TW202403137A - Method for producing polysaccharide fiber - Google Patents

Abstract

One of the purposes of the present disclosure is to provide a method for producing polysaccharide fiber, wherein said method enables the spinning of polysaccharide fiber that exhibits little physical property unevenness and an excellent skin feel. The present disclosure provides a method for producing polysaccharide fiber, said method comprising: a solution preparation step for dissolving polysaccharide in a mixed solvent of an aprotic polar solvent and a quaternary ammonium salt and/or quaternary phosphonium salt; a discharge step for discharging the prepared solution in a fibrous form from a spinneret; and a coagulation step for bringing about coagulation by bringing the discharged fiber into contact with a coagulation bath. The cation moiety in the quaternary ammonium salt and quaternary phosphonium salt has two or more species of alkyl groups. The anion moiety in the quaternary ammonium salt and quaternary phosphonium salt is a carboxylate anion. An air gap is disposed between the spinneret and the coagulation bath in the discharge step.

Description

Manufacturing method of polysaccharide fiber

The present invention relates to a method for manufacturing polysaccharide fiber.

In recent years, from the viewpoint of environmental protection, attention has been paid to the development of methods for manufacturing products containing natural polysaccharides, which are renewable resources, by further reducing environmental load. Since polysaccharides usually have a melting point higher than the thermal decomposition point due to intramolecular and intermolecular hydrogen bonds, wet molding in which the polysaccharide is dissolved in a solvent and then contacted with a non-solvent is used as a molding method. Representative products containing polysaccharides are regenerated cellulose fibers. Lyocell fibers, which use an aqueous solution of N-methylmethacrylate oxide (NMMO) as a solvent for dissolving cellulose, are known to have a lower environmental impact during the production process, but the hardness of the fibers obtained may There are problems with fibrillation, etc., so solvents that can replace them are sought.

For example, Patent Document 1 describes a solvent that can uniformly dissolve polysaccharides in a short time without requiring special pretreatment, and a molded article and polysaccharide using the solvent. Methods for manufacturing derivatives.

Patent Document 2 describes a spinning method of a cellulose solution, which is characterized by wet spinning a spinning stock solution obtained by dissolving cellulose in a mixed solvent of a tetraalkylammonium salt and dimethylstyrene. Or wet and dry spinning. This method uses a first spinning bath of dimethyltrisoxide-tetraalkylammonium salt-water system, and a second spinning bath of dimethylterousine-tetraalkylammonium salt-water system. The first spinning bath Contain dimethyl styrene at a concentration of less than 2/3 of the concentration of dimethyl styrene in the stock solution, and contain tetraalkylammonium salt at a concentration of less than 1/3 of the concentration of dimethyl styrene in the stock solution , the bath temperature does not exceed 60°C, and the second spinning bath contains dimethyl trisulfide at a concentration of less than 1/2 of the concentration of dimethyl trisulfide and the concentration of tetraalkylammonium salt in the first spinning bath. For water and tetraalkyl ammonium salt, the bath temperature is 60℃~normal temperature. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2012-211302 [Patent Document 2] Japanese Patent Application Publication No. Sho 60-199912

[Problem to be solved by the invention]

By dissolving polysaccharides in a solvent, molding the resulting solution into a desired shape and contacting it with a non-solvent, the resulting solution can be molded into molded articles of various shapes. The techniques described in Patent Documents 1 and 2 can be used to dissolve polysaccharides such as cellulose in a mixed solvent of a quaternary ammonium salt and an organic solvent to form a molded article. However, the production of polysaccharide fibers is more advanced. There is still room for improvement in spinning, for example, in producing fibers with less uneven physical properties and excellent skin feel.

In view of the problems of the prior art, one object of the present invention is to provide a method for producing polysaccharide fibers capable of spinning polysaccharide fibers with less unevenness in physical properties and excellent skin feel. [Technical means to solve problems]

The inventors of the present invention conducted intensive research and repeated experiments in order to solve this problem. As a result, they unexpectedly discovered that this problem can be solved by adopting the following configuration, and thus completed the present invention. Examples of embodiments of the present invention are listed below. [1] A method for manufacturing polysaccharide fibers, which includes: a solution preparation step in which polysaccharides are dissolved in a mixed solvent of an aprotic polar solvent and a quaternary ammonium salt and/or a quaternary phosphonium salt; and a spraying step , which is to spray the prepared solution from the spinning nozzle in the form of fibers; and the coagulation step, which is to make the sprayed fibers contact the coagulation liquid to solidify; and the cationic part of the above-mentioned quaternary ammonium salt and quaternary phosphonium salt has 2 The above alkyl group, the anion part of the quaternary ammonium salt and the quaternary phosphonium salt is a carboxylate anion, and in the above ejection step, an air gap is provided between the above spinning nozzle and the above coagulation liquid. [2] The method according to item 1, wherein in the cation part of the above-mentioned quaternary ammonium salt and the above-mentioned quaternary phosphonium salt, the carbon number C _L of the alkyl group with the largest carbon number and the carbon number of the alkyl group with the smallest carbon number are The number C _S satisfies 2< _CL /C _S . [3] The method according to item 1 or 2, wherein the moisture content of the solution in the ejection step is 0.05 mass% or more and 8 mass% or less based on the total mass of the solution. [4] The method according to any one of items 1 to 3, wherein the water content of the solution in the ejection step is 0.05 mass % or more and 2 mass % or less based on the total mass of the solution. [5] The method as described in any one of items 1 to 4, wherein the atmosphere in the air gap has a relative humidity of 90% or less. [6] The method according to any one of items 1 to 5, wherein the length of the air gap from the spinning nozzle to the coagulation liquid is 1 mm or more and 30 mm or less. [7] The method as described in any one of items 1 to 6, wherein the mass ratio of the above-mentioned aprotic polar solvent and the quaternary ammonium salt and/or the quaternary phosphonium salt in the above solution preparation step is 40:60~ 95:5. [8] The method according to any one of items 1 to 7, wherein the aprotic polar solvent is dimethylstyrene. [9] The method as described in any one of items 1 to 8, wherein the above-mentioned quaternary ammonium salt is selected from the group consisting of triethypentylammonium acetate, triethyhexylammonium acetate, triethyheptyl ammonium acetate, acetic acid At least one of the group consisting of triethyloctyl ammonium, triethynonylammonium acetate, and triethydecyl ammonium acetate, the above-mentioned quaternary phosphonium salt is selected from the group consisting of triethylpentylphosphonium acetate, acetic acid At least one of the group consisting of triethylhexylphosphonium, triethylheptylphosphonium acetate, and triethyloctylphosphonium acetate. [10] A polysaccharide fiber with a tensile strength of 1.6 cN/dtex or more, a coefficient of variation of the tensile strength of 10% or less, and a fibrillation degree of 170% or less. [11] The polysaccharide fiber as described in item 10, which is a continuous long fiber. [Effects of the invention]

According to the method for producing polysaccharide fibers of the present invention, polysaccharide fibers with less uneven physical properties and excellent skin feel can be obtained.

Hereinafter, exemplary aspects of the present invention will be described, but the present invention is not limited to these aspects. In the present invention, the upper limit and lower limit of each numerical range can be combined arbitrarily.

"Method for Manufacturing Polysaccharide Fiber" The manufacturing method of polysaccharide fiber of the present invention includes the following steps: The solution preparation step is to dissolve polysaccharides in a mixed solvent of an aprotic polar solvent and a quaternary ammonium salt and/or a quaternary phosphonium salt; The spraying step is to spray the prepared solution from the spinning nozzle in the form of fibers; and The solidification step is to solidify the sprayed fibers.

The polysaccharide fiber manufacturing method of the present invention may be a multifilament or monofilament manufacturing method, and may be a long fiber or short fiber manufacturing method. The manufacturing method of the polysaccharide fiber is preferably a long fiber manufacturing method, and more preferably a multifilament long fiber manufacturing method.

Long fibers in the present invention refer to those with a fiber length of 3 mm or more. The fiber length is preferably 5 mm or more, more preferably 10 mm or more. Regarding the fiber length, continuous long fibers are more preferred. The continuous long fibers mentioned here refer to continuous fibers with a length of more than 100 m. Compared with short fibers that are cut after spinning, long fibers have the following problems: they are prone to breakage during weaving or knitting due to fluffing, and they are prone to uneven dyeing due to uneven fiber diameters in the length direction. In order to prevent these problems, higher quality is required for long fibers. Therefore, a stable spinning technology that can suppress the occurrence of fluffing or fiber diameter unevenness is required.

