Yarn raw material, yarn, fiber product, and method for producing yarn
Patent Information
- Application Number
- JP2025524898
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Filing Date
- 2024-10-18
- Publication Date
- 2026-03-04
Abstract
Description
Yarn raw materials, yarns, textile products, and methods for producing yarns. The present invention relates to a yarn raw material, a yarn, a textile product, and a method for producing the yarn. In recent years, with the expansion of the clothing and textile industry and the popularity of fast fashion, the amount of textile waste has been increasing. Globally, 75% of this waste is disposed of, and 25% is recycled or reused. In general, increasing the rate of recycling or reuse can reduce the environmental impact, and there is a demand for the development of recycling methods for a wide range of textile products. As a method for recycling fibers contained in textile products, a technique of recovering the original cotton or hair-like short fibers by breaking up the weave of the textile product with a needle-like tool is known. The short fibers obtained in this way are called "recycled fibers" and are characterized by their short fiber length compared to the fibers before the textile product is manufactured. Therefore, the recycled fibers that can be recycled into yarns that constitute textile products are limited to relatively long fibers, and the short fibers are still discarded. Incidentally, Non-Patent Document 1 discloses treating paper with an aqueous solution of a polyvalent carboxylic acid for the purpose of improving the wet paper strength of the paper. YJ Zhou, P. Luner, P. Caluwe, Journal ofApplied Polymer science, (US),1995, Volume 58, Issue 9, p. 1523-1534 As mentioned above, only a small portion of discarded textile products are recycled or reused, and furthermore, the recycled fibers that can be recycled using the recycled fiber technology are limited to relatively long fibers. If it becomes possible to recycle fibers that are usually difficult to recycle, such as recycled fibers, the rate of recycling or reuse of textile products can be increased, and the environmental burden caused by the manufacture and use of textile products can be reduced. Therefore, an object of the present invention is to provide a yarn raw material, a yarn, and a method for producing a yarn raw material, which are capable of producing a useful yarn even from fibers that are normally difficult to recycle, such as dewool fibers. As a result of intensive research to achieve the above-mentioned object, the inventors discovered that fibers having multiple hydroxyl groups on the surface can be used as a useful raw material for yarn by modifying the fibers with a polymer having multiple carboxyl groups and / or phosphate groups through ester bonds and / or phosphate ester bonds, and thus arrived at the present invention. The gist of the present invention is as follows. (1) A fiber having a plurality of hydroxyl groups on its surface; A polymer having a plurality of carboxyl and / or phosphate groups disposed on the surface of the fiber, A yarn raw material, wherein at least a portion of the multiple hydroxyl groups and a portion of the carboxyl groups and / or phosphate groups form ester bonds and / or phosphate ester bonds. (2) The thread material according to (1), wherein the polymer contains polycarboxylic acid and / or polyphosphoric acid. (3) The thread raw material according to (2), wherein the polycarboxylic acid includes at least one selected from the group consisting of polyacrylic acid, polymethacrylic acid, acrylic acid / maleic acid copolymers, methacrylic acid / maleic acid copolymers, acrylic acid / methacrylic acid / maleic acid copolymers, alginic acid, carboxymethyl cellulose, partially oxidized cellulose, and derivatives thereof. (4) The thread material according to any one of (1) to (3), wherein the acid value of the polymer is 20 mg KOH / g or more and 3000 mg KOH / g or less. (5) The thread material according to any one of (1) to (4), wherein the number average molecular weight of the polymer is 300 or more and 1,000,000 or less. (6) The yarn material according to any one of (1) to (5), further comprising a polymer having a plurality of amino groups fixed to the fiber via the polymer having a plurality of carboxyl groups and / or phosphate groups. (7) The yarn material according to any one of (1) to (6), wherein the fibers are cellulosic fibers. (8) The yarn material according to any one of (1) to (7), wherein the fibers are repelled fibers. (9) The yarn material according to any one of (1) to (8), wherein the average length of the fibers is 0.10 mm or more and 6.0 mm or less. (10) A yarn comprising the yarn raw material according to any one of (1) to (9). (11) A textile product comprising the yarn raw material according to any one of (1) to (9) or the yarn according to (10). (12) A method for producing a yarn raw material, comprising a step of fixing a polymer having a plurality of carboxyl groups and / or a plurality of phosphate groups to at least a portion of the hydroxyl groups of a fiber having a plurality of hydroxyl groups on a surface thereof via an ester bond and / or a phosphate ester bond. (13) A method for producing a yarn, comprising producing a yarn using the yarn raw material according to any one of (1) to (9). With the above-mentioned configuration, it is possible to provide a yarn raw material, a yarn, and a method for producing a yarn raw material that can produce a useful yarn even from fibers that are normally difficult to recycle, such as recycled fibers. FIG. 1 is a photographic image of the gel of the yarn according to Example 1 before air drying. FIG. 2 is a photographic image of the yarn according to Example 1. FIG. 3 is a photographic image of the gel of the yarn according to Example 2 before air drying. FIG. 4 is a photographic image of the yarn according to Example 2. FIG. 5 is a graph showing the zeta potential measurement results of the yarn raw material according to Examples 3 to 5 and the reincarnation fiber of Reference Example 