Paper yarn, paper yarn woven or knitted fabric, and fiber fabric product

Abstract

To provide a paper yarn having deodorant, antibacterial, and antiviral properties, and uniform appearance and sufficient strength, and also to provide a woven or knitted fabric and a fiber fabric product, which have deodorant, antibacterial, and antiviral functionalities obtained from the paper yarn.SOLUTION: A paper yarn is obtained using paper yarn base paper including pulp and metal-containing anion-modified cellulosic fibers containing one or more kinds of metal ions and / or metal particles selected from a group 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 paper yarns (yarns made of paper), paper yarn knitted or woven fabrics, and fibrous fabric products made using the same.

Background Art

[0002] A variety of fibers are used in fabrics. For example, there are chemical synthetic fibers such as polyester, nylon, and acrylic, natural fibers such as cotton and wool, and types that are a mixture of natural and synthetic fibers. Synthetic fibers are excellent materials, but due to the increasing environmental awareness, attention has been focused on natural materials that decompose in nature. On the other hand, there is a problem that it is difficult to impart various functionalities like synthetic fibers. Patent Document 1 discloses a metal-supported twisted yarn having a deodorizing effect, but the processability of the twisted yarn into knitted or woven fabrics is insufficient, and it was unclear whether the functionality was maintained after processing.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide paper yarns having deodorizing, antibacterial, and antiviral properties, and having a uniform appearance and sufficient strength, and knitted or woven fabrics and fibrous fabric products having the functionalities of deodorizing, antibacterial, and antiviral properties obtained from the paper yarns.

Means for Solving the Problems

[0005] The present invention is as follows. A paper yarn obtained by using a base paper for paper yarn containing pulp and metal-containing anionic modified cellulose fibers 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. A woven or knitted fabric obtained by using the paper yarn according to [1]. A fibrous fabric product obtained by using the woven or knitted fabric according to [2]. [Advantages of the Invention]

[0006] According to the present invention, there can be provided a paper yarn having deodorizing, antibacterial, and antiviral properties, as well as a uniform appearance and sufficient strength, and a woven or knitted fabric and a fibrous fabric product having deodorizing, antibacterial, and antiviral functional properties obtained from the paper yarn. [Embodiments for Carrying Out the Invention]

[0007] (Paper Yarn) The paper yarn of the present invention is a paper yarn containing pulp and metal-containing anionic modified cellulose fibers. The metal-containing anionic modified cellulose fibers have deodorizing, antibacterial, and antiviral properties, and woven or knitted fabrics and fibrous fabric products obtained by using this paper yarn also have deodorizing, antibacterial, and antiviral properties after processing. The paper yarn of the present invention is obtained by twisting a tape obtained by thinly slitting a base paper for paper yarn. From the viewpoint of environmental protection, it is preferable that pulp + metal-containing anionic modified cellulose fibers are contained in an amount of 50% or more based on the total fiber weight constituting the base paper for paper yarn.

[0008] (Metal-Containing Anionic Modified Cellulose Fibers) The metal-containing anionic modified cellulose fiber of the present invention 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. The metal-containing anionic modified cellulose fiber has metal ions ionically bonded to a cellulose fiber having an anionic group. By using the anionic modified cellulose fiber, the metal ions are chemically bonded and less likely to desorb, and the anionic group improves the paper strength during wet and dry states, so that it can have sufficient strength as a base paper for paper yarn. Examples of the anionic modified cellulose fiber include oxidized cellulose, etherified cellulose (such as carboxymethylated cellulose), esterified cellulose (such as phosphoric acid esterified cellulose), sulfonated cellulose, and the like.

[0009] In the present invention, natural cellulose is preferably used as the raw material of the metal-containing anionic modified cellulose fiber. Examples of natural cellulose include various wood pulps obtained from coniferous trees and broad-leaved trees, kenaf, bagasse, straw, bamboo, cotton, non-wood pulp obtained from seaweed, cellulose obtained from jellyfish, cellulose produced by microorganisms, and the like.

[0010] The metal-containing anionic modified cellulose fiber preferably has a Canadian standard drainage degree of 200 to 700 ml, a fiber length of 0.5 to 2.5 mm, and a fiber diameter of 10 to 40 μm. Being in this range makes it less likely to break paper during papermaking. In this specification, the average fiber length and the average fiber width respectively mean the length-weighted average fiber length and the length-weighted average fiber width. For example, they can be measured by observing the fibers using an image analysis device such as a fiber tester manufactured by ABB Ltd., a fractionator manufactured by Valmet Corporation, FS5 manufactured by Valmet Corporation, Morfi manufactured by Voith Turbo GmbH, an optical microscope, an electron microscope, or the like.

[0011] Regarding the amount of anionic groups in the cellulose fiber having an anionic group, in a cellulose fiber having a carboxyl group, a carboxylate group, a phosphate group, or a sulfonic acid group, it can be measured by the following method.

[0012] (Quantification of the amount of anionic groups 1) Prepare 60 ml of a 0.5 mass% slurry (aqueous dispersion) of a cellulose-based fiber sample having an acid group, add 0.1 M hydrochloric acid aqueous solution to adjust the pH to 2.5, and then dropwise add 0.05 N sodium hydroxide aqueous solution until the pH reaches 11. Measure the electrical conductivity, and calculate from the amount of sodium hydroxide (a) consumed in the neutralization stage of the weak acid where the change in electrical conductivity is gentle using the following formula. Amount of anionic groups [mmol / g] of cellulose-based fibers having an acid group = a [ml] × 0.05 / mass of oxidized cellulose-based fibers having an acid group [g] / x. (x: value corresponding to the valence of the acid group (carboxyl group, carboxylate group, sulfonic acid group: 1, phosphate group: 2)

[0013] When quantifying the amount of anionic groups by carboxyalkylation treatment, the following method is used.

