°C, preferably 40 to 80°C. ° C. The reaction time is usually 30 minutes or more, preferably 1 hour or more. The reaction time is usually 10 hours or less, preferably 4 hours or less. The time is 10 hours, preferably 1 to 4 hours. During the carboxymethylation reaction, the reaction mixture may be stirred as needed.

[0068] When cellulose raw materials are modified by carboxymethylation, the resulting carboxymethyl The degree of carboxymethyl substitution per anhydroglucose unit in the cellulose-based fiber is 0.0 It is preferably 1 or more, more preferably 0.05 or more, and even more preferably 0.10 or more. The upper limit is preferably 0.50 or less, more preferably 0.40 or less, and particularly preferably 0.35 or less. Therefore, the degree of carboxymethyl group substitution is preferably 0.01 to 0.50, The range is more preferably 0.05 to 0.40, and even more preferably 0.10 to 0.30.

[0069] Carboxymethyl substitution per glucose unit in carboxymethylated cellulosic fibers. The degree of carboxymethylation can be measured, for example, by the following method. Accurately weigh out approximately 2.0 g of cellulose acetate (bone dry) and place it in a 300 mL Erlenmeyer flask with a stopper. 2) Methanol nitrate obtained by adding 100 mL of concentrated nitric acid to 1000 mL of methanol. Add 100 mL of carboxymethylcellulose solution and shake for 3 hours to obtain carboxymethylcellulose salt (carboxymethylcellulose). 3) Hydrogen type carboxymethyl cellulose is converted into hydrogen type carboxymethyl cellulose. Weigh out 1.5 to 2.0 g of carboxymethyl cellulose (bone dry) and add it to a 300 mL container with a stopper. Place in an Erlenmeyer flask. 4) Add 15 mL of 80% methanol to the hydrogen carboxymethylation cell. Wet the loin, add 100 mL of 0.1 N NaOH, and shake at room temperature for 3 hours. 5) Using phenolphthalein as an indicator, 0.1N H2SO4 with excess NaOH 6) Calculate the degree of carboxymethyl substitution (DS) using the following formula: A = [(100 × F' - (0.1 N H2SO4) (mL) × F) × 0.1] / (hydrogen Absolute dry mass of carboxymethyl cellulose (g) DS=0.162×A / (1-0.058×A) A: The amount required to neutralize 1 g of hydrogen-type carboxymethyl cellulose Amount of 1N NaOH (mL) F': Factor of 0.1N NaOH F: Factor of 0.1N H2SO4

[0070] (3-1-3. Esterification of cellulosic fibers) As for esterification, any method can be used as long as it is a method for introducing an anionic functional group. For example, phosphate esterification, sulfate esterification, etc. Among these, phosphate esterification and sulfate esterification are examples. The method is explained below.

[0071] (Cellulose phosphate, cellulose phosphite) Phosphate cellulose is a compound that contains a phosphate group or a phosphite group. It is an esterified cellulose. As a compound having a phosphate group or a phosphite group, Examples of the acid include phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, polyphosphonic acid, and the like. These compounds are low cost and easy to handle.

[0072] Compounds having a phosphate group or a phosphite group include phosphoric acid, sodium dihydrogen phosphate, Disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, metaphosphate Sodium, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, Pylori Potassium phosphate, potassium metaphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate ammonium, triammonium phosphate, ammonium pyrophosphate, ammonium metaphosphate, Phosphite, sodium hydrogen phosphite, ammonium hydrogen phosphite, potassium hydrogen phosphite, Sodium dihydrogen phosphate, sodium phosphite, lithium phosphite, potassium phosphite, Magnesium phosphite, calcium phosphite, triethyl phosphite, triphenyl phosphite Among them, phosphate ester or phosphite ester are preferred. phosphoric acid, sodium salts of phosphoric acid, Potassium salt of phosphoric acid, ammonium salt of phosphoric acid, phosphorous acid, sodium salt of phosphorous acid, Potassium salt of phosphoric acid and ammonium salt of phosphorous acid are preferred, sodium dihydrogen phosphate, Disodium hydrogen phosphate, sodium hydrogen phosphite, and sodium dihydrogen phosphite are more preferred. The compound having a phosphate group or a phosphite group may be used alone or in combination of two or more. A combination of the above may also be used.

[0073] In cellulose phosphate and cellulose phosphite, phosphate ester Phosphate groups per 1g (weight) of cellulose phosphate or cellulose phosphite Alternatively, the lower limit of the amount of phosphorous group introduced is preferably 0.1 mmol / g or more. If it exceeds 0 l / g, the desired physical properties may not be obtained. Phosphate or phosphate groups per 1g (weight) of cellulose or phosphite The amount of phosphate groups introduced is preferably 0.1 to 3.5 mmol.

[0074] Phosphate esterification or phosphite esterification is carried out, for example, on cellulose raw materials. The cellulose raw material is reacted with a compound having a phosphate group or a phosphite group. As a method for reacting a compound having a phosphate group or a phosphite group with a cellulose acetate compound, for example, A method of mixing a powder or an aqueous solution of a compound having a phosphate group or a phosphite group with a raw material for sucrose In this method, an aqueous solution of a compound having a phosphate group or a phosphite group is added to a slurry of a cellulose raw material. Among these, the method of adding phosphate esters is preferred as it increases the uniformity of the reaction and The efficiency of phosphate esterification and phosphorous esterification is high, so the cellulose raw material or its slag is A preferred method is to mix an aqueous solution of a compound having a phosphate group or a phosphite group into the slurry. The pH of an aqueous solution of a compound containing a phosphate or phosphite group varies depending on the amount of phosphate or phosphite. From the viewpoint of increasing the efficiency of introduction of the phosphate group, it is preferably 7 or less, and from the viewpoint of suppressing hydrolysis, 3 to 7 is more preferred.

[0075] The lower limit of the amount of the compound having a phosphate group or a phosphite group to be added is 100% of the cellulose raw material. The amount is preferably 0.2 parts by mass or more, more preferably 1 part by mass or more, calculated as phosphorus atoms, relative to parts by mass. When the content is in this range, the cellulose phosphate and the cellulose phosphate are On the other hand, the upper limit is preferably 500 parts by mass or less, and 4 It is more preferable that the amount is 00 parts by mass or less. A yield commensurate with the amount of the compound having an acid group added can be efficiently obtained.

[0076] The amount of the compound having a phosphate group or a phosphite group added is preferably 0.2 to 500 parts by mass. The amount is preferably 1 to 400 parts by mass, and more preferably 1 to 400 parts by mass.

[0077] When reacting a cellulose raw material with a compound having a phosphate group or a phosphite group, The basic compound may be added to the reaction system in the following manner. For example, a slurry of a cellulose raw material, a water solution of a compound having a phosphate group or a phosphite group, or a slurry of a cellulose raw material and a compound having a phosphate group or a phosphite group. The basic compound is not particularly limited, but a nitrogen-containing compound exhibiting basicity is The term "basic" generally refers to a compound that exhibits basicity in the presence of a phenolphthalein indicator. The aqueous solution of a basic compound is pink to red in color, or the pH of the aqueous solution of a basic compound is 7. It means bigger than.