1. FIG. 6 is a graph showing the infrared absorption spectrum results of the yarn raw material according to Example 6 and the reincarnation fiber of Reference Example 2. FIG. 7 is a graph showing the infrared absorption spectrum results of the yarn raw material according to Example 7 and the yarn raw material according to Example 6. FIG. 8 is a graph showing the fiber length distribution of the reincarnation fiber in each section after classification by each sieve. FIG. 9 is a result showing the stress-strain curve and breaking strength of the nonwoven fabric according to Example 8. Preferred embodiments of the present invention will now be described in detail. <1. Yarn raw materials> First, a yarn raw material according to one embodiment of the present invention will be described. The yarn raw material according to this embodiment is a raw material for yarn used in the manufacture of various textile products such as clothing. The yarn raw material according to this embodiment has fibers having a plurality of hydroxyl groups on the surface thereof, and a polymer having a plurality of carboxyl groups and / or phosphate groups arranged on the surface of the fibers, and at least a portion of the plurality of hydroxyl groups and a portion of the carboxyl groups and / or phosphate groups form ester bonds and / or phosphate ester bonds. 1.1. Fiber First, the fibers constituting the raw thread material according to the present embodiment will be described. The fibers constituting the raw thread material according to the present embodiment are the base material of the raw thread material according to the present embodiment. The material constituting the fibers is not particularly limited as long as it has a plurality of hydroxyl groups on the surface, and natural fibers and / or synthetic fibers can be used. Examples of natural fibers include cotton, hemp, kenaf, pulp (chemical pulp, mechanical pulp), other plant fibers, particularly natural cellulose fibers such as fibers derived from wood fibers, various cellulosic fibers such as regenerated cellulose fibers such as viscose rayon, cupra, and acetate, polysaccharide fibers such as chitin and chitosan, animal hair such as wool, cashmere, and angora, and silk, and any of these may be used alone or in combination of two or more. Examples of synthetic fibers include polyvinyl alcohol fibers and ethylene vinyl alcohol fibers. One of these fibers may be used alone or two or more of them may be used in combination. Among the above, the fibers are preferably cellulosic fibers, more preferably natural cellulose. The preferred cellulose fiber is a cellulose fiber, more preferably one or more selected from the group consisting of cotton, hemp, kenaf and pulp, and particularly preferably cotton. Such cellulose fibers have abundant hydroxyl groups on the surface and can be suitably used as the yarn raw material according to the present embodiment. Natural cellulose, especially cotton, is used in large amounts in textile products, and therefore is also disposed of in large amounts, so there is a demand for its effective use, and it is also suitable for recycling into textile products such as clothing. The shape of the fiber is not particularly limited and may be, for example, a single fiber, a twisted yarn, a hollow fiber, a staple fiber, cotton, etc., and one of these may be used alone or two or more may be used in combination. The fibers may be unused or may be fibers obtained from scraps or fluff generated during the manufacture of textile products. Fibers obtained by using a reclaiming technique to recover the original fluff or hair-like single fibers from used textile products or scraps generated during the manufacture of textile products by breaking up the weave with a needle-like tool are called reclaimed fibers. Such reclaimed fibers have a relatively short fiber length and are uneven in fiber length, making them difficult to recycle except for some reclaimed fibers with relatively long fibers. However, the yarn raw material according to the present embodiment can be suitably used for the manufacture of yarn even if it is such a reclaimed fiber. The average length of the fibers is not particularly limited, and may be, for example, 0.10 mm to 10.0 mm, preferably 0.10 mm to 6.0 mm, more preferably 0.20 mm to 6.0 mm, and even more preferably 0.20 mm to 2.0 mm. Generally, fibers with a length of 10.0 mm or less are difficult to recycle, except for some regenerated cellulose fibers, but the yarn raw material according to this embodiment can be suitably used for yarn production even if it is such a short fiber. The average diameter of the fibers is not particularly limited and is, for example, 1.0 μm to 30 μm, preferably 2.0 μm to 30 μm, and more preferably 5.0 μm to 20 μm. When the average fineness of the fibers is in such a range, the fibers can be suitably used for yarn production. (1.2.) Polymer having a carboxy group (first polymer) The polymer (first polymer) contained in the thread material according to this embodiment is disposed on the surface of the fiber and has a plurality of carboxyl groups and / or phosphate groups. At least a portion of the hydroxyl groups and a portion of the carboxyl groups and / or phosphate groups form ester bonds and / or phosphate ester bonds. That is, the thread material according to this embodiment is modified on the surface of the fiber with the polymer via ester bonds and / or phosphate ester bonds. As a result, the raw thread material according to this embodiment has a large number of carboxyl groups and / or phosphate groups exposed on the surface of the fiber due to the first polymer. These carboxyl groups and phosphate groups, for example, contribute to the formation of thread by adhesion or chemical bonding between the raw thread materials, either as is or after further chemical modification as appropriate. In addition, the raw thread material according to this embodiment can efficiently adsorb cationic dirt from the outside, such as dirt and dust from the user, due to the carboxyl groups and / or phosphate groups exposed on its