[0014] (Quantification of the amount of anionic groups 2) Precisely weigh about 2.0 g of carboxyalkylated cellulose fiber (bone-dry) and place it in a 300 mL Erlenmeyer flask with a stopper. Add 100 mL of a solution prepared by adding 100 mL of special grade concentrated nitric acid to 1000 mL of nitric acid methanol, shake for 3 hours to convert the carboxyalkyl cellulose salt (CM cellulose) to hydrogen-type CM cellulose. Precisely weigh 1.5 - 2.0 g of hydrogen-type CM cellulose (bone-dry) and place it in a 300 mL Erlenmeyer flask with a stopper. Moisten the hydrogen-type CM cellulose with 15 mL of 80% methanol, add 100 mL of 0.1 N NaOH, and shake at room temperature for 3 hours. Using phenolphthalein as an indicator, back-titrate the excess NaOH with 0.1 N H2SO4. The degree of carboxyalkyl substitution (DS) is calculated by the following formula. A = [(100 × W - (0.1 N H2SO4) (mL) × F) × 0.1] / (bone-dry mass of hydrogen-type carboxyalkylated cellulose (g)) DS = 0.162 × A / (1 - 0.058 × A) A: Amount of 1 N NaOH required for neutralization of 1 g of hydrogen-type carboxyalkylated cellulose (mL) Factor of 0.1N NaOH Factor of 0.1N H2SO4

[0015] The amount of anionic groups in the cellulose fiber having anionic groups is preferably 0.01 to 3.0 mmol / g. When the amount of acid groups is less than 0.01 mmol / g, in the step of supporting metal ions described later, the amount of metal ions present on the surface of the anionic modified cellulose fiber is insufficient, and the deodorizing, antibacterial, and antiviral functions may be inferior. On the other hand, when the amount of acid groups exceeds 3.0 mmol / g, cellulose cleavage tends to occur as a side reaction during the oxidation reaction, and the yield may decrease.

[0016] The metal-containing anionic modified cellulose fiber can be produced by chemically modifying a general cellulose fiber as follows to introduce an anionic modified group into the glucose unit on the surface, and then further supporting metal ions and / or metal particles. Hereinafter, the method for introducing an anionic modified group into the glucose unit on the surface of the cellulose fiber and the method for supporting metal ions and / or metal particles thereafter will be described respectively.

[0017] (Oxidized cellulose) Cellulose has three hydroxyl groups per glucose unit and can be subjected to various chemical modification treatments. Oxidized cellulose is a modification that introduces a carboxyl group or a carboxylate group into at least a part of the cellulose fiber in the step described later. Here, in this specification, the carboxyl group refers to a group represented by -COOH, the carboxylate group refers to a group represented by -COO-, and the counter ion of the carboxylate group is not particularly limited. Also, the carboxyl group or the carboxylate group is collectively referred to as an "acid group".

[0018] As a method of modification for introducing a carboxyl group or a carboxylate group, there is no particular limitation as long as the modified cellulose-based fiber contains a carboxyl group or a carboxylate group. Hereinafter, these will be described in detail.

[0019] (Oxidation of Cellulose-based Fibers) In the present invention, the method for oxidizing cellulose-based fibers is not particularly limited, and known methods can be used. As an example, there is a method of oxidizing a cellulose raw material in water using an oxidizing agent in the presence of a substance selected from the group consisting of N-oxyl compounds, bromides, iodides, and mixtures thereof. According to this method, the primary hydroxyl group at the C6 position of the glucopyranose ring on the cellulose surface is selectively oxidized, and a group selected from the group consisting of an aldehyde group, a carboxyl group, and a carboxylate group is generated. The concentration of the cellulose raw material during the reaction is not particularly limited, but is preferably 5% by mass or less.

[0020] The N-oxyl compound refers to a compound capable of generating a nitroxyl radical. Examples of the nitroxyl radical include 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO). As the N-oxyl compound, any compound can be used as long as it promotes the target oxidation reaction. The amount of the N-oxyl compound used is not particularly limited as long as it is a catalytic amount capable of oxidizing cellulose-based fibers. For example, for 1 g of absolutely dry cellulose, 0.01 mmol or more is preferable, and 0.02 mmol or more is more preferable. The upper limit is preferably 10 mmol or less, more preferably 1 mmol or less, and still more preferably 0.5 mmol or less. Therefore, the amount of the N-oxyl compound used is preferably 0.01 to 10 mmol, more preferably 0.01 to 1 mmol, and still more preferably 0.02 to 0.5 mmol with respect to 1 g of absolutely dry cellulose.

[0021] A bromide is a compound containing bromine, and examples thereof include alkali metal bromides that dissociate and can be ionized in water, such as sodium bromide. A iodide is a compound containing iodine, and examples thereof include alkali metal iodides. The amount of the bromide or iodide used may be selected within a range that can promote the oxidation reaction. The total amount of the bromide and iodide is preferably 0.1 mmol or more, more preferably 0.5 mmol or more, based on 1 g of absolutely dry cellulose. The upper limit is preferably 100 mmol or less, more preferably 10 mmol or less, still more preferably 5 mmol or less. Therefore, the total amount of the bromide and iodide is preferably 0.1 to 100 mmol, more preferably 0.1 to 10 mmol, still more preferably 0.5 to 5 mmol, based on 1 g of absolutely dry cellulose.

[0022] The oxidizing agent is not particularly limited, and examples thereof include halogens, hypohalous acids, halous acids, perhalic acids, salts thereof, halogen oxides, peroxides, and the like. In particular, hypohalous acid or its salt is preferable, sodium hypochlorite or its salt is more preferable, and sodium hypochlorite is still more preferable because of its low cost and low environmental impact. The amount of the oxidizing agent used is preferably 0.1 mmol or more, more preferably 1 mmol or more, still more preferably 3 mmol or more, based on 1 g of absolutely dry cellulose. The upper limit is preferably 500 mmol or less, more preferably 50 mmol or less, still more preferably 25 mmol or less.

[0023] When using an N-oxyl compound, the amount of the oxidizing agent used is preferably 1 mol or more per 1 mol of the N-oxyl compound, and the upper limit is preferably 40 mol. Therefore, the amount of the oxidizing agent used is preferably 1 to 40 mol per 1 mol of the N-oxyl compound.

[0024] The conditions such as pH and temperature during the oxidation reaction are not particularly limited. Generally, the oxidation reaction proceeds efficiently even under relatively mild conditions. The reaction temperature is preferably 4°C or higher, more preferably 15°C or higher. The upper limit is preferably 40°C or lower, more preferably 30°C or lower. Therefore, the temperature is preferably 4 to 40°C, and may be about 15 to 30°C, that is, room temperature. The pH of the reaction solution is preferably 8 or higher, more preferably 10 or higher. The upper limit is preferably 12 or lower, more preferably 11 or lower. Therefore, the pH of the reaction solution is preferably about 8 to 12, more preferably about 10 to 11. Generally, carboxyl groups are generated in cellulose as the oxidation reaction proceeds, so the pH of the reaction solution tends to decrease. Therefore, in order to efficiently proceed the oxidation reaction, it is preferable to add an alkaline solution such as an aqueous sodium hydroxide solution to maintain the pH of the reaction solution within the above range. As the reaction medium during oxidation, water is preferable for reasons such as ease of handling and low occurrence of side reactions.

