Lyocell fiber and method for manufacturing the same

Abstract

To provide a lyocell fiber capable of maintaining a temperature control function for a long period of time and absorbing formalin, and a method for manufacturing the same.SOLUTION: There is provided a lyocell fiber, that contains cellulose, micro-capsule having a core-cell structure, and a formalin scavenger. The micro-capsule is crosslinked with a lyocell fiber matrix and a formalin scavenger, a core of the micro-capsule contains a phase change material and a nano-nucleating agent, and cells of the micro-capsule contain a melamine-modified urea-formaldehyde resin prepolymer. A method for manufacturing a lyocell fiber includes: a spinning solution preparation step in which cellulose pulp, N-methylmorpholine-N-oxide, micro-capsule having a core-cell structure, and a formalin scavenger are mixed and post-treated; a spinning step in which the spinning solution obtained through the spinning solution preparation step is spun; and a microwave treatment step in which a yarn obtained through the spinning step is subjected to a microwave treatment step.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to lyocell fibers and methods for producing the same. [Background technology]

[0002] With the development of science and technology and the improvement of people's living standards, the textile industry is gradually developing in the direction of functionality and intelligence, and temperature-regulating fibers are an important part of this.Temperature-regulating fibers have two-way automatic temperature regulation function, and use phase change materials (PCMs) to release or absorb latent heat during the phase change process to achieve the purpose of temperature regulation.

[0003] Most existing temperature-regulating fibers are based on viscose fibers. For example, Patent Document 1 discloses a method for producing a temperature-regulating cellulose fiber with temperature-regulating properties. Patent Document 2 discloses a viscose fiber and a method for producing the same.

[0004] The spinning process of the fibers disclosed in Patent Documents 1 and 2 is lengthy and involves the use of corrosive chemical raw materials such as sodium hydroxide, carbon disulfide, and sulfuric acid, which causes serious environmental pollution. In light of this, temperature-regulating fibers based on lyocell fibers have been developed.

[0005] Lyocell fiber is a regenerated cellulose fiber produced by dissolving cellulose in N-methylmorpholine-N-oxide (NMMO) and using a dry-jet wet-spinning process. Compared to viscose fiber, the manufacturing process for lyocell fiber is simple and environmentally friendly, and it has excellent physical and mechanical properties and dimensional stability, making it popular with consumers. Patent Document 3 discloses the production of lyocell fiber with temperature control function by directly adding a semi-refined paraffin mixture, a phase change material that achieves temperature control, to the spinning slurry of the lyocell fiber. However, the phase change material in the lyocell fiber is easily lost from the lyocell fiber, and the temperature control function of the fiber is not maintained for a long period of time. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Chinese Patent Application Publication No. 1995497 [Patent Document 2] Chinese Patent Application Publication No. 101942706 [Patent Document 3] Chinese Patent Application Publication No. 110886026 Summary of the Invention [Problem to be solved by the invention]

[0007] The problem to be solved by the present invention is to provide a lyocell fiber that can maintain its temperature regulating function for a long period of time and can absorb formalin, and a method for producing the same. [Means for solving the problem]

[0008] The present inventors have conducted extensive research in light of the above-mentioned problems and have found that the temperature regulating function of lyocell fiber containing cellulose, specific microcapsules having a core-cell structure, and a formalin scavenger can be maintained for a long period of time. The present invention has been completed based on these findings.

[0009] The present invention provides a lyocell fiber comprising cellulose, microcapsules having a core-cell structure, and a formalin scavenger, the microcapsules are crosslinked with the cellulose and the formalin scavenger; the microcapsule core comprises a phase change material and a nano-nucleating agent; The microcapsule cells are made of lyocell fibers containing a melamine-modified urea-formaldehyde resin prepolymer.