[0078] The nitrogen-containing compound exhibiting basicity is not particularly limited as long as it exhibits the effects of the present invention. Compounds having an amino group are preferred. For example, urea, methylamine, ethylamine, thiamin, trimethylamine, triethylamine, monoethanolamine, diethanolamine, tri Ethanolamine, pyridine, ethylenediamine, hexamethylenediamine Among these, urea is preferred because of its low cost and ease of handling.

[0079] The amount of the basic compound added is preferably 2 to 1,000 parts by mass, more preferably 100 to 700 parts by mass. The reaction temperature is preferably 0 to 95°C, more preferably 30 to 90°C. The time is not particularly limited, but is usually about 1 to 600 minutes, preferably 30 to 480 minutes. If the reaction conditions are within either of these ranges, excessive phosphate or nitrogen groups will be added to the cellulose. It is possible to prevent the introduction of phosphate groups, which makes the material more soluble, and This can improve the yield of cellulose phosphite.

[0080] After reacting a compound having a phosphate group or a phosphite group with a cellulose raw material, the following steps are usually performed: A suspension is obtained. The suspension is dehydrated as necessary. After dehydration, it is preferable to carry out a heat treatment. This makes it possible to suppress the hydrolysis of the cellulose raw material. The temperature is preferably 00 to 170°C, and 130°C or less (more preferably) while water is contained during the heat treatment. After removing the water, it is best to heat at 100-170°C. More preferable.

[0081] Cellulose phosphate and cellulose phosphite are boiled and then washed with cold water. It is preferable to carry out a cleaning treatment such as washing.

[0082] (sulfonated cellulose) Sulfonated cellulose is cellulose that has been sulfonated with a compound containing sulfate groups. Examples of compounds having a sulfuric acid group include sulfuric acid, sulfamic acid, and chlorosulfonic acid. These compounds are low cost and are often used in the manufacture of fluororesin, sulfur trioxide, and their esters and salts. , easy to handle.

[0083] As the sulfonating reagent, sulfamic acid is preferably used. Not only is cellulose dissolving less than sulfuric anhydride or sulfuric acid aqueous solution, but it also has low acidity. In addition, it is possible to maintain the degree of polymerization by using sulfuric anhydride and sulfuric acid aqueous solution, which are highly acidic and corrosive. However, there are no restrictions on its handling and it is not designated as a specific substance under the Air Pollution Control Act. , and has a small impact on the environment.

[0084] The amount of sulfamic acid used is adjusted appropriately taking into consideration the amount of substituents introduced into the cellulose fiber. Sulfamic acid can be used for example for one mole of glucose unit in a cellulose molecule. Preferably, the amount used is 0.01 to 50 mol, more preferably 0.1 to 30 mol, per mol. can be done. <3-2. Supporting of metal ions and / or metal particles> For cellulose-based fibers, Ag, Au, Pt, Pd, Ni, Mn, Fe, Ti, A ions or particles of one or more metal elements selected from the group consisting of I, Zn and Cu. This results in high antiviral, antibacterial and deodorizing effects. This further improves the antiviral, antibacterial and deodorizing functions.

[0085] In particular, anion-modified cellulose fibers are chemically bonded to the metal. Therefore, when it is contained in the sheet, the metal components are less likely to be released from the sheet, and the tensile strength The mechanical properties such as the above are also good.

[0086] The method for supporting the metal ions on the cellulosic fibers is not particularly limited. For example, the above-mentioned dispersion of cellulose-based fibers prepared in advance may be mixed with an aqueous solution of a metal compound. Alternatively, a dispersion containing the cellulose fiber may be applied to a substrate to form a film, and the film may be coated with gold. The membrane may be impregnated by dropping an aqueous solution of a metal compound onto the substrate. The film may be in a state where it is peeled off from the substrate.

[0087] By these methods, metal ions derived from metal compounds are converted into carboxylate groups. By exchanging the counter ion with the sodium ion that was already ionically bonded to the anionic modified group, In this case, metal ions are added to the cellulosic fibers. This is thought to be caused by the difference in ionization tendency between the two.

[0088] Here, the aqueous solution of a metal compound is an aqueous solution of a metal salt. Examples of metal salts include complexes (complex ions). These include nitrates, halides, sulfates, and acetates. The concentration is not particularly limited, but is preferably 0.2 to 2.2 mmol per 1 g of cellulose fiber. The contact time of the metal compound is adjusted appropriately. That's fine.

[0089] The temperature during contact is not particularly limited, but is preferably in the range of 2 to 50°C. The pH of the liquid during contact is not particularly limited, but if the pH is low, the anion-modified group may be easily degraded. The pH range is preferably 7 to 13, and more preferably 8 to 13, since metal ions are less likely to bind to the solution. A range of 2 is particularly preferred.

[0090] In the present invention, it is possible to introduce metal ions into cellulosic fibers as described above. However, some of the metal ions may be reduced to form metal particles. Some of the metal ions bound to the metal ion-supported cellulose fiber can be removed by adding a reducing agent. By reducing the cellulose fiber, metal particles are partially formed on the surface of the cellulose fiber. It is also possible.

[0091] However, it is possible to use the entire amount of metal compounds as metal ions without any special reduction treatment. It is preferable in terms of antiviral, antibacterial and deodorizing effects.

[0092] The metal compounds in the metal-containing cellulose fiber obtained above are reduced to obtain metals. The mechanism by which particles are generated in cellulosic fibers is unclear, but is presumed to be as follows: The reduction reaction causes the metal compounds in the metal compound-containing cellulose fiber or metal compound-derived The ions are reduced to metals. At this time, the metals formed adhere to the surface of the cellulose fiber. Similarly, the metal particles that are generated are integrated with each other, and the particles grow to form nanoparticles. On the other hand, molecules that exist near the cellulosic fibers are bonded to the cellulosic fibers. Metal compounds that were not combined are also reduced to produce metals. It combines with the metal on the surface of the cellulose fibers to form metal particles.

[0093] The reduction reaction may be carried out by a known method, but it is preferable to reduce the metal compound while the metal compound and the acid group are reacted. It is preferable to carry out the reduction so as not to cleave the bond with hydrogen. and liquid-phase reduction using a reducing agent such as an aqueous solution of sodium borohydride. The conditions for the gas phase reduction, such as time and temperature, are appropriately adjusted. The reaction can be carried out at 0°C for 1 to 3 hours. The gas-phase reduction reaction is carried out by converting the metal-containing cellulose fiber into water. It is preferable to carry out the reduction reaction in a state where the film does not contain any solvent or solvent. The substrate may remain attached to the substrate or may be peeled off from the substrate. In this case, a membrane is obtained from the dispersion and is subjected to the reduction reaction with or without drying. The dispersion can also be subjected to a liquid phase reduction reaction without drying it. The reaction temperature in the liquid phase reduction is preferably 4 to 40°C, more preferably room temperature.