[0025] The reaction time in oxidation can be appropriately set according to the degree of progress of oxidation, and is usually 0.5 hours or more. The upper limit is usually 6 hours or less, preferably 4 hours or less. Therefore, the reaction time in oxidation is usually 0.5 to 6 hours, for example, about 0.5 to 4 hours. The oxidation may be carried out in two or more stages. For example, the oxidized cellulose obtained by filtration after the completion of the first-stage reaction is oxidized again under the same or different reaction conditions, so that it can be efficiently oxidized without being inhibited by the sodium chloride by-produced in the first-stage reaction. Another example of the oxidation method is a method of oxidizing by ozone treatment. By this oxidation reaction, at least the hydroxyl groups at the 2nd and 6th positions of the glucopyranose ring constituting cellulose are oxidized, and the decomposition of the cellulose chain occurs.

[0026] The ozone treatment is usually carried out by bringing a gas containing ozone into contact with the cellulose raw material. The ozone concentration in the gas is preferably 50 g / m3 or more. The upper limit is preferably 250 g / m3 or less, more preferably 220 g / m3 or less. Therefore, the ozone concentration in the gas is preferably 50 to 250 g / m3, more preferably 50 to 220 g / m3. The ozone addition amount is preferably 0.1 part by mass or more, more preferably 5% by mass or more, based on 100% by mass of the solid content of the cellulose raw material. The upper limit is usually 30% by mass or less. Therefore, the ozone addition amount is preferably 0.1 - 30% by mass, more preferably 5 - 30% by mass, based on 100% by mass of the solid content of the cellulose raw material. The ozone treatment temperature is usually 0°C or higher, preferably 20°C or higher. The upper limit is usually 50°C or lower. Therefore, the ozone treatment temperature is preferably 0 - 50°C, more preferably 20 - 50°C. The ozone treatment time is usually 1 minute or more, preferably 30 minutes or more. The upper limit is usually 360 minutes or less. Therefore, the ozone treatment time is usually about 1 - 360 minutes, preferably about 30 - 360 minutes. When the ozone treatment conditions are within the above range, it is possible to prevent the cellulose from being excessively oxidized and decomposed, and the yield of oxidized cellulose becomes good.

[0027] Further, post - oxidation treatment may be performed on the product obtained after ozone treatment using an oxidizing agent. The oxidizing agent used for the post - oxidation treatment is not particularly limited, and examples include chlorine - based compounds such as chlorine dioxide and sodium chlorite; oxygen, hydrogen peroxide, persulfuric acid, peracetic acid, etc. As a method of the post - oxidation treatment, for example, a method of dissolving these oxidizing agents in a polar organic solvent such as water or alcohol to prepare an oxidizing agent solution and immersing the cellulose raw material in the oxidizing agent solution can be mentioned.

[0028] The amounts of carboxyl groups, carboxylate groups, and aldehyde groups contained in the oxidized cellulose - based fibers can be adjusted by controlling oxidation conditions such as the addition amount of the oxidizing agent and the reaction time.

[0029] (Etherification of Cellulose - based Fibers) As for the etherification, any method may be used as long as the functional group after the reaction contains a carboxyl group or a carboxylate group for the convenience of introducing metal ions into the cellulose-based fiber in the subsequent process, and known methods can be used. Examples include carboxymethyl (ether)ification, carboxyethyl (ether)ification, carboxypropyl (ether)ification, carboxybutyl (ether)ification, etc., such as carboxyalkyl etherification, and carboxyphenyl (ether)ification. As an example among these, the method of carboxymethylation will be described below.

[0030] The method of carboxymethylation is not particularly limited, and known methods can be used. For example, a method of mercerizing the cellulose raw material as the starting material and then etherifying it can be mentioned. A general solvent is used during the carboxymethylation reaction. Examples of the solvent include water, alcohol (for example, lower alcohol), and a mixed solvent thereof. Examples of the lower alcohol include methanol, ethanol, N-propyl alcohol, isopropyl alcohol, N-butyl alcohol, isobutyl alcohol, and tertiary butanol. The mixing ratio of the lower alcohol in the mixed solvent is usually 60% by mass or more or 95% by mass or less, and preferably 60 - 95% by mass. The amount of the solvent is usually 3 times the mass of the cellulose raw material. The upper limit is not particularly limited, but it is 20 times the mass. Therefore, the amount of the solvent is preferably 3 - 20 times the mass.

[0031] Mercerization is usually carried out by mixing the cellulose raw material and a mercerizing agent. Examples of the mercerizing agent include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. The amount of the mercerizing agent used is preferably 0.5 times the mole or more per anhydrous glucose residue of the starting material, more preferably 1.0 mole or more, and even more preferably 1.5 times the mole or more. The upper limit is usually 20 times the mole or less, preferably 10 times the mole or less, and more preferably 5 times the mole or less. Therefore, 0.5 - 20 times the mole is preferred, 1.0 - 10 times the mole is more preferred, and 1.5 - 5 times the mole is even more preferred. The reaction temperature for mercerization is usually 0°C or higher, preferably 10°C or higher. The upper limit is usually 70°C or lower, preferably 60°C or lower. Therefore, the reaction temperature is usually 0 to 70°C, preferably 10 to 60°C. The reaction time is usually 15 minutes or longer, preferably 30 minutes or longer. The upper limit is usually 8 hours or shorter, preferably 7 hours or shorter. Therefore, it is usually 15 minutes to 8 hours, preferably 30 minutes to 7 hours.

[0032] The etherification reaction is usually carried out by adding a carboxymethylating agent to the reaction system after mercerization. Examples of the carboxymethylating agent include sodium monochloroacetate. The addition amount of the carboxymethylating agent is preferably usually 0.05 times mol or more, more preferably 0.5 times mol or more, and even more preferably 0.8 times mol or more per glucose residue of the cellulose raw material. The upper limit is usually 10.0 times mol or lower, preferably 5 mol or lower, and more preferably 3 times mol or lower. Therefore, it is preferably 0.05 to 10.0 times mol, more preferably 0.5 to 5, and even more preferably 0.8 to 3 times mol. 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 80°C or lower. Therefore, the reaction temperature is usually 30 to 90°C, preferably 40 to 80°C. The reaction time is usually 30 minutes or longer, preferably 1 hour or longer. The upper limit is usually 10 hours or shorter, preferably 4 hours or shorter. Therefore, the reaction time is usually 30 minutes to 10 hours, preferably 1 hour to 4 hours. During the carboxymethylation reaction, the reaction solution may be stirred as necessary.