[0010] Furthermore, the present invention also provides a spinning dope preparation step in which cellulose pulp, N-methylmorpholine-N-oxide, microcapsules having a core-cell structure, and a formalin scavenger are mixed and post-treated; a spinning step of spinning the spinning dope obtained through the spinning dope preparation step; and The present invention relates to a method for producing lyocell fiber, which includes a microwave treatment step in which the yarn obtained through the spinning step is subjected to a microwave treatment step.

[0011] The method for producing lyocell fiber of the present invention further includes a microcapsule production step of producing microcapsules having the core-cell structure, The microcapsule manufacturing process includes: an emulsion preparation step of mixing a phase change material, a nano-nucleating agent, an emulsifier, and water to obtain an emulsion for capsule cores; a prepolymer preparation step of mixing glutaraldehyde, formaldehyde, melamine, urea, and water to carry out a polycondensation reaction to obtain a melamine-modified urea-formaldehyde resin prepolymer; and It is preferable that the method further includes a crosslinking reaction step of crosslinking the capsule core emulsion obtained through the emulsion preparation step, the melamine-modified urea-formaldehyde resin prepolymer obtained through the prepolymer preparation step, and nano-zinc oxide. [Effects of the Invention]

[0012] The present invention provides a lyocell fiber that maintains its temperature regulating function for a long period of time and is capable of absorbing formalin. The present invention also provides a method for producing the lyocell fiber.

[0013] The method for producing lyocell fiber of the present invention can improve the stability of microcapsules in temperature-regulating lyocell fiber, and has a short production process without requiring the use of strong alkali or strong acid, which is environmentally friendly and non-polluting. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is an explanatory diagram showing the configuration of a lyocell fiber according to one embodiment of the present invention. [Figure 2]FIG. 2 is a schematic diagram showing the cross-sectional structure of a core cell of a microcapsule in the lyocell fiber of FIG. 1. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present invention will now be described in further detail. Unless otherwise specified, the symbol "to" in a numerical range indicates a range from above to below, and both ends of the range are included. Furthermore, when a numerical range is indicated, the upper and lower limits can be combined as appropriate, and the resulting numerical range is also considered to be disclosed. Furthermore, in the description of the drawings, the same elements are denoted by the same reference numerals, and duplicate explanations will be omitted. Also, the dimensional proportions of the drawings are exaggerated for the convenience of explanation and may differ from the actual proportions.

[0016] <Cellulose> The lyocell fibers of the present invention contain cellulose, which constitutes the matrix of the lyocell fibers of the present invention.

[0017] <Microcapsules> The lyocell fiber of the present invention contains microcapsules with a core-cell structure. For example, in the lyocell fiber according to one embodiment of the present invention shown in Figure 1, microcapsules 1 are crosslinked with a lyocell fiber matrix 2 and a formalin scavenger 3. The microcapsules 1 have the function of storing energy and regulating temperature. The microcapsules 1 are composed of a microcapsule core 4 and microcapsule cells 5, as shown in Figure 2, for example.

[0018] (microcapsule core) The core of the macrocapsule contains a phase change material and a nano-nucleating agent. The phase change material preferably contains at least one selected from the group consisting of paraffin, n-octadecane, n-nonadecane, and n-eicosane, more preferably paraffin, n-octadecane, n-nonadecane, or n-eicosane. The nano-nucleating agent preferably contains at least one selected from the group consisting of nano-zinc oxide, nano-titanium dioxide, nano-calcium carbonate, and nano-silica, more preferably nano-zinc oxide. The particle size of the nano-nucleating agent is preferably in the range of 15 to 50 nm, more preferably in the range of 25 to 38 nm. The mass ratio of the content of the nano-nucleating agent to the content of the phase change material is preferably in the range of 0.2 to 0.3:10, more preferably in the range of 0.25 to 0.28:10.

[0019] In the present invention, the nano-nucleating agent can act as a crystal nucleus to promote crystallization, reduce the degree of supercooling during the phase change process of the phase change material, and improve the efficiency of energy storage and temperature control of the phase change material.