[Solution preparation step] The manufacturing method of the polysaccharide fiber of the present invention includes a solution preparation step. In the solution preparation step, a mixed solvent of an aprotic polar solvent and a quaternary ammonium salt and/or a quaternary phosphonium salt (these are simply collectively referred to as "quaternary salts") is used to dissolve the polysaccharide to prepare a solution. In a mixed solvent of an aprotic polar solvent and a quaternary salt, from the viewpoint of dissolving polysaccharides well, the total content of the quaternary salt is based on the total mass of the mixed solvent, and is preferably 5 mass % or more. , more preferably 10% by mass or more, and still more preferably 15% by mass or more. From the viewpoint of not making the viscosity of the mixed solvent too high, the total content of the fourth-order salt is based on the total mass of the mixed solvent, and is preferably 60 mass % or less, more preferably 40 mass % or less, and further preferably 30 mass %. mass% or less. By setting the total content of the fourth-order salt to 5 mass % or more and 60 mass % or less, polysaccharides can be dissolved well and the viscoelasticity of the solution suitable for ejection can be ensured, so that continuous and stable spinning can be performed. Furthermore, regarding the solids among the quaternary salts, since the mixed solvent is in a liquid state, it must be mixed with a liquid aprotic polar solvent. If the total content of the fourth-order salts in the mixed solvent is 60% by mass or less, it can prevent the volume of the mixed solvent obtained in liquid form from becoming small and the viscosity of the mixed solvent from becoming too high, and the mixed solvent can be easily impregnated with polysaccharides. class raw materials. The total content of the fourth-grade salt is based on the total mass of the mixed solvent, and is preferably not less than 5% by mass and not more than 60% by mass, more preferably not less than 10% by mass and not more than 40% by mass, and still more preferably not less than 15% by mass and not more than 30% by mass. %the following.

The solvent for polysaccharides in this embodiment includes an aprotic polar solvent. Aprotic polar solvents are preferred because they do not hinder the interaction between quaternary ammonium salts and/or quaternary phosphonium salts and polysaccharides, and do not impair the solubility of polysaccharides. Examples of the aprotic polar solvent include trinity-based solvents, amide-based solvents, and pyridine-based solvents. Specific examples include: dimethylstyrene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidinone, N,N '-Dimethylpropamide, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, pyridine, and their derivatives. From the viewpoint of the solubility of polysaccharides, the aprotic polar solvent is particularly preferably dimethylsterine.

The content of the aprotic polar solvent in the mixed solvent is based on the total mass of the mixed solvent, and is preferably 40 mass% or more, more preferably 50 mass% or more, further preferably 60 mass% or more, and still more preferably More than 65% by mass. From the viewpoint of not making the viscosity of the mixed solvent too high, the content is preferably 95 mass% or less, more preferably 90 mass% or less, and further preferably 85 mass% or less, based on the total mass of the mixed solvent. More preferably, it is 82.5 mass % or less. This content can be selected considering the solubility of the polysaccharide or the solution physical properties of the obtained polysaccharide solution. The content of the aprotic polar solvent is based on the total mass of the mixed solvent, and is preferably not less than 40% by mass and not more than 95% by mass, more preferably not less than 50% by mass and not more than 85% by mass, and further preferably not less than 60% by mass and not more than 82.5% by mass. mass% or less, more preferably 65 mass% or more and 82.5 mass% or less.

In order to improve the solubility of polysaccharides and prevent the viscosity of the mixed solvent from being too high, the mass ratio of the aprotic polar solvent to the quaternary salt in the mixed solvent (aprotic polar solvent: quaternary salt) is relatively high. Preferably it is 40:60-95:5, more preferably 50:50-90:10, still more preferably 60:40-80:20, still more preferably 60:40-75:25.

The mixed solvent of the present invention includes any one or both of quaternary ammonium salts and quaternary phosphonium salts. The cation part of the quaternary ammonium salt and the quaternary phosphonium salt has two or more kinds of alkyl groups. "Two or more" alkyl groups means two or more alkyl groups that are bonded to the element in the cation center and have different carbon numbers, or two or more alkyl groups that are structural isomers although they have the same carbon number. By having two or more types of alkyl groups, the molecular skeleton of the cationic part becomes asymmetrical with respect to the cationic center, the diffusion coefficient of ions increases, and the solubility performance of the polysaccharide is improved. Thereby, a high-concentration solution can be utilized in the manufacturing process of the polysaccharide molded body. Furthermore, the solvent-removing property is improved when the solution in which polysaccharides are dissolved is brought into contact with a non-solvent to produce a molded article. This improves the step-by-step process of manufacturing polysaccharide shaped bodies.

In order for the cationic part to have sufficient hydrophobicity to interact with the hydrophobic surface of the polysaccharide, the total number of carbon atoms contained in the cationic part is preferably 11 or more. In order to moderately suppress hydrophobicity and improve the solubility of polysaccharides, the total number of carbon atoms in the cationic part is preferably 32 or less, more preferably 28 or less, further preferably 24 or less, still more preferably 20 or less. In addition, from the viewpoint of rapidly advancing the quaternary reaction that produces a quaternary ammonium salt and a quaternary phosphonium salt, the total number of carbon atoms in the cationic part is preferably 16 or less, more preferably 15 or less, and still more preferably 14 or less. The total number of carbon atoms in the cationic site is preferably 11 or more and 32 or less, more preferably 11 or more and 28 or less, still more preferably 11 or more and 24 or less, still more preferably 11 or more and 20 or less, particularly preferably 11 or more and 16 or less, especially preferably 11 or more and 16 or less. It should be between 11 and 15, preferably between 11 and 14.

The smaller the carbon number of the alkyl group, the smaller the size of the cationic skeleton, and the easier it is to approach the molecular chain of the polysaccharide. Therefore, the carbon number _CS of the alkyl group with the smallest carbon number in the cationic part is preferably 4 or less, and more preferably It is preferably 3 or less, and more preferably 2 or less. The lower limit of C _S is above 1 or above 2. On the other hand, if the number of alkyl chains (methyl) with a carbon number of 1 increases, the interaction between cations and anions becomes stronger, and the solubility of quaternary ammonium salts and quaternary phosphonium salts in aprotic polar solvents may decrease. The solubility of polysaccharides is reduced. Therefore, the number of methyl groups is preferably 3 or less, more preferably 2 or less. From the viewpoint of suppressing the aggregation of cations due to Van der Waals forces between alkyl chains, the carbon number C _L of the alkyl group with the largest number of carbon atoms in the cation part is preferably 12 or less, more preferably 10 or less, and further Preferably it is 8 or less, More preferably, it is 5 or less. The lower limit of _CL is 2 or more, preferably 3 or more. From the viewpoint of providing asymmetry in the number of carbon atoms in the cationic part, the value C _L /C _S obtained by dividing _CL of the cationic part by C _S is preferably more than 1, more preferably more than 2. Moreover, from the viewpoint of not excessively increasing hydrophobicity, _CL /C _S is preferably 10 or less, more preferably 8 or less, and still more preferably 5 or less. C _L /C _S is preferably more than 1 and less than 10, more preferably more than 1 and less than 8, still more preferably more than 1 and less than 5, or, preferably more than 2 and less than 10, still more preferably It is more than 2 and 8 or less, and it is more preferable that it is more than 2 and 5 or less.

The alkyl group constituting the cationic part may have a linear structure, a branched chain structure, or a cyclic structure. In addition, the alkyl chain may contain an ether bond or a thioether bond, and the terminal may have functional groups such as a hydroxyl group, a thiol group, and an amino group. Alkyl groups are preferably straight-chain structures consisting only of carbon and hydrogen. The number of types of alkyl groups may be 2 or more and 4 or less. From the viewpoint of the ease of obtaining raw materials, in one aspect, the types of alkyl groups are 2 types (alkyl groups with carbon number C _S and alkyl groups with carbon number C _L ). The number of alkyl groups having carbon number C _S is preferably 3 or less, more preferably 2 or less, and may be 1. From the viewpoint of suppressing the diffusion coefficient and the aggregation of cations, the number of alkyl groups having carbon number C _L is preferably 3 or less, more preferably 2 or less, and may be 1. More preferably, the number of one of the alkyl groups having carbon numbers C _S and C _L is 1, and the number of the other is 3.