[0033] When modifying a cellulose raw material by carboxymethylation, the degree of carboxymethyl substitution per glucose unit in the resulting carboxymethylated cellulose fiber is preferably 0.01 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 even more preferably 0.35 or less. Therefore, the degree of carboxymethyl group substitution is preferably from 0.01 to 0.50, more preferably from 0.05 to 0.40, and even more preferably from 0.10 to 0.30. The measurement of the degree of carboxymethyl substitution per glucose unit of the carboxymethylated cellulose fiber can be carried out, for example, by the following method. That is, 1) Weigh accurately about 2.0 g of carboxymethylated cellulose (absolutely dry) and put it into a 300 mL conical flask with a stopper. 2) Add 100 mL of special grade concentrated nitric acid to 1000 mL of methanol, add 100 mL of the resulting nitric acid-methanol solution, shake for 3 hours, and convert the carboxymethyl cellulose salt (carboxymethylated cellulose) into hydrogen-type carboxymethylated cellulose. 3) Weigh accurately 1.5 - 2.0 g of hydrogen-type carboxymethylated cellulose (absolutely dry) and put it into a 300 mL conical flask with a stopper. 4) Moisten the hydrogen-type carboxymethylated cellulose with 15 mL of 80% methanol, add 100 mL of 0.1 N NaOH, and shake at room temperature for 3 hours. 5) Using phenolphthalein as an indicator, back-titrate the excess NaOH with 0.1 N H2SO4. 6) Calculate the degree of carboxymethyl substitution (DS) by the following formula: A = [(100×W - (0.1 N H2SO4)(mL)×F)×0.1] / (absolute dry mass of hydrogen-type carboxymethylated cellulose (g)) DS = 0.162×A / (1 - 0.058×A) A: Amount of 1 N NaOH (mL) required for neutralizing 1 g of hydrogen-type carboxymethylated cellulose W: Factor of 0.1 N NaOH F: Factor of 0.1 N H2SO4

[0034] (Esterification of Cellulosic Fibers) As the esterification method, any method may be used as long as it is a method for introducing a functional group having anionic properties, and known methods can be employed. Examples include phosphoric acid esterification and sulfuric acid esterification. As an example, the methods of phosphoric acid esterification and sulfuric acid esterification will be described below.

[0035] (Phosphoric Acid Esterified Cellulose, Phosphorous Acid Esterified Cellulose) Phosphoric acid esterified cellulose is cellulose esterified with a compound having a phosphoric acid group or a phosphorous acid group. Examples of the compound having a phosphoric acid group or a phosphorous acid group include phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, polyphosphonic acid, esters and salts thereof. These compounds are low-cost and easy to handle. Examples of the compound having a phosphate group or a phosphite group include phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, sodium metaphosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, potassium metaphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, ammonium metaphosphate, phosphorous acid, sodium hydrogen phosphite, ammonium hydrogen phosphite, potassium hydrogen phosphite, sodium dihydrogen phosphite, sodium phosphite, lithium phosphite, potassium phosphite, magnesium phosphite, calcium phosphite, triethyl phosphite, triphenyl phosphite, pyrophosphorous acid, etc. Among them, phosphoric acid, sodium salts of phosphoric acid, potassium salts of phosphoric acid, ammonium salts of phosphoric acid, phosphorous acid, sodium salts of phosphorous acid, potassium salts of phosphorous acid, and ammonium salts of phosphorous acid are preferred because of their high efficiency in phosphate esterification or phosphite esterification and ease of industrial application. 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.

[0036] In phosphorylated cellulose and phosphitized cellulose, the lower limit of the introduction amount of the phosphate group or phosphite group per 1 g (mass) of phosphorylated cellulose or phosphitized cellulose is preferably 0.1 mmol / g or more. If it exceeds 3.5 mmol / g, the desired physical properties may not be obtained. The introduction amount of the phosphate group or phosphite group per 1 g (mass) of phosphorylated cellulose or phosphitized cellulose is preferably 0.1 to 3.5 mmol.

[0037] The phosphorylation reaction or the phosphitization reaction is carried out, for example, by reacting a cellulose raw material with a compound having a phosphate group or a phosphite group. Examples of the method for reacting the cellulose raw material with the compound having a phosphate group or a phosphite group include a method of mixing a powder or an aqueous solution of the compound having a phosphate group or a phosphite group with the cellulose raw material, and a method of adding an aqueous solution of the compound having a phosphate group or a phosphite group to a slurry of the cellulose raw material. Among these, from the reasons that the uniformity of the reaction is enhanced and the phosphorylation efficiency and the phosphitization efficiency are increased, a method of mixing an aqueous solution of the compound having a phosphate group or a phosphite group with the cellulose raw material or its slurry is preferred. The pH of the aqueous solution of the compound having a phosphate group or a phosphite group is preferably 7 or less from the viewpoint of enhancing the efficiency of introducing the phosphate group or the phosphite group, and more preferably 3 to 7 from the viewpoint of suppressing hydrolysis.

[0038] The lower limit of the addition amount of the compound having a phosphate group or a phosphite group is preferably 0.2 parts by mass or more, more preferably 1 part by mass or more in terms of phosphorus atom, based on 100 parts by mass of the cellulose raw material. By being in such a range, the yield of phosphorylated cellulose or phosphitized cellulose can be improved. On the other hand, the upper limit is preferably 500 parts by mass or less, more preferably 400 parts by mass or less. By being in such a range, a yield commensurate with the addition amount of the compound having a phosphate group or a phosphite group can be efficiently obtained. The addition amount of the compound having a phosphate group or a phosphite group is preferably 0.2 to 500 parts by mass, more preferably 1 to 400 parts by mass.

[0039] When reacting a cellulose raw material with a compound having a phosphate group or a phosphite group, a basic compound may be further added to the reaction system. Examples of the method of adding the basic compound include adding it to a slurry of the cellulose raw material, an aqueous solution of the compound having a phosphate group or a phosphite group, or a slurry of the cellulose raw material and the compound having a phosphate group or a phosphite group. The basic compound is not particularly limited, but a nitrogen-containing compound showing basicity is preferable. "Showing basicity" usually means that an aqueous solution of the basic compound exhibits a peach to red color in the presence of a phenolphthalein indicator, or the pH of the aqueous solution of the basic compound is greater than 7.

[0040] The nitrogen-containing compound showing basicity is not particularly limited as long as the effects of the present invention are achieved. Among them, a compound having an amino group is preferable. For example, urea, methylamine, ethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, hexamethylenediamine can be mentioned. Among these, urea is preferable because of its low cost and easy handling. The addition amount of the basic compound is preferably 2 to 1000 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 reaction time is not particularly limited, but is usually about 1 to 600 minutes, preferably 30 to 480 minutes. When the reaction conditions are within any of these ranges, it is possible to prevent excessive introduction of phosphate groups or phosphite groups into the cellulose and make it easy to dissolve, and the yield of phosphoric acid esterified cellulose and phosphorous acid esterified cellulose can be improved.