surface. For example, it can adsorb polyvalent cations, alkali metal ions with a large ionic radius, ammonium ions of ammonia and organic amines, quaternary ammonium ions, and cationic organic dyes such as methylene blue. The first polymer is not particularly limited as long as it has a plurality of carboxyl groups and / or phosphate groups, and can include, for example, polycarboxylic acid and / or polyphosphoric acid. The polycarboxylic acid is not particularly limited, but may include, for example, one or more selected from the group consisting of polyacrylic acid, polymethacrylic acid, acrylic acid / maleic acid copolymer, methacrylic acid / maleic acid copolymer, acrylic acid / methacrylic acid / maleic acid copolymer, alginic acid, carboxymethyl cellulose, and partially oxidized cellulose, as well as derivatives thereof. Among the above, the first polymer preferably includes one or more selected from the group consisting of polyacrylic acid, polymethacrylic acid, alginic acid, carboxymethyl cellulose, and partially oxidized cellulose and derivatives thereof, and more preferably includes one or more selected from the group consisting of polyacrylic acid, polymethacrylic acid, alginic acid, and carboxymethyl cellulose. The acid value of the first polymer is not particularly limited, but is, for example, 20 mgKOH / g to 3000 mgKOH / g, preferably 100 mgKOH / g to 2000 mgKOH / g, more preferably 200 mgKOH / g to 1500 mgKOH / g, and even more preferably 500 mgKOH / g to 1000 mgKOH / g. With an acid value in such a range, the first polymer can be firmly fixed to the fiber surface, and the carboxyl group and / or phosphate group can be sufficiently exposed on the surface of the yarn material according to this embodiment, so that the above-mentioned effect can be obtained more significantly. In this specification, the "acid value" refers to the number of milligrams of potassium hydroxide required to neutralize the carboxyl group and phosphate group contained in 1 gram of the polymer, and is calculated from the molecular structure of the polymer. For example, when the polymer is polyacrylic acid, the molecular weight of the monomer unit is 72, the monomer unit contains one carboxyl group, and the formula weight of potassium hydroxide is 56.11, so the acid value is calculated to be 780 mgKOH / g (=1 / 72×56.11×1000 mg / g). Similarly, when the polymer is alginic acid, the acid value is calculated to be 319 mgKOH / g (=2 / 352×56.11×1000 mg / g). The number average molecular weight of the first polymer is not particularly limited, but is, for example, from 300 to 1,000,000, preferably from 500 to 100,000, and more preferably from 600 to 50,000. This allows the number of carboxy groups and / or phosphate groups per molecule to be increased, making it possible to more firmly fix the first polymer to the fiber surface by the many carboxy groups and / or phosphate groups, and also generating a large number of adhesion points when thread raw materials are brought into contact with each other, making it possible to more reliably adhere the thread raw materials to form a strong thread. The number average molecular weight of the first polymer can be determined by gel permeation chromatography using a calibration curve prepared using polystyrene. (1.3.) Polymer having amino groups (second polymer) The thread material according to the present embodiment may further include a polymer (second polymer) having a plurality of amino groups. For example, the second polymer is attached to the fiber surface via the polymer having a carboxyl group or a phosphate group by forming an amide bond or a phosphoric acid amide bond with the amino group of the second polymer and the second polymer is attached to the fiber surface. The polymer having an amino group attached to the fiber surface can bond to the other thread material by forming an amide bond with the carboxyl group of the other thread material through the amino group, or can bond to the other thread material electrostatically via another anionic substance, such as clay. Examples of such a second polymer include polyamines and polyammoniums. Examples of polyamines include polyaminoalkyl alkylenes such as polyallylamine, polyalkyleneimines, and polymers having secondary and / or tertiary amines in their skeletons. Examples of polyammoniums include poly(diallyldimethylammonium salts) and polyionenes. Examples of polyalkyleneimines include homopoly C1-6 alkyleneimines (preferably poly C2-4 alkyleneimines) such as polyethyleneimine, polypropyleneimine, polyisopropyleneimine, polybutyleneimine, and polyisobutyleneimine, and copolyalkyleneimines corresponding to these homopolyalkyleneimines. The polyalkyleneimine may be a branched polymer or a linear polymer. The polyalkyleneimine may be a mixture of a branched polymer and a linear polymer. Preferably, the polyalkyleneimine contains at least a branched polymer. The number average molecular weight of the second polymer is not particularly limited, but is, for example, from 500 to 1,000,000, preferably from 600 to 50,000, and more preferably from 1,000 to 20,000. The number average molecular weight of the second polymer can be measured in the same manner as that of the first polymer. The thread material according to the present embodiment described above has a first polymer having a carboxyl group and / or a phosphate group arranged on the fiber surface. The carboxyl group and the phosphate group contribute to the formation of thread by adhesion or chemical bonding of the thread materials, for example, as is or after further chemical modification as appropriate. Therefore, the thread material according to the present embodiment can be suitably used for thread production even when fibers that are usually difficult to recycle, such as ripped fibers, or relatively short fibers are used. In addition, the yarn raw material according to this embodiment has carboxyl groups and / or phosphate groups exposed on its surface, which enable it to efficiently adsorb cationic external dirt such as dirt and dust from users of the textile products in which the yarn raw material is used. Furthermore, when the yarn raw material according to this embodiment contains a second polymer, a textile product containing the yarn raw material can strongly adsorb and fix anionic contaminants such as carboxylic acids and phenols due to the amino groups exposed on the surface of the yarn raw material. As described above, the yarn raw material according to this embodiment can produce useful yarn even from fibers that are normally difficult to recycle, such as reclaimed fibers. 