The quaternary ammonium cation is preferably selected from the group consisting of triethypentylammonium (TEPenA), triethyhexylammonium (TEHexA), triethyheptylammonium (TEHepA), and triethyloctyl ammonium (TEOA). At least one of the group consisting of , triethylnonylammonium (TENA), and decyltriethylammonium (DTEA). Among them, a particularly preferred one is one selected from the group consisting of triethypentylammonium (TEPenA), triethyhexylammonium (TEHexA), triethyheptylammonium (TEHepA), and triethyloctyl ammonium (TEOA). At least one of them. The quaternary phosphonium cation is preferably selected from the group consisting of triethylpentylphosphonium (TEPenP), triethylhexylphosphonium (TEHexP), triethylheptylphosphonium (TEHepP), triethyloctylphosphonium (TEOP), At least one of the group consisting of triethylnonylphosphonium (TENP) and decyltriethylphosphonium (DTEP). Among them, a particularly preferred one is one selected from the group consisting of triethylpentylphosphonium (TEPenP), triethylhexylphosphonium (TEHexP), triethylheptylphosphonium (TEHepP), and triethyloctylphosphonium (TEOP) At least one of them.

The anion part of the quaternary ammonium salt and the quaternary phosphonium salt is a carboxylate anion. Carboxylate anions improve the solubility of polysaccharides and do not corrode metals, so they are suitable for dissolving or forming polysaccharides. From the viewpoint of dissolution of polysaccharides, the carboxylate anion is preferably at least one selected from the group consisting of formate anion, acetate anion, propionate anion, and methoxyacetate anion. Among them, the acetate anion is particularly preferable because it improves the solubility of polysaccharides.

Specific examples of the quaternary ammonium salt include those selected from the group consisting of tributylmethylammonium acetate, tributylethylammonium acetate, ethyltripropylammonium acetate, triethypentylammonium acetate, and decyltriethyl acetate. methyl ammonium, dodecyl triethylammonium acetate, tributyldecyl ammonium acetate, methyl trioctyl ammonium acetate, butyl trioctyl ammonium acetate, dibutyl diethylammonium acetate, decyl diacetate The group consisting of ethyl methyl ammonium, tributyl methyl ammonium methoxyacetate, triethylhexylammonium acetate, triethyheptyl ammonium acetate, triethyloctyl ammonium acetate, and triethyl nonylammonium acetate At least one of them. As the quaternary ammonium salt, a more preferred example is selected from the group consisting of triethypentylammonium acetate, triethyhexylammonium acetate, triethyheptylammonium acetate, triethyloctyl ammonium acetate, and triethynonyl acetate. At least one of the group consisting of ammonium and decyltriethylammonium acetate. Specific examples of the quaternary phosphonium salt include those selected from the group consisting of tributylmethylphosphonium acetate, tributylethylphosphonium acetate, ethyltripropylphosphonium acetate, triethylpentylphosphonium acetate, and decyltriethyl acetate. Phosphonium acetate, dodecyltriethylphosphonium acetate, tributyldecylphosphonium acetate, methyltrioctylphosphonium acetate, butyltrioctylphosphonium acetate, dibutyldiethylphosphonium acetate, decyldiacetate The group consisting of ethylmethylphosphonium, tributylmethylphosphonium methoxyacetate, triethylhexylphosphonium acetate, triethylheptylphosphonium acetate, triethyloctylphosphonium acetate, and triethylnonylphosphonium acetate At least one of them. As the quaternary phosphonium salt, a more preferred example is one selected from the group consisting of triethylpentylphosphonium acetate, triethylhexylphosphonium acetate, triethylheptylphosphonium acetate, and triethyloctylphosphonium acetate. At least one.

Typical examples of polysaccharides include cellulose. Examples of cellulose raw materials include microcrystalline cellulose, so-called wood pulp such as softwood pulp and hardwood pulp, and non-wood pulp. Examples of non-wood pulp include cotton-derived pulp such as cotton linters, hemp-derived pulp, bagasse-derived pulp, kenaf-derived pulp, bamboo-derived pulp, and straw-derived pulp. Pulp. Pulp derived from cotton, pulp derived from hemp, pulp derived from sugarcane bagasse, pulp derived from kenaf, pulp derived from bamboo, and pulp derived from straw respectively refer to the use of lint, cotton linters, and linen. Raw materials such as abaca (for example, most of them are produced in Ecuador or the Philippines), sisal, bagasse, kenaf, bamboo, straw, etc., have been delignified by cooking to remove hemicellulose. The refined pulp obtained by the refining step and the bleaching step. In addition, refined products such as seaweed-derived cellulose and ascidian cellulose can also be used as cellulose raw materials.

The concentration of the cellulose raw material in the mixed solvent is preferably 20 mass% or less, and more preferably 15 mass% or less based on the mass of the entire solution to be prepared, from the viewpoint of ensuring a homogeneous dissolved state. From the viewpoint of reducing the amount of solvent used and ensuring the spinnability or the strength of the fiber, the concentration of the cellulose raw material in the mixed solvent is preferably 3 mass% or more, more preferably 4.5 mass% or more. The concentration of the cellulose raw material in the mixed solvent is preferably not less than 3% by mass and not more than 20% by mass, and more preferably not less than 4.5% by mass and not more than 15% by mass.

The solvent for polysaccharides in the present invention can also dissolve polysaccharides other than cellulose. Examples of polysaccharides other than cellulose include xylan, glucomannan, α-1,4-glucan, α-1,3-glucan, and β-1,3-glucan. Polysaccharides (cardranan, paramylon), pullulan, chitin, chitosan, etc.

Regarding the order of inputting raw materials in the above-mentioned solution preparation step using a mixed solvent, the following (1) or (2) can be exemplified: (1) Prepare a mixed solvent of an aprotic polar solvent and a quaternary ammonium salt and/or a quaternary phosphonium salt, and then add polysaccharides to the mixed solvent; (2) Add polysaccharides to the aprotic polar solvent to swell the polysaccharides, and then add quaternary ammonium salts and/or quaternary phosphonium salts; From a practical point of view, it is preferable to use the method (1) in which the quaternary salt and the aprotic polar solvent are mixed with a solvent by recovering the solvent in the following method for producing a polysaccharide molded article. State recovery allows the mixed solvent to be reused.

The solution temperature in the above solution preparation step can be 20°C or above, and from the viewpoint of dissolving the polysaccharides uniformly in a short time, it is particularly preferably 50°C or above. From the viewpoint of reducing energy costs in solution preparation, the temperature is preferably below 90°C, and particularly preferably below 85°C. The solution temperature in the solution preparation step is preferably above 20°C and below 90°C, more preferably above 50°C and below 85°C.

The device used in the above solution preparation step is not particularly limited. Examples of the device include a magnetic stirrer, a microwave device, a single-shaft mechanical stirrer, a double-shaft planetary mixer, and a kneader. If the polysaccharide concentration in the solution is high, the viscosity of the solution will become high. Therefore, from the viewpoint of uniformly stirring the high-viscosity solution, devices with a biaxial mechanism such as a planetary mixer or a kneader are particularly preferred.

The moisture content in the mixed solvent in the above solution preparation step is based on the total mass of the mixed solvent, and is preferably 7% by mass or less, more preferably 6.5% by mass or less, and even more preferably 5% by mass or less. When the moisture content in the mixed solvent is 7% by mass or less, the interaction between the quaternary ammonium salt and the quaternary phosphonium salt and the polysaccharide is good, and the solubility is excellent.

From the viewpoint of the spinnability of the fiber, the moisture content in the solution prepared through the above solution preparation step is based on the total mass of the solution, and is preferably 8 mass% or less, more preferably 5 mass% or less, and further The content is preferably 4% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less. By suppressing the moisture content in the solution to 8% by mass or less, the viscoelasticity and fluidity of the solution suitable for spraying can be ensured, allowing continuous and stable spinning. Based on the energy load in drying the solvent and raw materials before solution preparation, the moisture content of the solution is based on the total mass of the solution, and is preferably 0.05 mass% or more, and more preferably 0.1 mass% or more. Furthermore, if the solution prepared by the above solution preparation step is directly used in the ejection and solidification steps, the moisture content of the solution prepared by the solution preparation step corresponds to the moisture content of the solution during ejection in the molding step. . The moisture content of the solvent during the ejection and solidification steps can be adjusted by adjusting the humidity of the raw materials used in the solution preparation step. The moisture content in the solution prepared by the solution preparation step is based on the total mass of the solution, and is preferably 0.05 mass% or more and 8 mass% or less, more preferably 0.05 mass% or more and 5 mass% or less, and further preferably 0.05 mass% or more and 5 mass% or less. 0.05 mass % or more and 4 mass % or less, and more preferably 0.05 mass % or more and 3 mass % or less.