[0041] After reacting a cellulose raw material with a compound having a phosphate group or a phosphite group, a suspension is usually obtained. The suspension is dehydrated as necessary. After dehydration, heat treatment is preferably performed. Thereby, hydrolysis of the cellulose raw material can be suppressed. The heating temperature is preferably 100 to 170°C. When water is contained during the heat treatment, it is heated at 130°C or lower (more preferably 110°C or lower), and after removing the water, it is more preferably heated at 100 to 170°C. Phosphoric acid esterified cellulose and phosphorous acid esterified cellulose are preferably subjected to a washing treatment such as washing with cold water after boiling.

[0042] (Sulfonated cellulose) Sulfonated cellulose is cellulose sulfonated with a compound having a sulfate group. Examples of the compound having a sulfuric acid group include sulfuric acid, sulfamic acid, chlorosulfonic acid, sulfur trioxide, esters and salts thereof. These compounds are low-cost and easy to handle.

[0043] As the sulfonation reagent, sulfamic acid is preferably used. Sulfamic acid not only has a lower solubility in cellulose than sulfuric anhydride or sulfuric acid aqueous solution, but also has a low acidity, so that the degree of polymerization can be maintained. In addition, there are no handling restrictions on sulfuric anhydride or sulfuric acid aqueous solution, which is strongly acidic and highly corrosive, and it is not designated as a specified substance under the Air Pollution Control Law, so the environmental load is small. The amount of sulfamic acid used can be appropriately adjusted in consideration of the amount of substituents introduced into the cellulose fiber. Sulfamic acid can be used, for example, preferably in an amount of 0.01 to 50 mol, more preferably 0.1 to 30 mol, per mol of glucose unit in the cellulose molecule.

[0044] (Loading of metal ions and / or metal particles) By supporting ions or metal particles of one or more metal elements selected from the group consisting of Ag, Au, Pt, Pd, Ni, Mn, Fe, Ti, Al, Zn, and Cu on anionic modified cellulose fibers, a high antiviral, antibacterial, and deodorizing effect can be imparted. In particular, by using Ag and Cu, the antiviral, antibacterial, and deodorizing functions are further improved. In particular, in the anionic modified cellulose fibers, since this metal and the anionic modified cellulose fibers are chemically bonded, when contained in a sheet, the metal component is less likely to desorb from the sheet, and the mechanical properties such as tensile strength are also good.

[0045] The method of supporting the metal ions on the anionic modified cellulose fibers is not particularly limited. For example, a previously prepared dispersion of the anionic modified cellulose fibers and an aqueous solution of a metal compound may be mixed, or a dispersion containing the anionic modified cellulose fibers may be coated on a substrate to form a film, and the film may be impregnated by contacting and dropping an aqueous solution of a metal compound. At this time, the film may remain fixed on the substrate or may be in a state of being peeled off from the substrate. By these methods, the metal ions derived from the metal compound perform counterion exchange with the sodium ions that have already been ionically bonded to anionic modified groups such as carboxylate groups, so that metal ions are added to the anionic modified cellulose fibers. This counterion exchange is considered to occur due to the difference in the ionization tendency between metal ions.

[0046] Here, the aqueous solution of the metal compound is an aqueous solution of a metal salt. Examples of metal salts include complexes (complex ions), halides, nitrates, sulfates, and acetates. The usage concentration of the aqueous solution of the metal compound is not particularly limited, but 0.2 to 2.2 mmol of metal ions per 1 g of cellulose fiber is preferable, and 0.4 to 1.8 mmol is more preferable. The time for contacting the metal compound may be adjusted as appropriate.

[0047] The temperature during contact is not particularly limited, but is preferably in the range of 2 to 50° C. Furthermore, the pH of the liquid during contact is not particularly limited, but since a low pH makes it difficult for metal ions to bind to the anion-modified group, it is preferably in the range of 7 to 13, and particularly preferably in the range of 8 to 12.

[0048] In the present invention, it is possible to introduce metal ions into the anion-modified cellulose fiber as described above, but some of the metal ions may be reduced to form metal particles. If necessary, it is also possible to partially form metal particles on the surface of the anion-modified cellulose fiber by reducing some of the metal ions bound to the metal ion-supported anion-modified cellulose fiber by adding a reducing agent or the like. However, it is preferable to use the entire amount of the metal compound as metal ions without carrying out any special reduction treatment from the viewpoint of antiviral, antibacterial, and deodorizing effects.

[0049] The mechanism by which metal particles are generated in the anion-modified cellulose fiber by reducing the metal compound in the metal-containing anion-modified cellulose fiber obtained above is not clear, but is presumed to be as follows. The metal compound or ions derived from the metal compound in the metal compound-containing anion-modified cellulose fiber are reduced to metal by the reduction reaction. At this time, the generated metal is supported on the surface of the anion-modified cellulose fiber. Since the metals generated in the same manner and adjacent to each other are integrated, the particles grow to form nanoparticles. Meanwhile, metal compounds and the like that exist in the vicinity of the anion-modified cellulose fiber but are not bonded to the anion-modified cellulose fiber are also reduced to generate metal. The metal is quickly integrated with the metal on the surface of the anion-modified cellulose fiber to form metal particles.

[0050] The reduction reaction may be carried out by a known method, but it is preferably carried out while reducing the metal compound without cleaving the bond between the metal compound and the acid group. Examples of such reduction methods include a gas-phase reduction method using hydrogen and a liquid-phase reduction method using a reducing agent such as an aqueous solution of sodium borohydride. The conditions such as time and temperature in the gas-phase reduction are appropriately adjusted. For example, the reaction may be carried out at 50 to 60 °C for about 1 to 3 hours. The gas-phase reduction reaction is preferably carried out in a state where the metal-containing anion-modified cellulose-based fiber does not contain water or a solvent. In the reduction reaction, the membrane may remain fixed on the substrate or may be in a state of being peeled off from the substrate. In the case of liquid-phase reduction, a membrane can be obtained from the above dispersion and subjected to the reduction reaction with or without drying. In the reduction reaction, the membrane may remain fixed on the substrate or may be in a state of being peeled off from the substrate. Also, the dispersion can be subjected to the liquid-phase reduction reaction without drying. The reaction temperature in the liquid-phase reduction is preferably 4 to 40 °C, more preferably room temperature.