2. Manufacturing method of yarn raw material Next, a method for producing a thread raw material according to a preferred embodiment of the present invention will be described. The method for producing a thread raw material according to this embodiment includes a first polymer modification step in which a first polymer having multiple carboxyl groups and / or phosphate groups is fixed to at least a portion of the hydroxyl groups of a fiber having multiple hydroxyl groups on its surface by ester bonds and / or phosphate ester bonds. The method for producing a thread raw material according to this embodiment includes a fiber preparation step in which a fiber having multiple hydroxyl groups on its surface is prepared prior to the first polymer modification step, and optionally includes a second polymer modification step in which a second polymer having multiple amino groups is fixed to the fiber surface via the first polymer after the first polymer modification step. (2.1.) Fiber Preparation First, in this step, a fiber having a plurality of hydroxyl groups on its surface is prepared. Examples of the fiber having a plurality of hydroxyl groups on its surface include various fibers that can be used as the above-mentioned fiber. In addition, the fiber may be subjected to a known processing and cleaning treatment as necessary. In this step, the fibers may be purchased from a market or may be discarded. Alternatively, the fibers may be obtained from purchased or discarded textile products by various means such as garnishing. (2.2.) First polymer modification step Next, in this step, a first polymer having a plurality of carboxyl groups and / or phosphate groups is fixed to at least a portion of the hydroxyl groups of the fiber via ester bonds and / or phosphate ester bonds. Fixation of the first polymer to the fiber, i.e., formation of ester bonds and / or phosphate ester bonds by reaction between hydroxyl groups on the fiber surface and ester bonds and / or phosphate esters in the first polymer, can be carried out, for example, by contacting the fiber with a first treatment liquid containing the first polymer. The first treatment liquid usually contains a solvent. Examples of the solvent include water and various organic solvents such as alcohol-based solvents. Examples of the organic solvent include alcohol-based solvents such as methanol, ethanol, n-propyl alcohol, 2-methylpropyl alcohol, 1-butanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1,3-butanediol, 1,4-butanediol, 2-ethylhexanol, and benzyl alcohol; ketone-based solvents such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclohexanone, and diacetone alcohol; dimethyl ether, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-t-butyl ether, t-butyl methyl ether; and 1,2-dimethylphenyl ether.4-Dioxane, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol monomethyl ether propionate, tetrahydrofuran Examples of the solvent include ether solvents such as fluorouran, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, ester solvents such as ethyl acetate, methyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, n-propyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, and butyl lactate, carbonate solvents such as dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate, halogen solvents such as methylene chloride, trichloroethylene, perchloroethylene, 1-bromopropane, chloroform, and carbon tetrachloride, 2-pyrrolidone N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, sulfolane, morpholine, acetonitrile, propionitrile, dimethyl sulfoxide, methyl ethyl sulfoxide, and diethyl sulfoxide, and these can be used alone or in combination of two or more. Among the above, the solvent preferably contains one or more selected from the group consisting of water and alcohol-based solvents, and more preferably contains 2-ethoxyethanol. The concentration of the first polymer in the first treatment liquid is not particularly limited, but can be, for example, 0.10 mass % or more and 20 mass % or less, preferably 1.0 mass % or more and 10 mass % or less, and more preferably 2.0 mass % or more and 5.0 mass % or less. In addition, the first treatment liquid may contain an acid or a base as a catalyst, if necessary. Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and one of these may be used alone or two or more may be used in combination. Examples of the base include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and ammonia, and one of these may be used alone or two or more may be used in combination. Furthermore, examples of the base include alkali metal alkoxides such as sodium ethoxide, sodium n-propoxide, sodium i-propoxide, sodium n-butoxide, sodium i-butoxide, sodium t-butoxide, potassium ethoxide, potassium n-propoxide, potassium i-propoxide, potassium n-butoxide, potassium i-butoxide, and potassium t-butoxide, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and organic bases such as diazabicycloundecene and tetraalkylammonium hydroxide. The contact of the first treatment liquid with the fiber may be carried out by any method, for example, by immersing the fiber in the first treatment liquid, or by applying or spraying the first treatment liquid onto the fiber. Heating may be performed in order to promote the formation of ester bonds and / or phosphate ester bonds. The reaction temperature during heating is not particularly limited, but may be, for example, 30° C. to 200° C., preferably 60° C. to 160° C., and more preferably 100° C. to 140° C. The reaction time is also not particularly limited, but may be, for example, 10 minutes to 240 