[0094] The presence of metal ions or particles in cellulosic fibers is confirmed by scanning electron microscope images. This can be confirmed by ICP emission spectrometry of the extract with strong acid. The presence of metals could not be confirmed by the electron microscope image, but the ICP emission spectrometry revealed that they contained metals. On the other hand, for example, the above metals are reduced from ions and exist as metal particles. If the metal particles are present, they can be seen in the scanning electron microscope image, so it is possible to identify the metal ions. In addition, the presence or absence of ions can be determined by scanning electron microscope images and energy dispersive X-ray analysis (EDS). The presence or absence of metal ions can also be determined by elemental mapping using a scanning electron microscope. Metal ions cannot be seen in the image, but elemental mapping reveals their presence. You can confirm this.

[0095] In the step of supporting metal ions or metal particles, The content of the cellulose fiber is preferably in the range of 10 to 100 mg / g. The range of 15 to 80 mg / g is more preferable, and the range of 20 to 60 mg / g is particularly preferable. If it is less than 10 mg / g, the antiviral, deodorizing and antibacterial functions will be deteriorated. On the other hand, if it exceeds 100 mg / g, metal ions may be easily eluted during manufacturing. This increases the burden on wastewater treatment.

[0096] The metal-containing cellulose fiber of the present invention is a fiber containing the metal-containing cellulose fiber. After the holding treatment, the beating treatment may be carried out at least once or more. Beating is a process that applies mechanical shear force to fibers. Some of the fibers are fibrillated, increasing the surface area, which generally reduces the interfiber space when dry. In addition to strengthening the bond, the specific surface area can be increased, allowing metal ions to be attracted to the surface. Therefore, in the present invention, the antiviral effect, deodorizing effect, and anti- On the other hand, excessive beating can cause the cellulose fibers to become too fine. If it is too thin, the yield will decrease when it is mixed with pulp and manufactured, or it will not remain in the paper. (No residue remains), and the antiviral, deodorizing, and antibacterial effects of metal-containing cellulose fibers have decreased. As an index of the degree of beating, the CSF can be used. Specifically, if the freeness factor (CSF) is less than 30 ml, the yield of the sheet decreases. The antiviral, deodorizing and antibacterial effects will decrease as the freeness factor (CSF) exceeds 600 ml. In this way, metal ions are insufficiently fibrillated, resulting in a decrease in the antiviral, deodorizing, and antibacterial effects. Alternatively, the freeness factor (CSF) of the cellulose fiber containing metal nanoparticles can be set to 30 to 600 ml. This improves the antiviral, deodorizing and antibacterial effects.

[0097] The apparatus used for beating is not particularly limited, and any known apparatus can be used. Examples of equipment include refiners, beaters, PFI mills, kneaders, dispersers, etc. A metal or blade is used to work with pulp fibers around a rotating shaft. By rubbing, as well as high pressure homogenizers, ultra-high pressure homogenizers, nanomizers, various Examples of such equipment include a mill, a stone mill, and the like.

[0098] In addition, prior to beating or, if necessary, dispersion treatment before beating, a preliminary Pretreatment may be carried out. Examples of pretreatment include mixing, stirring, emulsification, and dispersion. This may be carried out using a known device (for example, a high-shear mixer).

[0099] The metal ion-containing cellulose-based fiber may be made into nanofibers. The surface area increases in the affected area, enhancing the antiviral, deodorizing, and antibacterial effects. On the other hand, if the fibers are completely nanofiberized, the fibers will be completely disintegrated and will not blend with the pulp. When manufacturing, the yield is reduced, and the metal ion-containing cells do not remain in the paper. Here, the nanofiberization is the process of forming nanofibers by using metal ion-containing cellulose fibers. Nanofiber refers to the process of defibrating cellulose fibers to a diameter of 100 nm or less. For the purpose of beating, any known apparatus similar to that used for beating can be used.

[0100] <4. Synthetic Fibers> The antiviral sheet of the present invention may be a nonwoven fabric, and may be made of synthetic fibers, i.e., petroleum-based or other useful fibers. It contains at least one type of fiber made of synthetic resin polymerized from low molecular weight organic materials. Although the fiber is inferior to the above-mentioned cellulose fiber in terms of moisture absorption, water absorption, flexibility, etc., it has the advantage of being It is excellent in terms of stability and light resistance.

[0101] The content of synthetic fibers is preferably 5% by mass or more of the nonwoven fabric from the viewpoint of dimensional stability. It is also preferable that the content of the metal ion-containing cellulose fiber is 1% by mass or more relative to the nonwoven fabric. Therefore, the content of synthetic fibers is 99% by mass or less of the nonwoven fabric. It is preferable.

[0102] The type of synthetic fiber is not particularly limited, and examples thereof include polyethylene terephthalate (PET). Fiber, Polybutylene terephthalate (PBT) fiber, Polyethylene naphthalate (PEN ), polyester fibers such as polyethylene isophthalate (PEI) fibers, polypropylene Polypropylene (PP) fiber, polyethylene (PE) fiber, ethylene-vinyl alcohol copolymer fiber , polyolefin fibers such as ethylene-vinyl acetate copolymer fibers, polyacrylic fibers, Polyamide fiber, polyvinyl alcohol (PVA) fiber, polylactic acid (PLA) fiber, Polyester copolymer resin - polyester resin, polyethylene resin - polyester resin, Ethylene-vinyl alcohol copolymer resin - polyester resin, polyester copolymer resin -Polypropylene resin, polyethylene resin -Polypropylene resin, ethylene vinyl alcohol Copolymer resin - Polypropylene resin, Ethylene vinyl acetate copolymer resin - Polypropylene Examples include composite fibers such as polyethylene resin.

[0103] The synthetic fibers may also be primarily fibers having a single concentric structure, and may also be fibers having a core and a sheath. In a preferred embodiment, the synthetic fiber is a fiber dispersion. From the viewpoint of the performance, the fineness is 0.5 to 4.5 dtex, and the fiber length is 3 to 30 mm (preferably 5 to It is desirable that the thickness of the synthetic fiber is 20 mm, and more preferably 5 to 15 mm. Measurement of fineness and fiber length is based on JIS L 1015:2010. Also, the melting point of synthetic fibers is, for example, in the range of 110 to 300°C, preferably in the range of 110 to 280°C. Considering the high temperature processing such as embossing at high temperature in the later stage and the stability, It is more preferable that the melting point is in the range of 110°C to 260°C. When making base paper for nonwoven fabric, dirt (lint) from synthetic fibers occurs in the papermaking dryer. On the other hand, blending synthetic fibers with melting points above 300°C does not make sense from a technical standpoint. When using a core-sheath type synthetic fiber, the melting point of the sheath The melting point of synthetic fibers is measured in accordance with JIS K 7121: Based on 2012.