[0051] Whether the anion-modified cellulose-based fiber contains metal ions or metal particles can be confirmed by a scanning electron microscope image and ICP emission analysis of the extract with strong acid. That is, the metal ions cannot be confirmed to be present in the scanning electron microscope image, while it can be confirmed by ICP emission analysis that the metal is contained. On the other hand, for example, when the above metal is reduced from ions and exists as metal particles, the metal particles can be confirmed in the scanning electron microscope image, so the presence or absence of metal ions can be determined. Also, the presence or absence of metal ions can be determined by element mapping by a scanning electron microscope image and energy-dispersive X-ray analysis (EDS). That is, metal ions cannot be confirmed in the scanning electron microscope image, but the presence of metal ions can be confirmed by performing element mapping.

[0052] In the step of supporting the metal ions or metal particles, the metal content in the anion-modified cellulose fiber is preferably in the range of 10 to 100 mg / g, more preferably in the range of 15 to 80 mg / g, and particularly preferably in the range of 20 to 60 mg / g, based on the anion-modified cellulose fiber. If it is less than 10 mg / g, the antiviral, deodorizing, and antibacterial functions may be inferior. On the other hand, if it exceeds 100 mg / g, the metal ions are likely to elute during production, increasing the load of wastewater treatment. Note that the metal content of the anion-modified cellulose fiber can be measured by the following method. (1) Before measurement, dry the measurement sample (50 °C, 1 day). (2) Weigh 0.25 g of the dried measurement sample and put it into a 50 ml beaker. (3) Pipette 10 ml of concentrated nitric acid and add it to the beaker containing the measurement sample to prepare a measurement sample solution (10-fold dilution). (4) Let it stand for 120 minutes, and then pass it through a syringe filter to remove the fiber fraction from the measurement sample solution (filtration). (5) Pipette 1 ml of the filtered measurement sample solution and add it to a test tube containing 49 ml of distilled water (50-fold dilution). (6) Close the lid of the test tube tightly and shake it to stir. (7) Use ICP-OES (manufactured by Agilent Technology, ICP-OES 5110) to measure (quantify) the content of metal ions and metal particles. (8) Calculate the metal content (mg / g) per 1 g of the anion-modified cellulose fiber from the quantitative results by ICP-OES.

[0053] (Pulp) The pulp constituting the base paper for paper yarn of the present invention can be chemical pulp such as softwood bleached kraft pulp (NBKP), softwood unbleached kraft pulp (NUKP), softwood semi-bleached kraft pulp (NSBKP), softwood sulfite pulp, etc., or mechanical pulp such as stone ground pulp (SGP), pressure stone ground pulp (TGP), chemiground pulp (CGP), groundwood pulp (GP), thermomechanical pulp (TMP), etc., dissolving pulp, pulp using softwood or hardwood such as mercerized pulp as raw materials. In the present invention, as the wood pulp, softwood pulp with a long fiber length is preferably used. In addition, non-wood pulp such as bast fibers such as flax, kenaf, paper mulberry, and mitsumata, hard fibers such as bagasse, bamboo, and esparto, seed hair fibers such as cotton pulp, and leaf sheath / leaf fibers such as abaca pulp and sisal pulp can be used. In the present invention, as the non-wood pulp, hemp is preferred, and in particular, abaca pulp having a long fiber length and an appropriate fiber width is preferably used. The drainage degree (Canadian standard freeness) of the pulp is usually about 300 to 680 ml, and it is preferably adjusted as appropriate according to the physical properties required for the base paper for paper yarn.

[0054] (Pulp formulation) The blending ratio (weight mass ratio) of pulp and metal-containing anionic modified cellulose fibers is not particularly limited, but is usually pulp / metal-containing anionic modified cellulose fibers = 95 to 75 / 25 to 5 (solid content). If the blending amount of the metal pulp is small, the deodorizing, antibacterial, and antiviral effects may not be sufficiently exhibited. On the other hand, if the blending amount is too large, the strength of the base paper for paper yarn may not be obtained.

[0055] (Additives) It is preferable to blend at least one of a dry paper strength agent (dry paper strength enhancer) and a wet paper strength agent (wet paper strength enhancer) in the base paper for paper yarn of the present invention. As dry paper strength agents, carboxymethyl cellulose (CMC), carboxymethyl guar gum, polyacrylamide, glyoxal-modified polyacrylamide, hydroxypropyl guar gum, etc. can be used. As wet paper strength enhancers, dialdehyde guar gum, glyoxal-modified polyacrylamide, polyamide epichlorohydrin, polyamide polyamine epichlorohydrin, polyamine epichlorohydrin, polyethyleneimine, etc. can be used. In particular, adding both amphoteric dry paper strength agents and wet paper strength agents is preferable from the viewpoints of water resistance and washing resistance.

[0056] The addition amount of the dry paper strength enhancer is 0.20% by mass or more, preferably 0.30% by mass or more, more preferably 0.35% by mass or more, and the upper limit is 1.2% by mass or less, preferably 1.1% by mass or less, more preferably 1.0% by mass or less, based on the total amount of pulp and metal-containing anionic modified cellulose fibers. The addition amount of the wet paper strength enhancer is 0.3% by mass or more, preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and the upper limit is 4.0% by mass or less, preferably 3.0% by mass or less, more preferably 2.0% by mass or less, based on the total amount of pulp and metal-containing anionic modified cellulose fibers.

[0057] Also, the compounding amount of the aluminum water-soluble salt (aluminum sulfate) is 0.3% by mass or less, preferably no addition, based on the total amount of pulp and metal-containing anionic modified cellulose fibers. When papermaking is carried out using a paper stock containing an aluminum water-soluble salt, problems such as the metal contained in the metal-containing anionic modified cellulose fibers being replaced by aluminum, resulting in the inability to exhibit the desired performance, and the wastewater being contaminated with heavy metals may occur. In addition, the presence of an aluminum water-soluble salt in the base paper for paper yarn inhibits the expression of the deodorizing, antibacterial, and antiviral effects of the metal-containing anionic modified cellulose fibers.

[0058] (Other auxiliaries) In the present invention, examples of various auxiliaries include dry paper strength enhancers such as polyacrylamide-based polymers, polyvinyl alcohol-based polymers, cationized starches, various modified starches, urea-formalin resins, and melamine-formalin resins, wet paper strength enhancers, retention aids, drainage improvers, coagulants, bulking agents, dyes, fluorescent brighteners, pH adjusters, defoamers, ultraviolet ray inhibitors, anti-fading agents, pitch control agents, slime control agents, etc., and they can be appropriately selected and used as necessary.