Since the solution used in the above solution preparation step has excellent smoothness, in the production of fibers, especially the production of continuous long fibers, it is possible to suppress uneven physical properties of the fibers obtained and provide an excellent skin feel. The smoothness mentioned here refers to the smooth touch.

[Spraying step] The method of manufacturing polysaccharide fibers of the present invention includes a spraying step, which is to spray the solution prepared by the above solution preparation step from the spinning nozzle in the form of fibers. In the spraying step, the solution obtained in the above solution preparation step is sprayed in the form of fibers through the spinning nozzle. The spinning nozzle can be a multifilament spinning nozzle or a monofilament spinning nozzle, just choose appropriately. In the case of multifilament, the number of holes is not particularly limited and can be selected according to the purpose. The temperature of the solution when sprayed can be selected based on the balance between spinnability and viscoelasticity. However, from the viewpoint of ensuring the spinnability of the sprayed solution, it is preferably 40°C or higher, and more preferably 50°C or higher. .

As described below, the ejected fibers are brought into contact with the coagulating liquid to be coagulated. An air gap is provided between the spinning nozzle and the coagulating liquid, more specifically, between the spinning nozzle surface and the coagulating liquid surface. From the viewpoint of ensuring the independence of the sprayed solution in the air gap, the temperature during spraying is preferably 90°C or lower, more preferably 85°C or lower. The discharge speed can be appropriately selected based on the required winding speed and fiber properties.

Since the solution prepared through the solution preparation step will solidify rapidly due to contact with the coagulation liquid, it is preferable to extend the fiber in the air gap (after being sprayed and before contact with the coagulation liquid). By stretching between air gaps, defects in the fiber structure can be reduced compared to stretching the coagulated fiber, and fibers with excellent strength and elongation can be obtained.

From the viewpoint of sufficient extension between the air gaps, the length from the spinning nozzle to the coagulation liquid (air gap length) is preferably 1 mm or more, and more preferably 2.5 mm or more. From the viewpoint of suppressing the adhesion of the filaments between the air gaps, the air gap length is preferably 75 mm or less, more preferably 50 mm or less. Generally, if the length of the air gap is made shorter, the tension on the filament increases rapidly, which may cause single filament breakage or a decrease in the draw ratio of the fiber. On the other hand, since the solution of the present invention will solidify rapidly due to contact with the coagulating liquid, the thread can withstand the increase in tension, so the air gap length can be set shorter than in general. For this reason, from the viewpoint of continuous stable spinning or reduction of uneven physical properties, the air gap length in the present invention is preferably 30 mm or less, more preferably 20 mm or less. The air gap length is preferably not less than 1 mm and not more than 75 mm, more preferably not less than 2.5 mm and not more than 50 mm, further preferably not less than 2.5 mm and not more than 30 mm, still more preferably not less than 2.5 mm and not more than 20 mm.

The polysaccharide fiber manufacturing method of the present invention can further suppress ejection defects such as single filament breakage or filament bending by controlling the humidity in the air gap. In a high-humidity environment, local solidification of the ejected yarn or condensation on the surface of the spinning nozzle may sometimes lead to the following ejection defects, that is, the nozzle is clogged, gelatinous material is produced, single filament breaks, and/or the inability to fully perform its extension. From the viewpoint of fully suppressing the ejection failure as described above, the relative humidity between the air gaps is preferably 90% or less, more preferably 85% or less, and still more preferably 80% or less. From this point of view, a lower limit should not be set, but realistically, the lower limit is preferably at least 10%. The relative humidity between the air gaps is preferably not less than 10% and not more than 90%, more preferably not less than 10% and not more than 85%, and still more preferably not less than 10% and not more than 80%.

The method of controlling the humidity in the air gap is not particularly limited, but examples include a method of controlling the atmosphere of the surrounding environment by surrounding the air gap with a humidity adjustment booth, a method of blowing dry air into the air gap, and the like.

From the viewpoint of the spinnability of the fiber, the moisture content in the solution in the ejection step is based on the total mass of the solution, and is preferably 8 mass% or less, more preferably 5 mass% or less, and further preferably 4 mass%. % or less, preferably 3 mass% or less, particularly preferably 2 mass% or less. By suppressing the moisture content in the solution to 8% by mass or less, the viscoelasticity and fluidity of the solution suitable for spraying can be ensured, allowing continuous and stable spinning. Based on the energy load in drying the solvent and raw materials before solution preparation, the moisture content of the solution is based on the total mass of the solution, and is preferably 0.05 mass% or more, and more preferably 0.1 mass% or more. Furthermore, if the solution prepared by the above solution preparation step is directly used in the spraying step, the moisture content of the solution prepared by the solution preparation step corresponds to the moisture content of the solution in the spraying step. The moisture content of the solution in the spraying step can be adjusted by adjusting the humidity of the raw materials used in the solution preparation step. In particular, in order to reduce the water content to 2% by mass or less, it is necessary to dry an aprotic polar solvent using a dehydrating agent such as molecular sieve, and to dry quaternary salts and polysaccharide raw materials by heating and/or reducing pressure. Any kind of drying process. The water content in the solution in the spraying step is based on the total mass of the solution, and is preferably 0.05 mass% or more and 8 mass% or less, more preferably 0.05 mass% or more and 5 mass% or less, and still more preferably 0.05 mass% or more. 4 mass% or less, preferably 0.05 mass% or more and 3 mass% or less, particularly preferably 0.05 mass% or more and 2 mass% or less.

[Coagulation step] The method for producing polysaccharide fibers of the present invention includes a coagulation step in which the fibers ejected by the above ejection step are brought into contact with a coagulating liquid to solidify. The coagulation liquid is not particularly limited as long as it is not a solvent for polysaccharides and can be mixed with the above-mentioned mixed solvent. As the coagulation liquid, water, alcohol, and a mixed liquid of one or more of these and the above mixed solvent can be used. Preferably, the fibers are impregnated and ejected into an aqueous coagulation bath containing water and the above mixed solvent. Since quaternary ammonium salts and quaternary phosphonium salts have high solubility in water, desolvation and coagulation can be performed efficiently by using an aqueous coagulation liquid. The temperature of the coagulation liquid is preferably 15°C or higher, more preferably 18°C or higher, from the viewpoint of the efficiency of removing solvent from the solution. From the viewpoint of reducing energy load, the temperature is preferably 60°C or lower, and more preferably 50°C or lower. The temperature of the coagulating liquid is preferably 15°C or more and 60°C or less, more preferably 18°C or more and 50°C or less.

The coagulation bath can be a static bath or a flowing bath. When setting up an air gap in the ejection step, in order to reduce the resistance when the filament enters the coagulation liquid from the air gap, it is better to use a flow bath. From the viewpoint of suppressing rapid coagulation, the content of the above-mentioned mixed solvent in the coagulation liquid is preferably 1.5 mass% or more, and more preferably 3 mass% or more. From the viewpoint of fully coagulating the fibers in the coagulation step, the content of the mixed solvent in the coagulation liquid is preferably 50 mass% or less, more preferably 45 mass% or less, and still more preferably 40 mass% or less. The content of the above-mentioned mixed solvent in the coagulation liquid is preferably 1.5 mass% or more and 50 mass% or less, more preferably 3 mass% or more and 45 mass% or less, and further preferably 3 mass% or more and 40 mass% or less.

Since the quaternary ammonium salt and quaternary phosphonium salt of the present invention have an asymmetric cationic skeleton, the diffusion coefficient is relatively large. In addition, since the above-mentioned mixed solvent contains an aprotic polar solvent, its viscosity is low. Therefore, when the above solution is brought into contact with a non-solvent, coagulation proceeds smoothly. Furthermore, even when the ratio of the above-mentioned mixed solvent contained in the coagulation liquid is increased, coagulation proceeds sufficiently, which is advantageous in this regard. This can also reduce the amount of water used in the molding process.

[Wash step] The method of manufacturing the polysaccharide fiber of the present invention preferably includes a washing step, which is to remove the above-mentioned mixed solvent from the coagulated fiber by washing with water. In this step, the mixed solvent remaining in the fiber coagulated in the coagulation step is removed by washing with water. The refining method is not particularly limited, and examples include a refining bath, a washing drum, and the like. Regarding the temperature of the water used for washing, from the viewpoint of washing efficiency, it is preferably 15°C or higher, and more preferably 18°C or higher. From the viewpoint of reducing energy load, the temperature is preferably 60°C or lower, and more preferably 50°C or lower. The temperature of the water used for washing is preferably between 15°C and below 60°C, more preferably between 18°C and below 50°C.