[0104] For core-sheath fibers, the core / sheath is polypropylene (PP) / polyethylene (PE). , polyethylene terephthalate (PET) / polyethylene (PE), polyethylene terephthalate Polyethylene terephthalate (PET) / low melting point polyethylene terephthalate (PET) or polypropylene Polypropylene (PP) / polypropylene (PP) are examples of core-sheath type polyester composite fibers. The fiber is made of modified polyester (low melting point component) and polyethylene (high melting point component) as the core. Examples of composite fibers (sheath-core fibers) made of polyethylene terephthalate include sheath-core polyolefins. Polyethylene composite fibers have a sheath (low melting point component) and a core (high melting point component). Examples of such fibers include composite fibers (sheath-core fibers) made of polypropylene.

[0105] If necessary, a binder may be used. Examples of binders include heat-fusible fibers, Examples of heat-fusible fibers include the above-mentioned core-sheath type polyamide fiber. Ester composite fiber, polyethylene terephthalate (PET) fiber, core-sheath polyolefin Examples of the hydrophilic pulp include polyaniline composite fibers and pulp-like multi-branched fibers. The pulp-like hyperbranched fiber is also called polyolefin synthetic pulp, and is available from, for example, Mitsui Chemicals An example is the product sold by Gakushu Co., Ltd. under the trade name SWP. Water-soluble fibers are those that do not dissolve in water at room temperature and maintain their fiber form, but after papermaking, When heated on the dryer surface, it begins to melt easily, and then re-solidifies during subsequent dehydration and drying to form a strong This refers to the fibers that make up the paper layer. Hot water soluble fibers include polyvinyl alcohol fibers. Fibrous binders are typically made from short cut polyvinyl alcohol fibres. It only swells in water at room temperature and does not dissolve, but dissolves in hot water at 60-90°C. It functions as a binder. Water-based adhesives include casein and sodium alginate. , hydroxyethyl cellulose, carboxymethyl cellulose sodium salt, polyvinyl Alcohol (PVA), water-soluble adhesives such as sodium polyacrylate, polyacrylic ester , acrylic-styrene copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, acrylic methyl methacrylate-butadiene copolymer, methyl methacrylate-butadiene copolymer, Emulsion adhesives such as ethylene-butadiene copolymers can be used.

[0106] <5. Other ingredients> In the antiviral sheet of the present invention, the above-mentioned metal-containing cellulose fiber, general cellulose In addition to the starch-based fibers and synthetic fibers, one or more other materials may be included as needed. The types of other materials are not particularly limited, but examples thereof include stabilizers such as heat stabilizers and weather stabilizers. Fixing agents, fillers, antistatic agents, slip agents, antiblocking agents, anti-fogging agents, lubricants, dyes, Examples of the additives include pigments, natural oils, synthetic oils, waxes, etc. These may be used alone or in combination of two or more. The total content of these materials shall not exceed 10% by mass of the sheet. It is preferable that the range is .

[0107] Stabilizers include, for example, 2,6-di-t-butyl-4-methyl-phenol (BHT ) and other antioxidants; tetrakis[methylene-3-(3,5-di-t-butyl-4-hydro] β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane Diphenyl)propionic acid alkyl ester, 2,2'-oxamidobis[ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate], phenolic Antioxidants: Zinc stearate, calcium stearate, 1,2-hydroxystearic acid Fatty acid metal salts such as calcium phosphate; glycerin monostearate, glycerin distearate stearate, pentaerythritol monostearate, pentaerythritol distearate and polyhydric alcohol fatty acid esters such as pentaerythritol tristearate. can be done.

[0108] Examples of fillers include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, Pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate Nesium, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite Sium, talc, clay, mica, asbestos, calcium silicate, montmorillonite, Examples include bentonite, graphite, aluminum powder, and molybdenum sulfide.

[0109] Examples of colorants include inorganic colorants such as titanium oxide and calcium carbonate, and phthalocyanine. Examples of suitable colorants include organic colorants such as ginseng.

[0110] Examples of lubricants include oleic acid amide, erucic acid amide, and stearic acid amide. Examples include: <6. Antiviral Sheet> The antiviral sheet of the present invention is made of pulp slurry (paper stock) in the same manner as ordinary paper sheets. The metal-containing cellulose fiber is mixed with the above-mentioned sample, and paper is made using the sample. For papermaking, known papermaking machines such as a Fourdrinier papermaking machine, a twin-wire papermaking machine, and a cylinder papermaking machine are used. The papermaking conditions are not limited.

[0111] The antiviral sheet of the present invention further comprises the above-mentioned metal-containing cellulose fiber, and optionally Synthetic fibers, common cellulosic fibers, and other materials are used to form a layer of fibers called fleece. The fibers are then bonded together and, if necessary, dyed, laminated, coated, or other processing is carried out. It can be produced by

[0112] The method for forming the fleece is not particularly limited, and any known method can be used. For example, dried fibers are mixed in a machine called a card or in a constant air flow called an air laying. Dry-laid method: forming fibers in a directional or random arrangement; similar to the process of making paper, The wet method involves dispersing the resin in the mixture and then raising it onto a mesh net; and the melted resin is then directly poured into the nozzle. The spunbond method involves dissolving and spinning the fibers from the beginning to form fleece with continuous, long fibers. It can be done.

[0113] In particular, it is preferable to use a wet method since cellulosic fibers are hydrophilic. In the case of the papermaking method, the paper can be produced by a conventional papermaking method. Various types of machines are used, such as cylinder paper machines, inclined short wire paper machines, Fourdrinier paper machines, and short wire paper machines. The papermaking process can be carried out in a variety of ways, and papermaking machines can be combined appropriately according to the required properties. Drying processes include Yankee dryer type, multi-cylinder type, hot air type, infrared heating type, etc. It is possible.

[0114] The method for bonding the fibers together is not particularly limited, and any known method can be used. For example, the fleece can be impregnated with emulsion adhesive resin or sprayed. Chemical bonding method in which fibers are attached to a material and then heated and dried to bond the intersections of the fibers; low-melting point heat fusion The fleece containing the mixed fibers is heat-pressed by passing it between heated rolls or by applying hot air. The thermal bonding method bonds the fibers together using a high-speed needle. The needle repeatedly pierces the fabric, entangling the fibers with the barbs on the needle. Noodle punch method; Hydroentanglement method in which high-pressure water is sprayed onto fleece in a columnar fashion to entangle the fibers; etc. In particular, the chemical bonding method is preferred.

[0115] In the production of dry nonwoven fabrics, synthetic fibers, paper strength agents, binders, fillers ( As a dry method, a card method ( Carding method), air laying method, web bonding, chemical bonding method, thermal bonding method Examples of methods include the spunlace method, the needle punch method, and the like.