[0059] (Papermaking) The papermaking method of the paper yarn base paper is not particularly limited, and it can be carried out using a Fourdrinier paper machine, a cylinder paper machine, a twin-wire paper machine, an inclined twin-wire paper machine, etc. Among these, it is preferable to use a cylinder paper machine that can increase the fiber orientation significantly. Also, for the drying process, a multi-cylinder cylinder dryer, a Yankee dryer, a hot air dryer, etc. can be appropriately selected.

[0060] (Metal content) The paper yarn base paper of the present invention preferably has a metal content of 0.25 mass% by weight or more. By having a metal content of 0.25 mass% by weight or more, a high deodorizing, antibacterial, and antiviral effect can be exhibited. The metal content of the paper yarn base paper can be measured by the following method. The content of metal per 1 g of the sample (mg / g) was measured by inductively coupled plasma optical emission spectrometry (ICP-OES) according to the following procedure. (1) Before measurement, dry the measurement sample (50°C, 1 day). (2) Weigh 0.25 g of the dried measurement sample and put it into a 50 ml beaker. (3) Take 10 ml of concentrated nitric acid with a whole pipette and add it to the beaker containing the measurement sample to prepare a measurement sample solution (10-fold dilution). (4) After standing for 120 minutes, pass it through a syringe filter to remove the fiber component from the measurement sample solution (filtration). (5) Take 1 ml of the filtered measurement sample solution with a micropipette and add it to a test tube containing 49 ml of distilled water (50-fold dilution). (6) Close the test tube lid tightly and shake to mix well. (7) Use ICP-OES (manufactured by Agilent Technology, ICP-OES 5110) to measure (quantify) the content of metal ions and metal particles. (8) Calculate the amount of metal per 1 g of sample in the base paper for paper yarn from the quantification results by ICP-OES (weight mass % mg / g). The metal content can be adjusted by the blending amount of metal-containing anionic-modified cellulose fibers.

[0061] (Manufacture of paper yarn) The obtained base paper for paper yarn can be slit into strips and twisted spirally to obtain paper yarn (twisted yarn). The paper yarn can be blended with flame retardants, pigments, water repellents, oil repellents, resins, and other functional additives within the range that does not impair the effects of the present invention. The timing of blending can be imparted not only in the papermaking process but also in separate processes such as coating, dipping, and dyeing. For example, the obtained base paper for paper yarn is slit into a width of 1 to 5 mm, and the obtained strips are wound. The slit width can be changed according to the count of the paper yarn. For example, to make a paper yarn of 180 to 220 dtex, it is slit to a width of about 1.3 to 1.7 mm, 230 to 350 dtex to a width of about 1.8 to 2.2 mm, and thick yarns of 360 dtex or more are slit to a width of 3.0 mm or more. Preferably, it is slit to a width of 1.5 to 2.0 mm.

[0062] (Woven and knitted fabrics) The paper yarn of the present invention can be used for woven and knitted fabrics. The woven and knitted fabrics in the present invention refer to knitted fabrics or woven fabrics.

[0063] (Woven fabric) As woven fabrics, there are many types according to various classification methods such as plain weave, twill weave, satin weave, etc. according to the number of yarns used, classification methods according to materials, for example, typical weaves of cotton such as dobby, boil, gauze, etc., weaves of wool such as twill, damask, etc., and others such as jacquard, towel, etc. The weaving method of the paper yarn can be any of these various weaving methods.

[0064] For the yarns used in the interlacing of the fabric, yarns other than paper yarns may be used, or both may be paper yarns. From the viewpoints of improving the washability while suppressing the rough feeling peculiar to paper, and improving the tensile strength, it is preferable that the paper yarns and the yarns other than the paper yarns are woven or interlaced.

[0065] Examples of the yarns other than the paper yarns include one or more kinds of fibers selected from the group consisting of synthetic fibers, semi-synthetic fibers, regenerated fibers, and natural fibers. Examples of the synthetic fibers include nylon fibers, aramid fibers, vinylon fibers, polyacrylonitrile-based fibers, or polyester-based synthetic fibers. Examples of the polyester-based synthetic fibers include PET (polyethylene terephthalate) fibers. Examples of the semi-synthetic fibers include acetate fibers. Examples of the regenerated fibers include viscose fibers such as rayon. Examples of the natural fibers include silk, cotton fibers, or hemp fibers. As long as paper yarns are used in at least one of the warp and weft, any yarns may be used and the paper fabric may be woven by any method.

[0066] (Knitted fabric) Examples of the knitted fabrics include warp knitting, which is knitted vertically such as lace knitting, raschel knitting, tricot knitting, and bandage knitting, and weft knitting, which is knitted horizontally such as flat knitting, rubber knitting, tube knitting, Japanese plain weave, dotted swiss, jacquard knitting, etc. Any knitting method may be used according to the application. Also, various knitting machines such as warp knitting machines, weft knitting machines, circular knitting machines, and raschel knitting machines may be used. For the yarns used in the interlacing of the fabric, yarns other than paper yarns may be used, or both may be paper yarns. From the viewpoints of improving the washability while suppressing the rough feeling peculiar to paper, and improving the tensile strength, it is preferable that the paper yarns and the yarns other than the paper yarns are woven or interlaced.

[0067] Examples of threads other than paper threads include one or more threads selected from the group consisting of synthetic fibers, semi-synthetic fibers, regenerated fibers, and natural fibers. Examples of synthetic fibers include nylon fibers, aramid fibers, vinylon fibers, polyacrylonitrile-based fibers, or polyester-based synthetic fibers. Examples of polyester-based synthetic fibers include PET (polyethylene terephthalate) fibers. Examples of semi-synthetic fibers include acetate fibers. Examples of regenerated fibers include viscose fibers such as rayon. Examples of natural fibers include silk, cotton fibers, or hemp fibers. As long as paper threads are used in at least one of the warp and weft threads, the paper fabric may be woven using any thread and in any method.

[0068] (Coloring) The knitted or woven fabric made from paper threads may be colored. Coloring can be performed by impregnating the object with a liquid containing a dye or pigment, or by printing on the knitted or woven fabric. The paper thread base paper or paper threads before making them into a knitted or woven fabric of paper threads may be colored.

[0069] (Other additives) As long as it is a small amount that does not go against the purpose of the present invention, for example, it may include other threads such as decorative threads. A decorative thread is a decorative thread having a special appearance or structure.