minutes, preferably 30 minutes to 120 minutes, and more preferably 40 minutes to 80 minutes. (2.3.) Second polymer modification step Next, in this step, a second polymer having a plurality of amino groups is fixed to the fiber surface via the first polymer. The second polymer is fixed to the fiber surface, for example, by reacting the carboxyl and / or phosphate groups remaining in the first polymer fixed to the fiber surface with at least a part of the amino groups of the second polymer to form amide bonds and / or phosphate amide bonds. Specifically, the second polymer can be fixed to the fiber surface by contacting the fiber with the second treatment liquid containing the second polymer. The first treatment liquid usually contains a solvent. Examples of the solvent include various organic solvents such as water and alcohol-based solvents. Examples of the organic solvent include the organic solvents that can be used in the first treatment liquid described above, and these can be used alone or in combination of two or more. Among the above, the solvent preferably contains an alcohol-based solvent, more preferably ethanol, which is less harmful to the human body and has a small environmental impact. The concentration of the second polymer in the second treatment liquid is not particularly limited, but is, for example, 0.10 g / L or more and 200 g / L or less, preferably 0.50 g / L or more and 100 g / L or less, and more preferably 5.0 g / L or more and 50 g / L or less. The second treatment liquid may be contacted with the fibers by any method, for example, by immersing the fibers in the second treatment liquid, or by applying or spraying the second treatment liquid onto the fibers. Heating may be performed in order to promote the formation of amide bonds and / or phosphoric acid amide bonds. The reaction temperature during heating is not particularly limited, but may be, for example, 30° C. to 150° C., preferably 60° C. to 100° C., and more preferably 80° C. to 100° C. The reaction time is also not particularly limited, but may be, for example, 5 minutes to 300 minutes, and preferably 20 minutes to 100 minutes. This step may be performed as necessary and may be omitted. Through the above steps, the yarn raw material according to this embodiment can be manufactured. 3. Yarn and manufacturing method of yarn Next, some preferred embodiments of the yarn and the yarn manufacturing method of the present invention will be described. The yarn of the present invention includes the yarn raw material of the present invention. In addition, the yarn manufacturing method of the present invention uses the yarn raw material of the present invention to manufacture the yarn. (3.1.) First embodiment The thread according to this embodiment is obtained by bonding the thread raw materials according to the embodiment described above together via ester bonds and / or phosphate ester bonds. For example, adjacent thread raw materials are bonded together by forming ester bonds and / or phosphate ester bonds between hydroxyl groups remaining on the fiber surface of the thread raw material and carboxyl groups and / or phosphate groups of the first polymer of another thread raw material. In this embodiment, the thread raw material preferably does not include the second polymer described above. In this way, the yarn of the present embodiment has a relatively high strength even when the yarn raw material is a relatively short fiber, because the yarn raw material is bonded to each other by covalent bonds. Furthermore, the carboxyl group and / or phosphate group of the first polymer can efficiently adsorb cationic dirt from the outside, such as dirt from the user and dust. (3.2.) Second embodiment The thread according to the present embodiment is obtained by bonding the thread raw materials according to the present embodiment described above together via amide bonds and / or phosphoric acid amide bonds. For example, adjacent thread raw materials are bonded together by forming amide bonds and / or phosphoric acid amide bonds between a carboxy group and / or a phosphoric acid group of a first polymer of a thread raw material and an amino group of a second polymer of another thread raw material. Note that in the present embodiment, for example, the thread raw material not including the second polymer and a thread raw material including the second polymer are mixed and reacted to obtain the thread raw material. As in the first embodiment described above, the yarn raw materials are bonded to each other by covalent bonds, so that the yarn in this embodiment has relatively high strength even when the yarn raw materials are relatively short fibers. Furthermore, since the yarn according to this embodiment contains a second polymer, a textile product containing the yarn according to this embodiment can strongly adsorb and fix anionic contaminants, such as carboxylic acids and phenols, by the amino groups exposed on the surface of the yarn. (3.3.) Third embodiment The thread according to this embodiment is obtained by electrostatically bonding the above-mentioned thread raw materials according to this embodiment together via a compound that forms a counterion to the anions or cations present on the surface of the thread raw materials. (3.4.) Fourth embodiment The yarn according to the present embodiment is obtained by mixing a known yarn material with the yarn material according to the present embodiment. Usually, it is difficult to use relatively short fibers such as rewind fibers as a yarn material. However, the yarn material according to the present embodiment as described above has carboxyl groups and / or phosphate groups exposed on its surface due to the first polymer, and these groups enable it to be firmly bonded to other adjacent yarn materials via electrostatic or covalent bonds. Therefore, even if the yarn material according to the present embodiment is relatively short, it can be suitably used as a yarn material. Furthermore, the carboxyl group and / or phosphate group of the first polymer can efficiently adsorb cationic contaminants from among