[0116] The carding method involves feeding the composite and thermoplastic synthetic fibers into a carding machine to form an accumulated layer of fibers (nonwoven web). This is then heat treated at a temperature above the melting point of the thermoplastic fiber to form a thermoplastic composite. A thermal bonding method in which a portion of the fibers is melted to bond the fibers together, or the nonwoven web The fiber can be produced by hydroentangling the fiber and then heat treating it. The web manufacturing methods are parallel web, cross web, random web, crisscross web, etc. Examples of the web include a random web and a semi-random web.

[0117] In the air-laying method, defibrated raw fiber is transported in an air current to form a web. A binder is applied to the fiber web, and the fibers of the fiber web are bonded together by the binder. The air-laying method is the Honshu Paper Manufacturing Method (Kinochrome). method), Karl Kroyer method, Scanweb method (Dunweb method), J&J method, KC method, Examples include the Scott Paper Act.

[0118] When the dry nonwoven fabric of the present invention is produced by the air-laying method, a method for bonding the fibers together is used. A binder may be used for this purpose. The binder to be used can be selected appropriately as needed. Examples include casein, sodium alginate, hydroxyethyl cellulose, and calcium carbonate. Sodium carboxymethylcellulose, polyvinyl alcohol (PVA), polyacrylic acid Water-based binders such as soda, polyacrylic ester, acrylic styrene Copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene Emulsions of styrene copolymers, methyl methacrylate-butadiene copolymers, etc. Emulsion-type binders such as ethylene-butadiene copolymer latex can be used. is.

[0119] The nonwoven antiviral sheet of the present invention may have a single layer structure or a multi-layer structure. In the case of a multi-layer structure, at least one layer may contain the metal-containing cellulose fiber. must contain

[0120] The content of metal ions and / or metal particles in the antiviral sheet of the present invention is 0.2 to 1.0 μm. The content of metal ions and / or metal particles is preferably 0.2 mass % or more. If the content is less than 50% by mass, the antiviral, antibacterial and deodorizing effects will be insufficient. Improvements in antiviral, antibacterial, and deodorizing effects have plateaued.

[0121] The basis weight (grammage) of the antiviral sheet is not particularly limited, but is preferably 10 to 300 g / m 2 of The range is preferably 15 to 200 g / m 2 It is more preferable that the range is: If the nonwoven fabric has a multi-layer structure, the basis weight of each layer is 10 g / m 2 The above conditions must be met in order to ensure uniformity and quality. This is preferable in terms of producing a sheet that has the minimum strength required for handling during manufacturing. The basis weight of the antiviral sheet in this invention is 0.05m 2 More than 105% nonwoven fabric After drying at 20°C until a constant mass was reached, the sample was left in a constant temperature room at 20°C and 65% RH for at least 16 hours. The mass of the nonwoven fabric was measured. 2 This is the mass (g) per unit.

[0122] The thickness of the antiviral sheet is preferably in the range of 20 to 500 μm, and more preferably in the range of 30 to 500 μm. It is more preferable that the thickness of each layer is in the range of 100 μm. The thickness is preferably 20 μm or more in order to produce a uniform sheet. There is no particular limitation on the

[0123] The antiviral sheet of the present invention can be used as it is, or can be combined with other nonwoven fabrics, etc. as needed. and / or various processes such as embossing and pleating are applied to the substrate. The filter can be suitably used for various purposes such as a filter for filtering gases or liquids.

[0124] The antiviral sheet of the present invention may include three or more nonwoven fabric layers. In this case, it is preferable that the inner layer is a nonwoven fabric layer containing metal ion-containing cellulosic fibers. The outer layer other than the inner layer can be made of a nonwoven fabric used in known mask substrates.

[0125] In the present invention, the antiviral sheet may be subjected to a mesh treatment. Specific examples of the shape include a lattice shape, a polka dot shape, and a polygonal shape. However, the present invention is not limited to these.

[0126] In the present invention, the antiviral sheet and the metal-containing cellulose fiber having antiviral properties are The uses of the fiber are not particularly limited, but are suitable for applications where antiviral, deodorizing, and antibacterial properties are required. In addition, when the antiviral sheet is made of nonwoven fabric, it can be used as it is. It can be used as is, or laminated with other substrates such as nonwoven fabrics as required, and / or embossed. After various processes such as pleating and other processes are performed, it is used for various purposes such as gas or liquid filtration filters. Examples of applications include packaging materials (paper containers, cardboard, resin films, etc.). Film, wrapping paper, etc.), building materials (wallpaper, decorative paper, floor coverings, etc.), sanitary products (diapers, sanitary products, Empty, masks, wet towels, gauze, cotton swabs, etc.) Daily necessities (deodorizing agents, fragrances, food filters, etc.) Filter, clean filter, placemat, tray mask, tablecloth, drainer Net, cooking paper, cooking sheet, scum removal sheet, kitchen towel, cloth Dishcloths, aprons, pot holders, toilet seat covers, splash-proof sheets for toilet floors, foot mats, Wet tissues, disposable slippers, carpet base material, shoe insoles, suit covers, Tote bags, condensation sheets, book covers, vacuum cleaner paper bags, sticky notes, bookmarks, notebooks, (Notebook covers, pet sheets, disposable sheets, pillowcases, futon covers, wipes, etc.) , industrial products (industrial filters, industrial wipers, automotive interior materials, etc.), medical products (masks, Protective clothing, surgical gowns (caps, aprons, tops and bottoms), antibacterial mats, cleaning cloths, medical tape etc.), clothing (disposable underwear etc.), gardening and agricultural materials (gardening sheets, agricultural sheets, seedbeds seat covers, fruit bags, etc.), headrest covers (for bullet trains and automobiles), other paper products (curtains, etc.) Examples include: [Example]

[0127] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. It's not something like that.

[0128] [Example 1] <Production of oxidized cellulose fibers> 5.00g (bone dry) of bleached unbeaten kraft pulp (brightness 85%) derived from softwood was added to the EMPO (2,2,6,6-tetramethylpiperidine-1-oxyl; Sigma Al drich) 39 mg (0.05 mmol per 1 g of bone-dry cellulose) and sodium bromide 514 mg of cellulose (1.0 mmol per 1 g of bone-dry cellulose) was dissolved in 500 ml of water. ml and stirred until the pulp was uniformly dispersed. A sodium hypochlorite aqueous solution was added to the reaction system, and the sodium hypochlorite concentration was 5.5 mmol / g. The oxidation reaction was started at room temperature. During the reaction, the pH in the system decreased, The pH was adjusted to 10 by gradually adding 3M aqueous sodium hydroxide solution. The reaction was terminated when the pH in the system no longer changed. After the reaction, the mixture was filtered through a glass filter, washed with a sufficient amount of water, and filtered twice. By repeating this process several times, oxidized cellulose fibers impregnated with water having a solid content of 10% by mass were obtained. The pulp yield was 90%, the oxidation reaction took 90 minutes, and the amount of carboxyl groups was was 1.68 mmol / g.