[0020] (microcapsule cells) The cells of the microcapsules contain a melamine-modified urea-formaldehyde resin prepolymer. Preferably, the cells of the microcapsules further contain nano-zinc oxide particles. The particle size of the nano-zinc oxide is preferably in the range of 15 to 50 nm, more preferably in the range of 20 to 35 nm. The mass ratio of the nano-zinc oxide particles to the melamine-modified urea-formaldehyde resin prepolymer in the cells of the microcapsules is preferably in the range of 0.1 to 0.3:1, more preferably in the range of 0.16 to 0.25:1.

[0021] In the present invention, the addition of nano zinc oxide to the cells of the microcapsules can impart antibacterial properties to the thermoregulating lyocell fiber.

[0022] <Formalin scavenger> The formalin scavenger of the present invention is preferably an amide compound.The mass ratio of the content of the formalin scavenger to the content of the microcapsules is preferably in the range of 1 to 1.5:20. The mass ratio of the contents of cellulose, microcapsules, and formalin scavenger in the lyocell fiber is preferably in the range of 100:49.8-99.7:2.5-5, and more preferably in the range of 100:67.5-89.2:3.3-4.5.

[0023] In the present invention, the formalin scavenger plays a role in absorbing formalin generated by formaldehyde, melamine, etc. in the cells of the microcapsules. By adding the formalin scavenger, more microcapsules can be added to the lyocell fiber, thereby achieving a better temperature control effect.

[0024] <Lyocell fiber manufacturing method> (Spinning dope preparation process) The method for producing lyocell fiber of the present invention includes a spinning dope preparation step. In the spinning dope preparation step, cellulose pulp, N-methylmorpholine-N-oxide, microcapsules having a core-cell structure, and a formalin scavenger are mixed and then post-treated. The average degree of polymerization of the cellulose pulp in the spinning dope preparation step is preferably in the range of 600 to 800, more preferably in the range of 680 to 750. The content of α-cellulose contained in the cellulose pulp is preferably in the range of 92 to 99% by mass, more preferably in the range of 96% to 98% by mass. The cellulose pulp preferably contains α-cellulose in an amount of 92 to 99% by mass. The mass ratio of the content of the microcapsules, the content of the formalin scavenger, and the content of the α-cellulose contained in the cellulose pulp is preferably in the range of 50.6 to 101.8:2.5 to 5:100, and more preferably in the range of 68.2 to 91.0:3.4 to 4.55:100. The content of α-cellulose in the spinning dope is preferably in the range of 10 to 20% by mass, and more preferably in the range of 12 to 16% by mass. The N-methylmorpholine-N-oxide is preferably provided in the form of an aqueous N-methylmorpholine-N-oxide solution, the concentration of which is preferably in the range of 80 to 87% by mass, more preferably in the range of 82 to 85% by mass.

[0025] The post-treatment preferably includes at least one step selected from the group consisting of heating, evacuation, dehydration, dissolution, homogenization, degassing, and filtration, and more preferably includes the steps of heating, evacuation, dehydration, dissolution, homogenization, degassing, and filtration, performed in this order. There are no particular limitations on the methods for heating, evacuation, dehydration, dissolution, homogenization, degassing, and filtration, and any method known in the art may be used.

[0026] (Spinning process) The method for producing lyocell fiber of the present invention includes a spinning step. In the spinning step, the spinning dope obtained through the spinning dope preparation step is spun. The spinning speed in the spinning step is preferably in the range of 25 to 45 m / min, more preferably in the range of 32 to 40 m / min. The concentration of the coagulation bath used in the spinning step is preferably in the range of 10 to 20 mass%, more preferably in the range of 13 to 18 mass%, and the temperature of the coagulation bath is preferably in the range of 15 to 25°C, more preferably in the range of 18 to 22°C.