[Drying Step] The method for producing the polysaccharide fiber of the present invention preferably includes a drying step, which is to dry the washed fiber. In this step, the fibers from which the mixed solvent has been removed by the washing step are dried. The drying method is not particularly limited, and examples include a hot air dryer, a contact dryer, and a radiation dryer. If the fibers are dried using a contact dryer, the surface of the fibers will be damaged and the fibers will be damaged. Therefore, from the viewpoint of suppressing this, a hot air dryer that can dry the fibers in a non-contact manner is particularly preferred. Regarding the drying temperature, from the viewpoint of drying efficiency, it is preferably 60°C or higher, and more preferably 70°C or higher. From the viewpoint of reducing energy load and preventing deterioration of cellulose fibers, the temperature is preferably 200°C or lower, more preferably 180°C or lower, and still more preferably 170°C or lower. Drying can be performed continuously on the fiber after the washing step, or it can be performed on the fiber that is temporarily rolled up in an undried state after washing. The drying temperature is preferably not less than 60°C and not more than 200°C, more preferably not less than 70°C and not more than 180°C, still more preferably not less than 70°C and not more than 170°C.

[Solvent Recovery Step] The method of manufacturing the polysaccharide fiber of the present invention preferably includes a solvent recovery step, which is to recover the solvent mixed in the coagulating liquid and the cleaning liquid. In this step, the solvent mixed in the coagulation liquid and the cleaning liquid is recovered through methods such as distillation, membrane separation, atomization separation, etc. By implementing high-efficiency solvent recovery, the discharge of solvent components into the environment can be suppressed, and the environmental load can be kept to an extremely low level. Furthermore, the process includes a step of using a polymer adsorbent to remove polysaccharides remaining in the coagulation bath, a step of using activated carbon to remove coloring components, and a step of using electromagnetic separation to remove metal components eluted from raw materials or pipes. , enabling solvent recovery with higher purity.

"Polysaccharide fiber" According to the manufacturing method of polysaccharide fiber of the present invention, a polysaccharide fiber with a tensile strength of 1.6 cN/dtex or more and a fibrillation degree of 170% or less can be provided. The polysaccharide fiber having the above-mentioned physical properties can be obtained by the above-mentioned manufacturing method of polysaccharide fiber. The polysaccharide fiber obtained by the polysaccharide fiber manufacturing method of the present invention can preferably be used directly without going through a spinning step. Therefore, the shape and other characteristics of the fiber itself can be effectively utilized. In addition, fibers with smooth and shiny fiber surfaces can be obtained. Therefore, the polysaccharide fiber is preferably a long fiber, and more preferably a continuous long fiber.

The tensile strength of the polysaccharide fiber of the present invention is 1.6 cN/dtex or more. The higher the tensile strength, the stronger the thread, which is less likely to break during the dyeing step and processing into fabrics, and improves the yield, so it is preferable. If the tensile strength is 1.6 cN/dtex or more, the specific effect in the subsequent steps is that it can withstand the stretching of the thread when producing a fine-structured fabric in the weaving step.

The tensile strength of the polysaccharide fiber of the present invention is preferably 1.8 cN/dtex or more, more preferably 2.0 cN/dtex or more, further preferably 2.2 cN/dtex or more, particularly preferably 2.5 cN/dtex or more. Since a higher value is better, an upper limit should not be set, but a realistic upper limit is preferably 5 cN/dtex or less. The tensile strength of the polysaccharide fiber is preferably 1.6 cN/dtex or more and 5 cN/dtex or less, more preferably 1.8 cN/dtex or more and 5 cN/dtex or less, more preferably 2.0 cN/dtex or more and 5 cN/dtex or less. Furthermore, it is more preferable that it is 2.2 cN/dtex or more and 5 cN/dtex or less, and it is especially preferable that it is 2.5 cN/dtex or more and 5 cN/dtex or less.

The elongation rate of the polysaccharide fiber of the present invention is preferably 7% or more. The greater the elongation, the less broken wires will be when tension is applied to the threads during the weaving step, allowing for fine processing. Furthermore, it is preferable to use the fabric for clothing because the wearing experience will be improved. The elongation of the long fiber of the present invention is preferably 8% or more, more preferably 10% or more, and further preferably 15% or more. Since the higher the value, the better, there should be no upper limit, but a realistic upper limit is preferably 30% or less. The elongation rate of the polysaccharide fiber is preferably from 7% to 30%, preferably from 8% to 30%, more preferably from 10% to 30%, and further preferably from 15% to 30%.

The yarn unevenness of the polysaccharide fiber of the present invention is preferably 12% or less, more preferably 10.5% or less, and further preferably 9% or less. In the present invention, "thread unevenness" means the coefficient of variation of tensile strength. The smaller the unevenness of the threads, the smoother the fiber obtained and the better the skin feel, and the more uniform dyeing can be performed. Since a lower value is better, a lower limit should not be set, but realistically, the lower limit is preferably at least 0.1%. The yarn unevenness of the polysaccharide fiber is preferably 0.1% or more and 12% or less, more preferably 0.1% or more and 10.5% or less, and further preferably 0.1% or more and 9% or less.

The degree of fibrillation of the polysaccharide fiber of the present invention is preferably 170% or less, more preferably 150% or less, further preferably 120% or less, especially 100% or less. The lower the degree of fibrillation, the more likely it is to suppress whitening when the fibers are made into fabrics. Furthermore, since fluffing can be suppressed, the step-by-step during weaving or knitting is improved. Since the lower the value, the better, a lower limit should not be set, but realistically, the lower limit is preferably at least 1%. The degree of fibrillation of the polysaccharide fiber is preferably 1% or more and 170% or less, more preferably 1% or more and 150% or less, still more preferably 1% or more and 120% or less, still more preferably 1% or more and 100% or less .

The polysaccharide fiber of the present invention has suppressed fibrillation and has excellent skin touch, so it can be preferably used for clothing applications such as dresses or dress linings, functional underwear or ethnic wear, or for home use such as bedding or towels. Textile uses, and accessories such as ties or scarves. [Example]

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. In addition, various physical properties were measured by the following methods.

"Measurement and Evaluation Methods" [Smoothness of Solution] The smoothness of the solution is evaluated by the following method. Pick up the obtained solution about 3 cm with a spatula and stretch it into a filament shape, and judge the feeling felt by the hand using the spatula based on the following criteria. As a negative control group, a mixed solvent before dissolving the polysaccharide as a solute was used. 5: Same as the control group, no resistance was felt. 3: Compared with the control group, resistance was felt. 1: Compared with the control group, great resistance was felt. Three men and seven women aged 25 to 60 years old conducted the above measurement with three repetitions. Based on the average score of each subject, the average score of all subjects was taken as the smoothness of the solution. cisgender. The smoothness mentioned here refers to the smooth touch.

[Relative humidity of the air gap] The relative humidity of the air gap is measured by the following method. That is, a digital temperature/humidity meter (EX-502) from Empex Instruments Co., Ltd. was used to measure the temperature and humidity of the laboratory environment. Also, bring the probe close to the air gap, and measure the temperature and humidity between the air gaps at a position of 5 mm above the coagulation liquid surface and 2 mm away from the spinning nozzle holder in the horizontal direction.

[Fineness] The obtained polysaccharide fiber is placed in an atmosphere of room temperature 23°C and humidity 50%RH, and the humidity is adjusted overnight in a relaxed stretching state. Cut out a 1 m humidity-adjusted sample, measure the weight at 10 locations, and multiply the average number by 10,000 to determine the fineness (dtex) of the sample.

[Strength and elongation of fiber] The strength and elongation of polysaccharide fiber were measured using A&D Co., Ltd.'s tensile universal testing machine (RTG-1250) and a load cell of 50 N, in accordance with JIS L 1013: 2010, 8.5.1 (Standard time test), measured by the following method. That is, the polysaccharide fiber was attached to the gripping part of the testing machine in a relaxed stretched state, and a tensile test was performed with a gripping interval of 30 cm and a stretching speed of 30 cm/min. Measure the load and elongation when the sample breaks at 10 places, calculate its strength and elongation respectively according to the following formulas, and use the numerical average as the strength (average strength) and elongation of the sample. In addition, when the breaking strength is less than the strength at the highest load, the strength at the highest load and the elongation at that time are measured. Strength (cN/dtex) = strength at break or strength at maximum load (cN)/density of the sample (dtex) Elongation (%) = elongation at break or elongation at maximum load (mm)/grabbing interval (mm)

[Unevenness of threads] Calculate unevenness of threads (coefficient of variation of strength) by dividing the standard deviation of the strength measured in the above [Strength and elongation of fibers] by the above-mentioned average strength.