[0070] (Fibrous fabric products) The paper threads of the present invention can be used in fibrous fabric products in various industrial fields. For example, interior applications (curtains, partitions, furniture fabrics, tatami mats, wallpapers, carpets, etc.), bedding and bedding applications (towels, handkerchiefs, pillowcases, sheets, mats, carpets, etc.), apparel applications (jackets, skirts, dresses, denim pants, knits, sweaters, underwear, scarves, socks, gloves, hats, socks, shoes, shoe insoles, bags, etc.), daily necessities (stationery, paper strings, etc.), and sanitary products (white coats, surgical masks, diapers, medical, nursing, and menstrual products, body cleaning sheets, hand towels, etc.).

Examples

[0071] · Preparation of Copper-Containing Anion-Modified Cellulose Fibers 500 g (bone-dry) of cellulose raw material (bleached unbeaten kraft pulp derived from coniferous trees) was added to 500 ml of an aqueous solution in which 780 mg of TEMPO (Sigma Aldrich) and 75.5 g of sodium bromide were dissolved, and the mixture was stirred until the pulp was uniformly dispersed. An aqueous sodium hypochlorite solution was added to the reaction system to a concentration of 6.0 mmol / g to initiate the oxidation reaction. During the reaction, the pH of the system decreased, but a 3M aqueous sodium hydroxide solution was sequentially added to adjust the pH to 10. The reaction was terminated when the sodium hypochlorite was consumed and the pH in the system no longer changed. The mixture after the reaction was filtered through a glass filter to separate the pulp and washed with water to obtain oxidized cellulose fibers with an acid value of 1.6 mmol / g. To the TEMPO-oxidized cellulose fibers obtained by the above operation, an aqueous solution of a metal salt (CuCl2) (1.6 mmol per 1 g of oxidized cellulose fibers) was added and stirred. Thereby, Cu ions were incorporated into the oxidized cellulose fibers, and the mixture was washed to remove unreacted metal salts. The average fiber length was 1.93 mm, the average fiber diameter was 31.2 μm, the drainage degree was 600 ml, and the copper content was 44.7 mg per 1 g of copper-containing oxidized cellulose fibers.

[0072] · Manufacture of Paper Yarn Base Paper 90 parts by mass of abaca pulp with a Canadian Standard Freeness (CSF) of 400 ml and 10 parts by mass of copper-containing oxidized cellulose fibers were mixed to obtain a slurry. As an amphoteric dry paper strengthening agent, polyacrylamide resin (Harmide KS2, non-volatile content 20%, pH 3.0 - 5.0, manufactured by Harima Kasei Co., Ltd.) was added to the slurry (dry mass) at a solid content of 0.9% while stirring. As a cationic wet paper strengthening agent, polyamide epichlorohydrin resin (WS4024, non-volatile content 25%, pH 2.5 - 5.0, manufactured by Starlight PMC Co., Ltd.) was added to the fiber (total of pulp and copper-containing oxidized cellulose fibers, dry mass) slurry (dry mass) at a solid content of 1.875% while stirring to adjust the papermaking raw material. Using this papermaking raw material, a paper yarn base paper was obtained by papermaking on a cylinder mold paper machine at a target basis weight of 15 g / m2.

[0073] ·Manufacture of paper yarn The above paper yarn base paper was processed into a slit shape with a width of 1.5 mm by a slitter device to produce a paper tape. Then, the paper tape was twisted by a twisting device (700 turns / m, Z twist) to produce paper yarn A. The obtained paper yarn had a uniform appearance and had a strength that was not easily cut even when pulled by hand.

[0074] (Production Example 1) Fabric Long fibers made of polyester were prepared. The warp was made of polyester yarn and the weft was made of paper yarn A, and they were woven and finished by a conventional method to obtain a fabric base material with a basis weight of 70 g / m2.

[0075] (Example 1) Sheet A sheet made of the base material of Production Example 1 was prototyped. Even in a hot and humid atmosphere where sweating was felt in the past, the surface hardly stuck to the skin, there was no feeling of stickiness, and it was rich in a refreshing feeling.

[0076] (Example 2) Slippers The base material of Production Example 1 was cut to create an insole and an upper, and a pair of slippers was prototyped.

[0077] (Example 3) Socks The above paper yarn A and cotton yarn with a surface count of 40 were used to manufacture socks on a flat knitting machine.

[0078] (Example 4) Knitted hat The above paper yarn A and cotton yarn with a surface count of 30 were used to manufacture a knitted hat on a flat knitting machine.

[0079] The following evaluations were conducted on the paper yarn obtained in the present invention and various fibrous fabric products obtained in Examples 1 to 4. The results are shown in Table 1.

[0080] (1) Deodorizing property The deodorizing function test was carried out on 1 g of the test piece using the method of the SEK Mark fiber product certification standard (JEC301, Fiber Evaluation Technology Council) with hydrogen sulfide as the target. The deodorizing function was evaluated according to the following criteria. ◎: The reduction rate of hydrogen sulfide is 80% or more ○: Hydrogen sulfide reduction rate is 70% or more and less than 80% ×: Hydrogen sulfide reduction rate is less than 70%

[0081] (2) Antibacterial property According to JIS L1902 "Test Method and Antibacterial Effect of Fiber Products", a qualitative test by the bacterial liquid absorption method was carried out. Specifically, 0.2 ml of the test bacterial liquid containing Escherichia coli and Staphylococcus aureus was dropped onto 0.4 g of the test piece. After culturing at 37 °C for 18 - 24 hours, 20 ml of the washing liquid was added to wash out the test bacteria from the test piece, and the viable bacteria count in the washing liquid was measured by the mixed plate culture or the issued measurement method, and the antibacterial function was evaluated according to the following criteria. ◎:: Antibacterial activity value A according to JIS ≧ 3.0 〇: Antibacterial activity value A according to JIS 3.0 > A ≧ 2.0 ×: Antibacterial activity value A according to JIS < 2.0

[0082] (3) Antiviral property The antiviral function test was carried out in accordance with JIS L 1922:2016, with the test piece mass being 0.4 g. As the test viruses, influenza virus (H3N2, ATCC VR―1679) and feline calicivirus (Strain: F - 9 ATCC VR - 782) were used. The antiviral activity value (Mv) was calculated and evaluated according to the following criteria. ◎: Antiviral activity value Mv according to JIS ≧ 3.0 〇: Antibacterial activity value Mv according to JIS 3.0 > Mv ≧ 2.0 ×: Antibacterial activity value Mv according to JIS < 2.0

[0083]

Table 1

Claims

1. A paper yarn obtained by using a base paper for paper yarn containing pulp and a metal-containing anionic modified cellulose 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.

2. A woven or knitted fabric obtained by using the paper yarn according to Claim 1.

3. A fibrous fabric product obtained by using the woven or knitted fabric according to Claim 2.

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