[0027] It is preferable to further include a step of sequentially washing the product obtained through the spinning step with water, bleaching, and applying oil after the spinning step and before the microwave treatment step. The water used for the water washing is preferably deionized water. The water temperature for the water washing is preferably in the range of 20 to 25°C, more preferably in the range of 38 to 40°C. The bleaching is preferably performed using an aqueous solution of hydrogen peroxide. The concentration of the aqueous solution of hydrogen peroxide is preferably in the range of 1.0 to 2.0 g / L, more preferably in the range of 1.5 to 1.8 g / L. The pH value of the aqueous solution of hydrogen peroxide is preferably in the range of 8.5 to 10, more preferably in the range of 9 to 9.5. The temperature of the aqueous solution of hydrogen peroxide is preferably in the range of 30 to 45°C, more preferably in the range of 36 to 41°C. The temperature of the oil bath used for the oil application is preferably in the range of 50 to 80°C, more preferably in the range of 65 to 72°C, and the pH value of the oil bath is preferably in the range of 6.0 to 9.0, more preferably in the range of 7.0 to 8.0. The oil used for the oil application is not particularly limited, and any oil known in the art may be used. The concentration of the oil in the oil bath is preferably in the range of 2.5 to 6.0 g / L, more preferably in the range of 3.5 to 5.0 g / L.

[0028] (Microwave treatment process) The method for producing lyocell fiber of the present invention includes a microwave treatment step in which the yarn obtained through the spinning step is subjected to a microwave treatment step. The frequency of the microwaves irradiated in the microwave treatment step is preferably in the range of 1560 to 1800 MHz, more preferably in the range of 1650 to 1720 MHz. The treatment time in the microwave treatment step is preferably in the range of 20 to 36 minutes, more preferably in the range of 26 to 33 minutes.

[0029] The microwave treatment step involves polycondensation of hydroxymethyl groups in the microcapsule cells with the hydroxyl groups in the formalin scavenger and cellulose to form methylene bonds, and hydrogen bonding of unreacted hydroxymethyl and amino groups in the microcapsule cells (i.e., hydroxymethyl and amino groups in the melamine-modified urea-formaldehyde resin prepolymer) with hydroxyl groups in the cellulose, thereby improving the stability of the microcapsules, reducing the risk of microcapsule loss due to washing or daily use, and absorbing formalin generated from the microcapsule cell material. The microwave frequency used in the microwave treatment step is preferably in the range of 1560 to 1800 MHz. This microwave frequency range prevents the formation or destruction of functional group bonds between the microcapsules, the formalin scavenger, and the cellulose, improving the stability of the microcapsules.

[0030] In the present invention, the microwave treatment also serves to dry the cellulose fibers. The moisture content of the cellulose fibers that have been subjected to the microwave treatment is preferably 8.5 to 11.6% by mass, and more preferably 9.7 to 10.2% by mass.

[0031] <Microcapsule manufacturing process> (Emulsion preparation process) The emulsion preparation step of the present invention comprises: a capsule core material preparation step of mixing the molten phase change material and the nano-nucleating agent to obtain a capsule core material; It is preferable that the method further comprises a capsule core material emulsion preparation step of mixing the capsule core material, an emulsifier, and water to obtain a capsule core material emulsion.

[0032] The phase-change material preferably includes at least one selected from the group consisting of paraffin, n-octadecane, n-nonadecane, and n-eicosane, more preferably n-octadecane or n-eicosane. The nano-nucleating agent preferably includes at least one selected from the group consisting of nano-zinc oxide, nano-titanium dioxide, nano-calcium carbonate, and nano-silica, more preferably nano-zinc oxide. The particle size of the nano-nucleating agent is preferably in the range of 15 to 50 nm, more preferably 25 to 38 nm. The emulsifier preferably includes at least one selected from the group consisting of polysorbate-80, sodium dodecyl sulfate (SDS), Span-80, and styrene maleic anhydride sodium salt, more preferably polysorbate-80 or Span-80. When the emulsifier includes two or more of the above-listed substances, the mass ratio of the specific substances is not particularly limited, and any desired ratio may be used. The water is preferably distilled water.