[Moisture content] The moisture content of the solution was measured twice using the Kyoto Electronics Co., Ltd. Karl Fischer Moisture Meter MKC-520 by amperometric titration, and the quantitative average was calculated.

[Degree of fibrillation] Cut the obtained polysaccharide fiber into a fiber length of 3 mm to prepare a short fiber sample. 0.2 g of short fiber sample was dispersed in 3 mass% sulfuric acid aqueous solution (51 g), immersed at 70°C for 30 minutes, and then washed with 600 mL of water. Disperse the above acid-treated short fiber sample in 300 g of water and stir it with a household mixer for 30 minutes to perform fibrillation treatment. The aqueous dispersion of the fibrillated short fiber sample was cast on a silicon substrate, a cover glass was installed, and a digital microscope (manufactured by Lasertec Co., Ltd.) was used for observation in 5 fields of view at a magnification of 185 times. The obtained image was converted into grayscale using the program CV2 using the Python language, and then binarized using the Otsu method. Calculate the area by setting the area corresponding to the fiber (including the fibril part) as black, and use the calculated area as the total area occupied by the fiber before fibrillation in an image (A1) and the area occupied by the fiber after fibrillation. The total area (A2) occupied in an image is used to calculate the degree of fibrillation using the following formula. Degree of fibrillation (%)={(A2-A1)/A1}×100

[Spinnability] After starting to wind up the filament at the winding speed of the following Examples and Comparative Examples, the number of single filament breaks within 10 minutes was visually measured, and the spinnability was evaluated based on the following criteria. A: No broken wires. B: There are broken wires (1 to 2 times/10 minutes). C: There are broken wires (more than 3 times/10 minutes).

[Sensory test on skin touch] Cut the polysaccharide fiber obtained into a length of 100 cm, and combine 10 fibers into a bundle. Wrap one end with Cellophane (registered trademark) tape and hold it in your right hand. Gently pinch the bundled side (the end of Cellophane (registered trademark) tape) with the index finger and thumb of your left hand, fix it with your left hand, and pull out the silk thread at a speed of 1 m per minute with your right hand. Judge what you feel in your left hand according to the following criteria. feel. As a negative control group, Bemberg (registered trademark) was used. 5: Extremely smooth compared to the control group. 3: Very smooth compared to the control group. 1: Smoother than the control group. Three men and seven women aged 25 to 60 years old conducted the above measurement three times. Based on the average of the scores of each subject, the average of the scores of all subjects was taken as the skin feel. .

[Sensory test of elasticity of fiber] Cut the obtained polysaccharide fiber into a length of 100 cm, and combine 10 fibers into a bundle. Pinch both ends with the index finger and thumb of your right hand, and grasp the center of the arc with the index finger and thumb of your left hand. Use the following criteria to determine the feeling you feel when you rub your fingers together. As a negative control group, Bemberg (registered trademark) was used. 5: Compared with the control group, it has a strong sense of elasticity. 3: Compared with the control group, it has a very strong sense of elasticity. 1: Compared with the control group, there is a sense of elasticity. Three men and seven women aged 25 to 60 years old conducted the above measurement three times. Based on the average of the scores of each subject, the average of the scores of all subjects was taken as the elasticity of the fiber. The elasticity mentioned here refers to the feeling of elasticity and firmness.

"Manufacture of Materials" [Fourth-grade ammonium salt and fourth-grade phosphonium salt] (Manufacturing Example 1) Acetonitrile (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.) (100 g) and tributylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) (102.2 g, 0.54 mol) were added to a 500 mL three-necked flask, and the process was carried out at 80°C. Stir. Methyl iodide (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.) (85.7 g, 0.6 mol) was added thereto, and the mixture was stirred under reflux at 80° C. for 9 hours. The solvent was distilled off under heating and reduced pressure conditions to obtain tributylmethylammonium iodide (TBMAI) (173.2 g, 0.53 mol, 98%) as a light yellow solid. TBMAI (49.1 g, 0.15 mol) was added to a 1 L two-necked flask, and dissolved in a 1/9 (mass ratio) mixed solution (200 g) of water/ethanol (manufactured by Kanto Chemical Co., Ltd.). At room temperature, while stirring, add ion exchange resin Amberlite IRN78 (300 g) obtained from Sigma-Aldrich, stir for 6 hours, and let it stand overnight. Amberlite was separated by filtration using a glass filter and washed with ethanol. Acetic acid (Fuji Film Wako Pure Chemical Industries, Ltd.) dissolved in ethanol (30 mL) was added dropwise to the solution obtained using a dropping funnel over 1 hour. (manufactured by our company) (9.0 g, 0.15 mol), stir at room temperature for 6 hours, and then let it stand overnight. After passing the reaction solution through an alkaline alumina column, ethanol and water were distilled off under heating and reduced pressure conditions to obtain tributylmethylammonium acetate (TBMAA) (37.1 g, 0.143 mol, Total yield 95%).

(Manufacturing example 2) Except using ethyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of methyl iodide, tributyl ethylammonium acetate (TBEAA) (TBEAA), which is a white solid state at room temperature, was obtained in the same manner as in Production Example 1. Total yield 96%).

(Manufacture example 3) Except using tripropylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of tributylamine, ethyl tripropylammonium acetate (ethyl tripropylammonium acetate) in a white solid state at room temperature was obtained in the same manner as in Production Example 2. ETPAA) (overall yield 97%).

(Manufacturing Example 4) The procedure was the same as Production Example 1 except that triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of tributylamine, and 1-bromopentane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of methyl iodide. Triethypentylammonium acetate (TEPenAA) was obtained in a yellow liquid state at room temperature (total yield 97%).

(Manufacturing Example 5) Decyltriethyl acetate in an orange solid state at room temperature was obtained in the same manner as in Production Example 4 except that 1-bromodecane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1-bromopentane. Ammonium (DTEAA) (overall yield 96%).

(Manufacturing Example 6) Dodecyl acetate which was an orange solid state at room temperature was obtained in the same manner as in Production Example 4 except that 1-bromododecane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1-bromopentane. Triethylammonium (DDTEAA) (overall yield 92%).

(Manufacturing Example 7) Tributyldecyl ammonium acetate (TBDAA) in a brown liquid state at room temperature was obtained in the same manner as in Production Example 1 except that 1-bromodecane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of methyl iodide. ) (total yield 98%).

(Manufacture example 8) Methyl trioctyl ammonium acetate in a yellow transparent liquid state at room temperature was obtained in the same manner as in Production Example 1 except that trioctylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of tributylamine. (MTOAA) (overall yield 99%).

(Manufacture Example 9) Except using 1-bromobutane (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of methyl iodide, butyl trioctyl ammonium acetate (butyl trioctyl ammonium acetate) in a yellow transparent liquid state at room temperature was obtained in the same manner as in Production Example 8. BTOAA) (overall yield 99%).

(Manufacturing Example 10) Dibutyldiacetate which was a white solid state at room temperature was obtained in the same manner as in Production Example 9 except that N,N-diethylbutylamine obtained from Sigma-Aldrich was used instead of trioctylamine. Ethylammonium (DBDEAA) (overall yield 95%).

(Manufacturing Example 11) Decyl acetate that was an orange solid state at room temperature was obtained in the same manner as in Production Example 5, except that N,N-diethylmethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of triethylamine. diethylmethylammonium (DDEMAA) (overall yield 95%).

(Manufacture Example 12) The same production examples were used except that triethylphosphine obtained from Fujifilm Wako Pure Chemical Industries, Ltd. was used instead of tributylamine, and 1-bromooctane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of methyl iodide. 1 Triethyloctylphosphonium acetate (TEOPA), which is liquid at room temperature, was obtained in the same manner (total yield 95%).

(Manufacturing Example 13) Except using methoxyacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of acetic acid, tributylmethylammonium methoxyacetate (TBMA (OMe) in a liquid state at room temperature was obtained in the same manner as in Production Example 1 )A) (Total yield 92%).

(Manufacture Example 14) In the same manner as in Production Example 2, tributylethylammonium bromide (TBEAB) in a white solid state at room temperature was obtained (yield 99%).

(Manufacturing Example 15) Triethylpropyl chloride in a white solid state at room temperature was obtained in the same manner as in Production Example 4 except that 1-chloropropane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1-bromopentane. Ammonium (TEProAC) (overall yield 97%).