[0129] <Supporting metal ions on oxidized cellulose fibers> Water was added to the above oxidized cellulose fiber to make a dispersion with a solids concentration of 2%, and the pH was adjusted to 9. After adjusting the temperature to 0, CuCl2 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 1 g of oxidized cellulose fiber. Add the solution while stirring so that the concentration becomes 1.0 mmol / g, and then stir for another 30 minutes. By doing so, Cu ions were incorporated into the oxidized cellulose fibers. In response to this, washing with sufficient amounts of water and filtering were repeated twice to remove unreacted metals. After removing salt, the copper ion-loaded cellulose fiber (metal) was impregnated with water and had a solid content of 30% by mass. The resulting fiber was ion-containing cellulosic fiber. The metal ion content of the oxidized cellulose fiber was 40 mg / g. The freeness of the contained cellulosic fiber was 500 ml.

[0130] <Manufacturing of antiviral sheets> 5% of the above metal ion-containing cellulose-based fibers, metal ion-free cellulose-based fibers (General cellulosic fiber) Hardwood bleached kraft pulp (LBKP with freeness of 600 ml) (manufactured by Nippon Paper Industries Co., Ltd.) was used with a 95% blend ratio, and water was added to make the solids concentration 0. A 0.5 wt% water dispersion was prepared. This is made into paper with a round hand-made papermaking machine, with a basis weight of 30 g / m 2 The paper is made so that it becomes like this, and then dewatered in a press. Then, by drying it at 85°C in a cylinder dryer, the diameter of the A round antiviral sheet was produced.

[0131] [Comparative Example 1] In the process of manufacturing the antiviral sheet, no metal-containing cellulose fiber is blended, As a cellulosic fiber that does not contain metal ions, bleached hardwood kraft pulp (freeness 600) was used. The blending ratio of 100 ml of LBKP (manufactured by Nippon Paper Industries Co., Ltd.) was 100%. An antiviral sheet was prepared in the same manner as in 1.

[0132] [Example 2] <Production of carboxymethyl cellulose-based fibers> Pulp (NBKP (Softwood Bleached Kraft Pulp)) is mixed in a mixer that can mix pulp. , manufactured by Nippon Paper Industries Co., Ltd.) in a dry mass of 200 g, and sodium hydroxide in a dry mass of 111 g. Then, water was added so that the pulp solid content became 20% (w / v). After stirring for 30 minutes, 216 g of sodium monochloroacetate (effective ingredient equivalent) was added. After stirring, the temperature was raised to 70°C and stirred for 1 hour. After that, the reaction product was taken out, neutralized, washed, and The carboxymethyl substitution degree per glucose unit was 0.25. Thus, cellulose-based fibers were obtained.

[0133] <Carboxymethylated cellulose fiber loaded with metal ions> The carboxymethylated cellulose fiber (carboxymethylated cellulose fiber) obtained by the above procedure The pH of the dispersion was adjusted to 8.5, and the concentration was adjusted to 1.0 mmol / g (1.0 mmol / g of carboxymethylcellulose fiber). A CuCl2 aqueous solution was added so that the concentration of CM was 100% (per 1000 mg), and the mixture was stirred for 15 minutes. By incorporating Cu ions into oxidized cellulose fibers and then washing them to remove unreacted metal salts, The obtained cellulose fiber carrying Cu ions (metal ion-containing cellulose fiber) The metal ion (Cu) content of the metal ion-containing cellulose fiber was 31.3 mg / It was g.

[0134] <Manufacturing of antiviral sheets> The metal ion-containing cellulose fiber is treated with the above-mentioned carboxylated cellulose fiber containing metal ions. An antiviral sheet was produced in the same manner as in Example 1, except that fiber was used instead.

[0135] [Example 3] <Production of cellulose phosphate> 6.75g of sodium dihydrogen phosphate dihydrate, 4.83g of disodium hydrogen phosphate in 19 The reaction mixture was dissolved in 0.62 g of water to obtain a reaction solution. The whiteness was 85% and water was added to make the concentration 4%. The mixture was beaten using an iner until the CSF was 200 ml and the average fiber length was 0.7 mm. The resulting cellulose suspension was diluted to 0.3% and the water content was 90%. A pulp sheet (weight: 3 g) was obtained. The pulp sheet was immersed in 31.2 g of the reaction solution. After heating in a blast dryer at 105°C for 1 hour, the cellulose was further heated at 150°C for 1 hour. Next, we introduced phosphate groups into cellulose-based fibers. 500 ml of ion-exchanged water was added to the sheet, and after stirring and washing, the sheet was dehydrated. Dilute with 0.00 ml of ion-exchanged water, and add 5 ml of 1N aqueous sodium hydroxide solution while stirring. was added little by little to obtain a cellulose suspension with a pH of 12 to 13. The suspension was dehydrated and washed with 500 ml of ion-exchanged water. Infrared absorption spectroscopy revealed that the phosphate group is present at 1230-1290 cm-1. The amount of phosphate groups introduced at this time was determined by the amount of phosphate groups introduced into the fine fiber. It was 2.1 mmol / g per 1 g (mass) of cellulose.

[0136] <Supporting metal ions on phosphate-esterified cellulose fibers> Water was added to the above phosphate esterified cellulose fiber to prepare a dispersion with a solid content of 2%. After adjusting the pH to 9.0, CuCl2 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the solution. Add the mixture while stirring until the concentration becomes 1.0 mmol / g per 1 g of cellulose fiber. The resulting mixture was stirred for another 30 minutes to allow the Cu ions to be attached to the phosphated cellulose fiber. It contained chlorine. In response to this, washing with sufficient amounts of water and filtering were repeated twice to remove unreacted metals. The salt was removed, and the water-impregnated Cu ion-loaded cellulose fiber (gold) with a solid content of 30% was used. Metal ion-containing cellulosic fibers were obtained. The metal ion content of the phosphate-esterified cellulose fiber was 41 mg / g. Ta.

[0137] <Manufacturing of antiviral sheets> The metal ion-containing cellulose fiber is then phosphated with the metal ion-containing phosphate ester. An antiviral sheet was prepared in the same manner as in Example 1, except that the fiber was changed to a cellulose-based fiber. Ta.

[0138] [Example 4] <Production of phosphite-esterified cellulose fiber> Mix 13g of sodium hydrogen phosphite pentahydrate, 10.8g of urea, and 76.2g of water. A reaction solution was prepared. 100 g of the reaction solution and bleached unbeaten kraft pulp (white) derived from softwood were mixed. The dried pulp was mixed with 10g of pulp (85% solubility) and dried at 105°C. The mixture was reacted for 2 hours, and then washed with water and filtered twice to remove the phosphorous acid containing cations consisting of inorganic substances. The phosphate-esterified cellulose fiber with the ester introduced was obtained. The value was 1.2 mmol / g per 1 g (mass) of fine fibrous cellulose.