dirt and external contaminants such as dirt and dust from the user. Materials constituting the yarn raw materials other than the yarn raw material according to this embodiment included in the yarn according to this embodiment are not particularly limited, and in addition to the materials that can be used for the yarn raw materials as described above, for example, include acrylic fibers, acrylic fibers such as modacrylic fibers, polyester fibers such as polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polylactic acid, polyether ester fibers, polyolefin fibers such as polyethylene and polypropylene, polyacrylate fibers, polyvinyl chloride fibers, nylon fibers such as nylon 6 and nylon 66, polyamide fibers, polyimide fibers, aramid fibers, polyetherimide fibers, polyphenylene sulfide fibers, polyurethane fibers, polyvinyl alcohol fibers, ethylene vinyl alcohol fibers, polyarylate fibers, and the like, and one of these can be used alone or two or more can be used in combination. In particular, it is preferable that the material constituting the yarn raw material other than the yarn raw material according to the present embodiment contained in the yarn according to the present embodiment contains a material having multiple hydroxyl groups as described above, which allows the yarn raw materials to be bonded to each other via ester bonds or phosphate ester bonds. <5. Textile products and manufacturing methods for textile products> The textile product according to the present invention comprises the yarn raw material and / or the yarn according to the present invention. The textile product can be, for example, a garment, a woven fabric, a knitted fabric, a lace fabric, etc. A preferred embodiment of the textile product and the method for producing the textile product according to the present invention will be described. For example, the textile product of the present invention can be formed into a nonwoven textile product by the following operations 1) to 3) using the above-mentioned yarn raw material or yarn of the present invention as cellulose. 1) Disperse cellulose in water The yarn raw material or yarn of the present invention is dispersed in an aqueous solution containing a first polymer to obtain a dispersion. 2) Filtration using a membrane filter The dispersion is filtered by suction through a membrane filter or a wire mesh to obtain a deposition film. 3) Esterification by dehydration condensation The filtered deposited film is placed on a boat and placed in a furnace where it is heated at high temperature. The above steps 1) to 3) are repeated for the obtained nonwoven fabric depending on its strength. The present invention has been described in detail above based on a preferred embodiment, but the present invention is not limited to this, and each component can be replaced with any component that can perform a similar function, or any component can be added. The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. <1. Manufacturing of yarn using reclaimed fibers> Example 1 First, cotton cloth made from discarded bed linen (100% cotton by mass) was crushed using a small crusher (manufactured by Sanriki Seisakusho, model number "SF-1") to obtain remoulded fibers from the cotton cloth. The remoulded fibers passed through a 20-mesh sieve but not a 50-mesh sieve were used as sample remoulded fibers in the following tests. The meshes are based on the JIS sieve mesh openings specified in JIS Z 8801-1:2006. Figure 8 shows the fiber length distribution in each section after classification by each sieve. In the figure, "20 mesh sieve on" indicates the section that did not pass through the 20-mesh sieve, "50 mesh sieve on" indicates the section that passed through the 20-mesh sieve and not the 50-mesh sieve, and "50 mesh sieve on" indicates the section that passed through the 50-mesh sieve. Next, the dehaired fibers were added to 50 ml of a 5% by mass aqueous solution of sodium alginate, and the mixture was thoroughly stirred with a magnetic stirrer to obtain a gel of sodium alginate and dehaired fibers. The sodium alginate used was manufactured by Wako Pure Chemical Industries, Ltd. ("Sodium Alginate 80-120", viscosity 80-120 cP). The sodium alginate gel containing the dehaired fibers was sucked up by a syringe with a glass tube (inner diameter 4 mm) connected to the tip, and was continuously added to a 1M aqueous solution of hydrochloric acid. The linear gel after addition was air-dried to obtain a thread according to Example 1. FIG. 1 shows a photograph of the gel before air-drying, and FIG. 2 shows a photograph of the thread after air-drying. Example 2 A yarn according to Example 2 was obtained in the same manner as in Example 1, except that the concentration of sodium alginate in the sodium alginate aqueous solution was set to 3% by mass. Figure 3 shows a photographic image of the gel before air drying, and Figure 4 shows a photographic image of the yarn after air drying. In Example 2, compared to Example 1, the sodium alginate gel containing the depilated fibers could be added continuously to the 1M hydrochloric acid aqueous solution more smoothly, and the gel was not broken during the addition. 2. Observation of introduction of carboxyl and hydroxyl groups using a zeta potential meter Example 3 First, cotton cloth made from discarded bed linen (100% by mass of cotton) was crushed using a small crusher (manufactured by Sanriki Seisakusho, model number "SF-1") to obtain regenerated fibers from the cotton cloth. These were used as regenerated fibers in the following tests. Next, 3.0 g of the dehaired fiber was added to 100 ml of a 3% by mass aqueous solution of sodium alginate. Then, the mixture was heated in an oil bath at 120° C. for 1 hour while being thoroughly stirred with a magnetic stirrer. The resulting gel-like material was washed 4 to 5 times with distilled water and then air-dried to obtain the thread material according to Example 3. The zeta potential of the yarn material according to Example 3 was measured in the range of pH 9 to pH 2 using a zeta potential analyzer for solid surface analysis (SurPASS3, manufactured by Anton Parr). Specifically, the measurement was started from pH 9, and measurements were performed manually for pH 9 to 7, and in automatic measurement mode for pH 6 to 2. The results are shown in FIG. Example 4 A yarn material according to Example 4 was obtained in the same manner as in Example 3, except that a 3% by mass sodium alginate solution in which ethylene glycol was used as a solvent was used instead of the 3% by mass sodium alginate aqueous solution, and the zeta potential was measured. The results are shown in FIG. Example 5 A thread material according to Example 5 was obtained in the same manner as in Example 3, except that a 3% by mass sodium alginate solution in which 2-ethoxyethanol was used as a solvent was used instead of the 3% by mass sodium alginate aqueous solution, and the zeta potential was measured. The results are shown in FIG. (Reference example 1) The zeta potential of the untreated regenerated fiber used as the sample in Example 3 was measured for reference. The results are shown in FIG. As shown in Fig. 5, the zeta potential of the yarn material according to Examples 3 and 4 was shifted to the positive side compared to the untreated recycled fiber. This is thought to be because the carboxyl group of the alginic acid and the hydroxyl group on the surface of the recycled fiber were ester-bonded, and as a result, the hydroxyl group was consumed compared to the recycled fiber of Reference Example 1, resulting in an increase in the zeta potential. On the other hand, as shown in Fig. 5, the zeta potential of the yarn material according to Example 5 was shifted to the negative side compared to the untreated recoiled fibers. This is thought to be because the carboxyl groups of alginic acid and the hydroxyl groups on the surface of the recoiled fibers were bonded to each other more than in Examples 3 and 4, and as a result, more alginic acid molecules were bonded to the surface of the recoiled fibers, increasing the number of carboxyl groups present on the surface of the yarn material, resulting in a decrease in the zeta potential compared to the recoiled fibers of Reference Example 1. Example 6 Cotton cloth made from discarded bed linen (100% cotton by mass) was pulverized using a small pulverizer (manufactured by Sanriki Seisakusho, model number "SF-1") to obtain regenerated fibers from the cotton cloth. These were used as regenerated fibers in the following tests. 0.10 g of dehaired fiber was added to 10 ml of 1% by mass polyacrylic acid (number average molecular weight 25,000) aqueous solution, and immersed for 15 minutes. The fiber was filtered out with a filter, and the liquid was absorbed and removed with Kimwipe. The fiber was placed in an alumina boat and dried under air flow for 30 minutes. Next, the sample placed in the alumina boat was heated in a tubular furnace at 140° C. under air flow for 1 hour to partially The sample was removed from the tubular furnace, cooled to room temperature, washed with a large amount of tap water, and most of the water was absorbed and removed with Kimwipes to obtain a yarn material according to Example 6. The obtained yarn material was dried in an oven at 80° C. for 1 hour, and subjected to infrared spectroscopy analysis by the attenuated total reflection method (ATR method) to obtain an infrared absorption spectrum. The results are shown in FIG. 6. (Reference example 2) For reference, the untreated retentate fiber used as the sample in Example 6 was subjected to infrared spectroscopy analysis, and the results are shown in FIG. As shown in FIG. 6, the yarn material according to Example 6 has a thickness of 1700 cm －１ On the other hand, no such peak was observed in the untreated recycled fiber of Reference Example 2. －１ The peak at the wave number of is a peak derived from the C=O bond of the carboxy group. This carboxy group is presumed to be polyacrylic acid, and it was confirmed that polyacrylic acid was fixed to the surface of the recycled fiber in the yarn material of Example 6 by the treatment with polyacrylic acid. (Example 7) Cotton cloth made from discarded bed linen (100% cotton by mass) was pulverized using a small pulverizer (manufactured by Sanriki Seisakusho, model number "SF-1") to obtain regenerated fibers from the cotton cloth. These were used as regenerated fibers in the following tests. 5.0 g of the dehaired fiber was added to 95 ml of 10% by weight polyacrylic acid (number average molecular weight 25,000) aqueous solution, and immersed for 15 minutes. The fiber was filtered out with a filter, and the liquid was absorbed and removed with Kimwipes. This was dried in a 200 mL flask at 70°C under atmospheric airflow for 30 minutes. Next, the sample placed in a glass tube was heated in a tubular furnace at 140°C under atmospheric airflow for 1 hour to be partially esterified. The sample was removed from the tubular furnace, cooled to room temperature, washed with a large amount of tap water, and most of the water was absorbed and removed with Kimwipes. 2.8 g of the resulting polyacrylic acid-treated depilated fiber was added to 95 ml of a 5% by mass polyethyleneimine (number average molecular weight 600) aqueous solution and immersed for 15 minutes. After immersion, the depilated fiber was filtered through a filter, and the liquid was absorbed and removed with Kimwipes. This was dried for 30 minutes under atmospheric airflow in a 200 mL flask maintained at 70°C. Next, the sample placed in the glass tube was heated in a tubular furnace at 100°C under atmospheric airflow for 1 hour to be partially amidated. After removing the glass tube from the tubular furnace and cooling to room temperature, the sample was washed with a large amount of tap water, and most of the water was absorbed and removed with Kimwipes to obtain the yarn material according to Example 7. The obtained yarn material was dried in an oven at 80°C for 1 hour, and infrared spectroscopy was performed using the total reflection measurement method (ATR method) to obtain an infrared absorption spectrum. The results are shown in FIG. 7. The infrared absorption