"Manufacture of Polysaccharide Fiber" [Example 1] Heat-treated molecular sieve 3A (manufactured by Kanto Chemical Co., Ltd.) was added to dimethyl styrene (DMSO) (manufactured by Kanto Chemical Co., Ltd.), stirred and allowed to stand. Leave it overnight to dehydrate. Furthermore, the tributylmethylammonium acetate (TBMAA) of Production Example 1 was dried by stirring at 105° C. for 5 hours under vacuum. After returning to room temperature, it was allowed to stand overnight under vacuum.

Mix the above-mentioned dried DMSO and TBMAA in a mass ratio of 75:25, and use cotton linters pulp as natural cellulose, and dry the cotton linters pulp at 105°C for 1 hour to obtain a mass of 5 % is immersed in the above mixed solvent to obtain a mixture. Using a planetary mixer (manufactured by Primix Co., Ltd.), the above mixture was stirred at 30° C. and 50 rpm for 1 hour to fully impregnate the cellulose with the mixed solvent. The temperature was raised to 80°C and stirred for 7 hours to obtain a solution (500 g in total) of cellulose uniformly dissolved in the above mixed solvent. The moisture content of the solution was 2% by mass, and this value was taken as the moisture content of the solution at the time of spraying.

The solution obtained in the above manner was degassed by centrifugal separation, and then transferred to a plunger whose temperature was adjusted to 50°C in advance. Install a spinning nozzle (diameter 0.1 mm, 16 holes) on the plunger, and use a micro feeder to extrude the solution from the plunger pump at a discharge temperature of 80°C and a discharge speed of 30 m/min. At this time, an air gap of 10 mm is set between the spinning nozzle surface and the liquid level of the coagulation bath. At this time, the temperature in the air gap is 22°C and the humidity is 35%RH.

The filament ejected in the above manner is coagulated in a coagulation bath (pure water: the above mixed solvent = 90:10, 25°C), and then washed in a scouring bath (pure water, 25°C), and then rolled. Take coiling at a speed of 60 m/min (draw ratio 2.0).

The undried fiber rolled in the above manner was dried at 110° C. and then rolled to obtain fiber S1 of Example 1.

[Example 2] Fiber S2 of Example 2 was obtained in the same manner as in Example 1, except that TBEAA of Production Example 2 was used instead of TBMAA.

[Example 3] Fiber S3 of Example 3 was obtained in the same manner as in Example 1, except that ETPAA of Production Example 3 was used instead of TBMAA.

[Example 4] Fiber S4 of Example 4 was obtained in the same manner as in Example 1, except that TEPenAA of Production Example 4 was used instead of TBMAA.

[Example 5] Fiber S5 of Example 5 was obtained in the same manner as in Example 1, except that DTEAA of Production Example 5 was used instead of TBMAA.

[Example 6] Fiber S6 of Example 6 was obtained in the same manner as in Example 1, except that DDTEAA of Production Example 6 was used instead of TBMAA.

[Example 7] Fiber S7 of Example 7 was obtained in the same manner as in Example 1, except that TBDAA of Production Example 7 was used instead of TBMAAA.

[Example 8] Fiber S8 of Example 8 was obtained in the same manner as in Example 1, except that MTOAA of Production Example 8 was used instead of TBMAA.

[Example 9] Fiber S9 of Example 9 was obtained in the same manner as in Example 1, except that BTOAA of Production Example 9 was used instead of TBMAA.

[Example 10] Fiber S10 of Example 10 was obtained in the same manner as in Example 1, except that DBDEAA of Production Example 10 was used instead of TBMAA.

[Example 11] Fiber S11 of Example 11 was obtained in the same manner as in Example 1, except that DDEMAA of Production Example 11 was used instead of TBMAA.

[Example 12] Fiber S12 of Example 12 was obtained in the same manner as in Example 1, except that TEOPA of Production Example 12 was used instead of TBMAA.

[Example 13] Fiber S13 of Example 13 was obtained in the same manner as in Example 1, except that pure water was added to the mixed solvent to adjust the water content to 5.0 mass%.

[Example 14] Fiber S14 of Example 14 was obtained in the same manner as in Example 1, except that the fiber was rolled up at 48 m/min (draw ratio 1.6). At this time, the temperature in the air gap is 28°C and the humidity is 90%RH.

[Example 15] Fiber S15 of Example 15 was obtained in the same manner as Example 1 except that the air gap length was set to 30 mm.

[Example 16] Fiber S16 of Example 16 was obtained in the same manner as in Example 1 except that DMSO and TBMAA were mixed in a mass ratio of 90:10.

[Example 17] Fiber S17 of Example 17 was obtained in the same manner as in Example 1, except that DMSO and TBMAA were mixed in a mass ratio of 40:60.

[Example 18] Fiber S18 of Example 18 was obtained in the same manner as Example 1, except that DMAc (Dimethylacetamide) was used instead of DMSO.

[Example 19] Fiber S19 of Example 19 was obtained in the same manner as in Example 1, except that TBMA(OMe)A of Production Example 13 was used instead of TBMAA.

[Example 20] The implementation was performed in the same manner as in Example 1, except that pure water was added to the mixed solvent to set the water content to 9.0 mass %, and the winding was performed at a winding speed of 30 m/min (draw ratio 1.0). Example 20 fiber S20.

[Example 21] Fiber S21 of Example 21 was obtained in the same manner as in Example 1, except that the fiber was rolled up at 30 m/min (draw ratio 1.0). At this time, the temperature in the air gap is 27°C and the humidity is 95%RH.

[Example 22] Examples were obtained in the same manner as in Example 1, except that DMSO and TBMAA were mixed so that the mass ratio became 97:3, and the winding speed was 30 m/min (draw ratio 1.0). 22 fiber S22.

[Example 23] Examples were obtained in the same manner as in Example 1, except that DMSO and TBMAA were mixed so that the mass ratio became 30:70, and were wound up at a winding speed of 30 m/min (draw ratio 1.0). 23 fiber S23.

[Example 24] Fiber S24 of Example 24 was obtained in the same manner as Example 4 except that TEPenAA was not dried.

[Example 25] Fiber S25 of Example 25 was obtained in the same manner as Example 4, except that TEPenAA and DMSO were not dried.

[Comparative example 1] The fiber RS1 of Comparative Example 1 was obtained in the same manner as in Example 1, except that tetrabutylammonium acetate (TBAA) (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of TBMAA.

[Comparative example 2] The solution preparation operation was performed in the same manner as in Example 1 except that TBEAB of Production Example 14 was used instead of TBMAA. However, the cellulose fiber RS2 of Comparative Example 2 could not be produced because the cellulose was not dissolved.

[Comparative example 3] The fiber RS3 of Comparative Example 3 was obtained in the same manner as in Example 1, except that no air gap was provided, the spinning nozzle surface was immersed in the coagulation liquid, and the winding was performed at 48 m/min (draw ratio 1.6). .

[Comparative example 4] The fiber RS4 of Comparative Example 4 was obtained in the same manner as in Example 1, except that TEProAC of Production Example 15 was used instead of TBMAA.

[Comparative example 5] The fiber RS5 of Comparative Example 5 was obtained in the same manner as in Example 1 except that triethymethylammonium chloride (TEMAC) (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of TBMAA.

[Table 1] Table 1 Examples/Comparative Examples of Polysaccharide Fiber Production Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 raw material Quaternary ammonium salt or quaternary phosphonium salt Kind TBMAA TBEAA ETPAA TEPenAA DTEAA DDTEAA TBDAA MTOAA BTOAA DBDEAA C _L /C _S 4.0 2.0 1.5 2.5 5.0 6.0 2.5 8.0 2.0 2.0 Total number of carbon atoms in the cationic part 13 14 11 11 16 18 twenty two 25 28 12 Mass parts in mixed solvent 25 25 25 25 25 25 25 25 25 25 Solvent Kind DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO Mass parts in mixed solvent 75 75 75 75 75 75 75 75 75 75 Cellulose Mass % (in solution) 7 7 7 7 7 7 7 7 7 7 water Mass % (in solution) 2 2 2 2 2 2 2 2 2 2 solution Smoothness of solution - 4.8 4.8 4.6 4.8 3.8 3.4 3.4 3.6 3.4 3.6 Spinning conditions air gap temperature ℃ twenty two twenty four twenty three twenty two twenty three 20 twenty four twenty three twenty four twenty three air gap humidity %RH 35 61 55 53 45 60 48 39 59 38 air gap length mm 10 10 10 10 10 10 10 10 10 10 Fiber physical properties intensity cN/dtex 2.5 2.4 2.4 2.4 2.2 2.1 2.1 2.0 2.1 2.4 Elongation % 15 13 14 15 13 14 12 12 11 14 Uneven threads % 3 3 3 3 3 5 5 5 6 3 Degree of fibrillation % 1 1 1 1 1 3 3 4 5 2 Effect Spinnability - A A A A A A A A A A skin touch - 4.8 4.8 4.8 4.8 4.6 3.4 3.4 3.4 3.2 4.0 Fiber elasticity - 5.0 4.8 4.8 4.8 4.6 3.2 3.4 3.4 3.2 4.2