[0139] <Supporting metal ions on phosphite-esterified cellulose fibers> Add water to the above phosphite esterified cellulose fiber to make a dispersion with a solid content of 2%. After adjusting the pH to 9.0, CuCl2 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the solution containing phosphorous acid. Stir to make the concentration 1.0 mmol / g per 1 g of esterified cellulose fiber. Add the cellulose phosphate ester and stir for another 30 minutes. Cu ions were included. In response to this, washing with sufficient amounts of water and filtering were repeated twice to remove unreacted metals. The salt was removed, and the water-impregnated Cu ion-loaded cellulose fiber (gold) with a solid content of 30% was used. Metal ion-containing cellulosic fibers were obtained. The metal ion content of the phosphite esterified cellulose fiber was 42 mg / g. It was.

[0140] <Manufacturing of antiviral sheets> The metal ion-containing cellulose fiber is treated with the above-mentioned metal ion-containing phosphite esterified cellulosic fiber. An antiviral sheet was prepared in the same manner as in Example 1, except that cellulose-based fibers were used. did.

[0141] [Example 5] <Production of sulfonated cellulose-based fibers> A reaction solution was prepared by mixing 20 g of sulfamic acid, 10 g of urea, and 100 ml of water. 130 g of the reaction solution was mixed with 2 g of bleached unbeaten kraft pulp (brightness 85%) derived from softwood (dry The resulting slurry was stirred for 10 minutes. After stirring, the slurry was filtered using filter paper. The pulp sheet was placed in a dryer set at 50°C. The dried pulp was heated at 120°C for 30 minutes and dried until the moisture content reached equilibrium. After the heating reaction, the reacted pulp was washed with pure water until it became neutral, and then sulfamic acid / Urea-treated sulfonated cellulose fibers were prepared. The amount of sulfonic groups introduced was 0. 0.9mmol / g.

[0142] <Supporting metal ions on sulfonated cellulose fibers> Water was added to the sulfonated cellulose fiber to prepare a dispersion with a solid content of 2%, and the After adjusting H to 9.0, CuCl2 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to sulfonated cellulose Add the mixture while stirring so that the concentration per 1 g of fiber becomes 0.5 mmol / g. The mixture was stirred for 30 minutes to allow the sulfonated cellulosic fibers to incorporate Cu ions.

[0143] In response to this, washing with sufficient amounts of water and filtering were repeated twice to remove unreacted metals. The salt was removed, and the water-impregnated Cu ion-loaded cellulose fiber (gold) with a solid content of 30% was used. Metal ion-containing cellulosic fibers were obtained. The metal ion content of the sulfonated cellulose fiber was 21 mg / g.

[0144] <Manufacturing of antiviral sheets> The metal ion-containing cellulose fiber is converted into the above-mentioned sulfonated cellulose containing metal ions. An antiviral sheet was produced in the same manner as in Example 1, except that the fiber was changed to synthetic fiber.

[0145] The antiviral properties of the antiviral sheets obtained in the examples and comparative examples were evaluated as follows: did. Evaluation of antiviral properties The antiviral properties of the samples prepared in Example 1 and Comparative Example 1 were evaluated. The amount of sample used in the antiviral test was 0.4 g. The test was carried out in accordance with the 1922:2016 standard and the antiviral activity value was calculated. The following two types were used. Influenza virus (H3N2, ATCC VR-1679) Feline calicivirus (Strain: F-9 ATCC VR-782)

[0146] [Table 1]

[0147] As is clear from Table 1, in the case of Examples 1 to 5 containing metal-containing cellulose-based fibers, The comparative example, which did not contain metal-containing cellulose fibers, showed high antiviral properties. In the case of 1, the antiviral properties were poor.

[0148] [Example 6] <Production of metal ion-containing cellulose fibers> 5.00g (bone dry) of bleached unbeaten kraft pulp (brightness 85%) derived from softwood was added to the EMPO (Sigma Aldrich) 39 mg (0.01 g of bone-dry cellulose) 05 mmol) and 514 mg of sodium bromide (1.0 mmol per 1 g of bone-dry cellulose) l) was added to 500 ml of the aqueous solution, and the mixture was stirred until the pulp was uniformly dispersed. Next, the sodium hypochlorite aqueous solution was diluted to 5.5 mmol / g. The reaction mixture was added to the reaction system so that the pH value was adjusted to 100%. The oxidation reaction was initiated at room temperature. However, 3M aqueous sodium hydroxide solution was gradually added to adjust the pH to 10. The reaction was terminated when the sodium was consumed and the pH in the system no longer changed (the amount required for the oxidation reaction). Total time: 90 minutes. After the reaction, the mixture was filtered through a glass filter, washed with a sufficient amount of water, and filtered twice. By repeating this process several times, water-impregnated oxidized cellulose fibers were obtained (solid content: 10% by mass). , pulp yield: 90%, carboxyl group content: 1.68 mmol / g). Water was added to the obtained oxidized cellulose fiber to make a dispersion with a solid concentration of 2%, and the pH was adjusted to The pH was adjusted to 9.0. Next, CuCl2 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to cellulose oxide. Add the solution while stirring so that the concentration per 1 g of fiber becomes 1.6 mmol / g, and then add another 30 The mixture was stirred for 1 minute to allow Cu ions to be incorporated into the oxidized cellulose fibers. After that, the unreacted metal salts were removed by washing with a sufficient amount of water and filtering twice. The cellulose fibers were removed and impregnated with water to obtain Cu ion-supported cellulose fibers (solid content: 30% by mass). The metal ion content in the obtained metal ion-containing cellulose fiber was 50 mg / g. The freeness of the metal ion-containing cellulosic fiber was 500 ml. <Nonwoven fabric manufacturing> 10% of the above metal ion-containing cellulose fiber, 10% of the metal ion-free cellulose fiber Fiber (general cellulose fiber) is softwood bleached kraft pulp (NBK with freeness of 600 ml) P; Nippon Paper Industries Co., Ltd.) 20%, synthetic fiber: PET fiber (Teijin Frontier, Ecopet) ) cut into 5mm fiber length 30%, binder fiber (core-sheath type polyester composite fiber Fiber, sheath melting point: 100-160°C, core: polyethylene terephthalate (40%) Water was added to the blend to prepare an aqueous dispersion with a solid content concentration of 0.5% by mass. This is made into paper with a round hand-made papermaking machine, with a basis weight of 30 g / m 2 The paper is made so that it becomes like this, and then dewatered in a press. Then, by drying it at 85°C in a cylinder dryer, the diameter of the A round nonwoven fabric was produced.

[0149] Comparative Example 2 In the process of manufacturing nonwoven fabric, metal ions are not mixed in without using metal-containing cellulose fibers. Contains no cellulose-based fiber (NBKP pulp with a freeness of 600 ml, manufactured by Nippon Paper Industries Co., Ltd.) A nonwoven fabric was produced in the same manner as in Example 6, except that the ratio was changed to 30%. <Evaluation of nonwoven fabrics> The antiviral properties of the obtained nonwoven fabric were evaluated in the same manner as in Example 1. [Table 2] As is clear from the above results, the metal-containing cellulose fiber and the non-metallic fiber containing synthetic fiber The woven fabric showed high antiviral properties. On the other hand, the fabric that did not contain metal-containing cellulosic fibers The nonwoven fabric did not exhibit antiviral properties.