spectrum of the polyacrylic acid-treated fiber shown in Example 6 is superimposed on FIG. 7 for comparison. As shown in FIG. 7, the yarn material according to Example 7 has an infrared absorption spectrum of 1700 cm －１ It was observed that the wave number peak at 1560 cm was reduced compared to the yarn material of Example 6. －１ The wave number peak at 1700 cm －１ The peak at the wavenumber of 1560 cm is due to the C=O bond of the carboxyl group. －１ The peak at the wave number of － ) is a peak derived from the above. Therefore, it was presumed that, in the yarn material according to Example 7, the residual carboxyl group of the polyacrylic acid was dissociated by at least the amino group of the polyethyleneimine due to the treatment with polyethyleneimine, and interacted with the amino group, and the residual carboxyl group and the amino group formed a salt. In addition, in the infrared spectroscopy, the absorption of the amide bond derived from the carboxyl group of polyacrylic acid and the amino group of polyethyleneimine was not observed. This is because, considering the degree of polymerization of polyethyleneimine and polyacrylic acid, it is presumed that the amide bond formed in Example 7 is limited to the amino group of the polyethyleneimine and a part of the carboxyl group of the polyacrylic acid, and most of the amino group and the carboxyl group remain. Therefore, it is considered that this small amount of amide bond could not be detected in the infrared spectroscopy analysis by the total reflection measurement method this time. In any case, since dissociation of the carboxy group of polyacrylic acid was confirmed, it was presumed that the remaining carboxy group and the amino group formed a salt, and it was presumed that amino groups derived from polyethyleneimine were introduced onto the surface of the yarn material of Example 7. (Example 8) A nonwoven fabric was formed from the regenerated fibers by the following steps 1) to 3). 1) Disperse cellulose in water 0.11 g of the remnant fiber obtained in Example 7 was dispersed in 25 ml of a 5% by weight aqueous solution of polyacrylic acid (number average molecular weight 250,000), and the mixture was stirred overnight with a stirrer in an Erlenmeyer flask to obtain a dispersion. 2) Filtration using a filter 10 ml of the dispersion liquid 1) above was suction filtered through a stainless steel wire mesh (500 mesh, openings approximately 25 μm) to obtain a deposition film. 3) Esterification by dehydration condensation The filtered deposited film was placed on a boat made of aluminum foil and placed in a tube furnace and heated at 100° C. for about 2 hours. Thereafter, the product was removed from the furnace to obtain a prototype nonwoven fabric that had been crosslinked once. Furthermore, the nonwoven fabric that had been crosslinked once was used as the cellulose material, and the above-mentioned operations 1) to 3) were carried out to obtain a prototype nonwoven fabric that had been crosslinked twice. The resulting nonwoven fabric samples that had been crosslinked once and twice were used to measure the breaking strength using a tensile tester under the following conditions. The results are shown in FIG. Measurement conditions: Temperature 24°C, humidity 55%, low performance measured twice Fabric size: Width 10mm x Length 70mm, zipper spacing 20mm Tensile speed: 20 mm / min Measurement equipment: Tensile tester RTH-1310 type / AandD (load cell 50N) *Calculated from the tensile strength value of plain woven fabric (width 50 mm) (Daisuke Ikegami, Yuki Shimagami, Aichi Prefectural Industrial Technology Research Institute Research Report, No. 7, p. 132-135 (2008)) From the results shown in FIG. 9, it was confirmed that the nonwoven fabric formed from the recycled fibers had a strength adequate for practical use, even when compared with the cotton fabric before it was made into recycled fibers.
Claims
1. a recycled fiber having a plurality of hydroxyl groups on its surface; a polymer having a plurality of carboxyl groups and / or phosphate groups, the polymer being disposed on the surface of the fiber; A yarn raw material, wherein at least a portion of the plurality of hydroxyl groups and a portion of the carboxyl groups and / or phosphate groups form ester bonds and / or phosphate ester bonds.
2. The yarn material according to claim 1 , wherein the polymer comprises a polycarboxylic acid and / or a polyphosphoric acid.
3. 3. The yarn material according to claim 2, wherein the polycarboxylic acid comprises one or more selected from the group consisting of polyacrylic acid, polymethacrylic acid, acrylic acid / maleic acid copolymer, methacrylic acid / maleic acid copolymer, acrylic acid / methacrylic acid / maleic acid copolymer, alginic acid, carboxymethyl cellulose, partially oxidized cellulose, and derivatives thereof.
4. The yarn material according to claim 1, wherein the acid value of the polymer is 20 mg KOH / g or more and 3000 mg KOH / g or less.
5. The thread material according to claim 1, wherein the number average molecular weight of the polymer is 300 or more and 1,000,000 or less.
6. The yarn material according to claim 1, further comprising a polymer having a plurality of amino groups fixed to the fiber via the polymer having a plurality of carboxyl groups and / or phosphate groups.
7. The yarn material according to claim 1 , wherein the depilled fibers are cellulosic fibers.
8. (delete)
9. The yarn material according to claim 1, wherein the average length of the repulped fibers is 0.10 mm or more and 6.0 mm or less.
10. A yarn comprising the yarn material of claim 1.
11. A textile product comprising the yarn material according to claim 1 or the yarn according to claim 10.
12. A method for producing yarn raw material, comprising a step of fixing a polymer having multiple carboxyl groups and / or phosphate groups to at least some of the hydroxyl groups on the surface of recycled fibers via ester bonds and / or phosphate ester bonds.
13. A method for producing a yarn, comprising producing a yarn using the yarn raw material according to claim 1.