[Table 2] Table 2 Examples/Comparative Examples of Polysaccharide Fiber Production Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 S11 S12 S13 S14 S15 S16 S17 S18 S19 S20 raw material Quaternary ammonium salt or quaternary phosphonium salt Kind DDEMAA TEOPA TBMAA TBMAA TBMAA TBMAA TBMAA TBMAA TBMA(OMe)A TBMAA C _L /C _S 10.0 4.0 2.0 2.0 2.0 4.0 4.0 4.0 4.0 2.0 Total number of carbon atoms in the cationic part 15 14 14 14 14 13 13 13 13 14 Mass parts in mixed solvent 25 25 25 25 25 10 60 25 25 25 Solvent Kind DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMAc DMSO DMSO Mass parts in mixed solvent 75 75 75 75 75 90 40 75 75 75 cellulose Mass % (in solution) 7 7 7 7 7 7 7 7 7 7 water Mass % (in solution) 2 2 5 2 2 2 2 2 2 9 solution Smoothness of solution - 3.4 3.6 3.8 1.4 4.8 3.6 3.4 3.4 3.4 1.4 Spinning conditions air gap temperature ℃ twenty two twenty two twenty four 28 twenty two twenty three twenty four twenty three twenty three twenty three air gap humidity %RH 40 45 55 90 39 51 53 49 61 72 air gap length mm 10 10 10 10 30 10 10 10 10 10 Fiber physical properties intensity cN/dtex 2.1 2.2 2.1 2.0 2.2 1.9 1.9 2.1 2.1 1.9 Elongation % 12 12 8 8 12 14 8 10 10 6 Uneven threads % 6 4 6 7 4 6 6 6 6 9 Degree of fibrillation % 4 3 2 5 3 1 3 3 1 3 Effect Spinnability - A A A B A A A A A B skin touch - 3.2 4.0 3.8 3.4 4.4 3.8 3.4 3.4 3.6 3.4 Fiber elasticity - 3.4 3.8 4.0 3.4 4.6 3.6 3.4 3.4 3.4 3.4

[table 3] table 3 Examples/Comparative Examples of Polysaccharide Fiber Production Example 21 Example 22 Example 23 Example 24 Example 25 S21 S22 S23 S24 S25 raw material Quaternary ammonium salt or quaternary phosphonium salt Kind TBMAA TBMAA TBMAA TEPenAA TEPenAA C _L /C _S 2.0 4.0 4.0 2.5 2.5 Total number of carbon atoms in the cationic part 14 13 13 11 11 Mass parts in mixed solvent 25 3 70 25 25 Solvent Kind DMSO DMSO DMSO DMSO DMSO Mass parts in mixed solvent 75 97 30 75 75 Cellulose Mass % (in solution) 7 7 7 7 7 water Mass % (in solution) 2 2 2 4 5 solution Smoothness of solution - 4.8 3.2 3.2 2.8 2.6 Spinning conditions air gap temperature ℃ 27 twenty two twenty one twenty three twenty two air gap humidity %RH 95 53 64 54 55 air gap length mm 10 10 10 10 10 Fiber physical properties intensity cN/dtex 1.9 1.8 1.8 2 1.8 Elongation % 7 7 5 10 8 Uneven threads % 9 9 8 6 8 Degree of fibrillation % 3 3 5 3 3 Effect Spinnability - C C C B B skin touch - 3.2 3.2 3.4 3 2.8 Fiber elasticity - 3.2 3.2 3.4 3 2.8

[Table 4] Table 4 Examples/Comparative Examples of Polysaccharide Fiber Production Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 RS1 RS2 RS3 RS4 RS5 raw material Quaternary ammonium salt or quaternary phosphonium salt Kind TBAA TBEAB TBMAA TEProAC TEMAC C _L /C _S 1.0 4.0 4.0 1.5 2.0 Total number of carbon atoms in the cationic part 16 13 13 9 7 Mass parts in mixed solvent 25 25 25 25 25 Solvent Kind DMSO DMSO DMSO DMSO DMSO Mass parts in mixed solvent 75 75 75 75 75 cellulose Mass % (in solution) 7 7 7 7 7 water Mass % (in solution) 2 2 2 2 2 solution Smoothness of solution - 2.0 - 4.8 2.0 1.8 Spinning conditions air gap temperature ℃ twenty three - - twenty three twenty one air gap humidity %RH 62 - - 56 45 air gap length mm 10 - 0 10 10 Fiber physical properties intensity cN/dtex 2.3 - 1.5 2.1 2.2 Elongation % 14 - 8 12 11 Uneven threads % 12 - 2 12 12 Degree of fibrillation % 3 - 1 10 10 Effect Spinnability - B - A B B skin touch - 2.0 - 1.6 1.8 2.1 Fiber elasticity - 2.0 - 1.6 1.8 2.2 [Industrial availability]

According to the method for producing polysaccharide fiber of the present invention, it is possible to suppress breakage during the spinning step and uneven physical properties of the fiber obtained, thereby enabling stable spinning, and therefore can be preferably used for a variety of purposes. Manufacture of carbohydrate fibers. Furthermore, the fiber obtained by the method for producing the polysaccharide fiber of the present invention has high strength, suppresses fibrillation, and has excellent skin feel. Therefore, it can be preferably used in functional clothing and the like.

Claims (11)

A method for manufacturing polysaccharide fiber, which includes: The solution preparation step is to dissolve polysaccharides in a mixed solvent of an aprotic polar solvent and a quaternary ammonium salt and/or a quaternary phosphonium salt; The spraying step is to spray the prepared solution from the spinning nozzle in the form of fibers; and The coagulation step is to coagulate the ejected fibers by contacting them with the coagulation liquid; and The cationic part of the above-mentioned quaternary ammonium salt and quaternary phosphonium salt has two or more alkyl groups, The anion part of the above-mentioned quaternary ammonium salt and quaternary phosphonium salt is a carboxylate anion, In the above-mentioned spraying step, an air gap is provided between the above-mentioned spinning nozzle and the above-mentioned coagulation liquid. The method of claim 1, wherein in the cation part of the above-mentioned quaternary ammonium salt and the above-mentioned quaternary phosphonium salt, the carbon number C _L of the alkyl group with the largest carbon number and the carbon number C _S of the alkyl group with the smallest carbon number satisfy 2＜C _L /C _S . The method of claim 1 or 2, wherein the moisture content of the solution in the spraying step is 0.05 mass% or more and 8 mass% or less based on the total mass of the solution. The method of claim 1 or 2, wherein the moisture content of the solution in the spraying step is 0.05 mass% or more and 2 mass% or less based on the total mass of the solution. Such as the method of claim 1 or 2, wherein the atmosphere in the above-mentioned air gap has a relative humidity of less than 90%. The method of claim 1 or 2, wherein the length of the air gap from the spinning nozzle to the coagulation liquid is 1 mm or more and 30 mm or less. The method of claim 1 or 2, wherein the mass ratio of the aprotic polar solvent to the quaternary ammonium salt and/or the quaternary phosphonium salt in the above solution preparation step is 40:60 to 95:5. The method of claim 1 or 2, wherein the aprotic polar solvent is dimethylsterine. The method of claim 1 or 2, wherein the above-mentioned quaternary ammonium salt is selected from the group consisting of triethypentylammonium acetate, triethyhexylammonium acetate, triethyheptylammonium acetate, triethyloctyl ammonium acetate, acetic acid At least one of the group consisting of triethylnonylammonium and triethyldecylammonium acetate, and the above-mentioned quaternary phosphonium salt is selected from the group consisting of triethylpentylphosphonium acetate, triethylhexylphosphonium acetate, and triethylhexylphosphonium acetate. At least one member from the group consisting of ethylheptylphosphonium and triethyloctylphosphonium acetate. A polysaccharide fiber with a tensile strength of more than 1.6 cN/dtex, a coefficient of variation of the tensile strength of less than 10%, and a fibrillation degree of less than 170%. For example, the polysaccharide fiber of claim 10 is a continuous long fiber.