Claims

1. An antiviral sheet having an antiviral activity value (Mv) of 2.0 or more against influenza virus or feline calicivirus in accordance with the antiviral testing method for textile products (JIS L1922:2016), the antiviral sheet comprises metal-containing cellulosic fibers in which metal ions are ionically bonded to cellulosic fibers having anionic groups, the metal-containing cellulosic fibers having a freeness of 30 to 800 mL; The antiviral sheet described above, wherein the content of the metal-containing cellulose fibers is 10 mass% or less, and the metal-containing cellulose fibers contain one or more metal ions and / or metal particles selected from the group consisting of Ag, Au, Pt, Pd, Ni, Mn, Fe, Ti, Al, Zn, and Cu.

2. 2. The antiviral sheet according to claim 1, wherein the content of the metal ions and / or metal particles in the metal-containing cellulosic fibers is 10 to 100 mg / g of the cellulosic fibers.

3. 3. The antiviral sheet according to claim 1, wherein the Cu ion content is 10 to 60 mg / g of the cellulosic fibers.

4. The antiviral sheet according to any one of claims 1 to 3, wherein the amount of anionic groups in the cellulose fibers having anionic groups is 0.01 to 3.0 mmol / g.

5. The antiviral sheet according to any one of claims 1 to 4, wherein the cellulose-based fibers having anionic groups are oxidized cellulose-based fibers having carboxyl groups or carboxylate groups.

6. The antiviral sheet according to any one of claims 1 to 4, wherein the cellulosic fibers having anionic groups are carboxyalkylated cellulosic fibers having carboxyalkyl groups.

7. The antiviral sheet according to any one of claims 1 to 4, wherein the cellulose-based fibers having anionic groups comprise phosphated cellulose-based fibers having phosphate groups, phosphite-esterified cellulose-based fibers having phosphite groups, or sulfonated cellulose-based fibers having sulfate groups.

8. The antiviral sheet according to any one of claims 1 to 7, wherein the antiviral sheet contains cellulosic fibers that do not contain metal.

9. The antiviral sheet according to any one of claims 1 to 8, wherein the antiviral sheet contains synthetic fibers.

10. The antiviral sheet according to any one of claims 1 to 9, wherein the antiviral sheet contains binder fibers.

11. The antiviral sheet according to any one of claims 1 to 10, wherein the antiviral sheet is a sheet of two or more layers, at least one of which contains the metal-containing cellulosic fiber.

12. The antiviral sheet according to any one of claims 1 to 11, wherein the content of metal ions and / or metal particles in the antiviral sheet is 0.2 to 50 mass%.

13. A method for producing the antiviral sheet according to any one of claims 1 to 12, comprising: The method further comprises the step of wet-laid papermaking from a slurry containing metal-containing cellulosic fibers.

14. A metal-containing cellulosic fiber in which a metal ion is ionically bonded to a cellulosic fiber having an anionic group, The fiber has antiviral activity of 2.0 or more against influenza virus or feline calicivirus according to JIS L 1922:2016 Testing Methods for Antiviral Activity of Textile Products, and contains one or more metal ions and / or metal particles selected from the group consisting of Ag, Au, Pt, Pd, Ni, Mn, Fe, Ti, Al, Zn, and Cu, and the content of the metal ions and / or metal particles is 10 to 100 mg / g of the cellulosic fiber, The metal-containing cellulose fiber has a freeness of 30 to 800 mL, and the cellulose fiber having an anionic group is an oxidized cellulose fiber having a carboxyl group or a carboxylate group.

15. A metal-containing cellulosic fiber in which a metal ion is ionically bonded to a cellulosic fiber having an anionic group, The fiber has antiviral activity of 2.0 or more against influenza virus or feline calicivirus according to JIS L 1922:2016 Testing Methods for Antiviral Activity of Textile Products, and contains one or more metal ions and / or metal particles selected from the group consisting of Ag, Au, Pt, Pd, Ni, Mn, Fe, Ti, Al, Zn, and Cu, and the content of the metal ions and / or metal particles is 10 to 100 mg / g of the cellulosic fiber, The metal-containing cellulose fiber has a freeness of 30 to 800 mL, and the cellulose fiber having an anionic group is a carboxyalkylated cellulose fiber having a carboxyalkyl group.

16. A metal-containing cellulosic fiber in which a metal ion is ionically bonded to a cellulosic fiber having an anionic group, The fiber has antiviral activity of 2.0 or more against influenza virus or feline calicivirus according to JIS L 1922:2016 Testing Methods for Antiviral Activity of Textile Products, and contains one or more metal ions and / or metal particles selected from the group consisting of Ag, Au, Pt, Pd, Ni, Mn, Fe, Ti, Al, Zn, and Cu, and the content of the metal ions and / or metal particles is 10 to 100 mg / g of the cellulosic fiber, The metal-containing cellulose fiber has a freeness of 30 to 800 mL, and the cellulose fiber having an anionic group is a phosphated cellulose fiber having a phosphate group.

17. A metal-containing cellulosic fiber in which a metal ion is ionically bonded to a cellulosic fiber having an anionic group, The fiber has antiviral activity of 2.0 or more against influenza virus or feline calicivirus according to JIS L 1922:2016 Testing Methods for Antiviral Activity of Textile Products, and contains one or more metal ions and / or metal particles selected from the group consisting of Ag, Au, Pt, Pd, Ni, Mn, Fe, Ti, Al, Zn, and Cu, and the content of the metal ions and / or metal particles is 10 to 100 mg / g of the cellulosic fiber, The metal-containing cellulose fiber has a freeness of 30 to 800 mL, and the cellulose fiber having an anionic group is a phosphite-esterified cellulose fiber having a phosphite group.

18. A metal-containing cellulosic fiber in which a metal ion is ionically bonded to a cellulosic fiber having an anionic group, The fiber has antiviral activity of 2.0 or more against influenza virus or feline calicivirus according to JIS L 1922:2016 Testing Methods for Antiviral Activity of Textile Products, and contains one or more metal ions and / or metal particles selected from the group consisting of Ag, Au, Pt, Pd, Ni, Mn, Fe, Ti, Al, Zn, and Cu, and the content of the metal ions and / or metal particles is 10 to 100 mg / g of the cellulosic fiber, The metal-containing cellulose fiber has a freeness of 30 to 800 mL, and the cellulose fiber having an anionic group is a sulfonated cellulose fiber having a sulfate group.

19. The metal-containing cellulose fiber according to any one of claims 14 to 18, wherein the amount of anionic groups in the cellulose fiber having anionic groups is 0.01 to 3.0 mmol / g.

20. The metal-containing cellulosic fiber according to any one of claims 14 to 19, wherein the content of Cu ions is 10 to 60 mg / g of the cellulosic fiber.

Images