[0033] The melting temperature is preferably in the range of 40 to 50°C, more preferably in the range of 42 to 48°C. The melting time is not particularly limited as long as it can melt the phase-change material. In the present invention, the capsule core material preparation step is preferably carried out under stirring conditions. The stirring speed is preferably in the range of 600 to 850 r / min, more preferably in the range of 680 to 800 r / min. The stirring time is not particularly limited as long as it can uniformly mix the mixture. In the present invention, the dispersing means for the dispersion is not particularly limited as long as it can uniformly disperse the material.

[0034] The content of the capsule core material in the capsule core material emulsion is preferably in the range of 30 to 40% by mass, more preferably in the range of 32.5 to 36.8% by mass. The content of the emulsifier in the capsule core material emulsion is preferably in the range of 2.5 to 4% by mass, more preferably in the range of 3.2 to 3.75% by mass.

[0035] The temperature in the capsule core material emulsion preparation step is preferably in the range of 40 to 50°C, more preferably in the range of 42 to 46°C. The capsule core material emulsion preparation step is preferably performed under stirring conditions. The stirring speed is preferably in the range of 1800 to 2300 r / min, more preferably in the range of 1980 to 2150 r / min. In the capsule core material emulsion preparation step, the particle size of the emulsion droplets is detected. The particle size of the emulsion droplets is preferably in the range of D90≦1.055 μm, more preferably in the range of 0.892 μm≦D90≦0.998 μm. The stirring time is not particularly limited as long as the particle size of the emulsion droplets reaches the above range.

[0036] The particle size of the emulsion droplets is detected by a laser particle size distribution analyzer.

[0037] (Prepolymer preparation process) In the prepolymer preparation step of the present invention, glutaraldehyde, formaldehyde, melamine, urea, and water are mixed together to carry out a polycondensation reaction to obtain a melamine-modified urea-formaldehyde resin prepolymer. The reaction temperature of the polycondensation reaction in the prepolymer preparation step is preferably in the range of 40 to 50°C.

[0038] The formaldehyde is preferably provided in the form of an aqueous formaldehyde solution. In the present invention, the concentration of the aqueous formaldehyde solution is preferably 35 to 39% by mass, more preferably 37% by mass. The mass ratio of the glutaraldehyde content to the formaldehyde content is preferably in the range of 1:1 to 1:3, more preferably in the range of 1:1.8 to 1:2.5. The mass ratio of the melamine content to the urea content is preferably in the range of 0.05 to 0.15:1, more preferably in the range of 0.08 to 0.12:1. In the present invention, the mass ratio of the total mass of the glutaraldehyde and the formaldehyde to the total mass of the melamine and the urea is preferably in the range of 2 to 4:1, more preferably in the range of 2.5 to 3:1.

[0039] The mixing is not particularly limited as long as it can achieve uniform mixing. In the present invention, it is more preferable to include a step of adjusting the pH value of the mixture to a range of 7.5 to 8.5, more preferably to 8, prior to the polycondensation reaction. The pH adjuster for adjusting the pH value of the mixture preferably contains triethanolamine or sodium hydroxide, more preferably triethanolamine. The amount of the pH adjuster to be administered is not particularly limited as long as it can adjust the pH to the desired value.

[0040] The polycondensation reaction is preferably accompanied by stirring, and the rotation speed of the stirring is preferably in the range of 200 to 400 r / min, more preferably in the range of 260 to 320 r / min. In the present invention, the temperature of the polycondensation reaction is preferably in the range of 60 to 90° C., more preferably in the range of 70 to 80° C. In the present invention, the time of the polycondensation reaction is not particularly limited as long as the reaction system is a colorless, transparent solution.

[0041] (Crosslinking reaction process) In the crosslinking reaction process of the present invention, the capsule core emulsion obtained through the emulsion preparation process, the melamine-modified urea-formaldehyde resin prepolymer obtained through the prepolymer preparation process, and nano-zinc oxide are crosslinked to obtain the microcapsule dispersion. The reaction temperature in the crosslinking reaction step is preferably in the range of 65 to 75° C., more preferably in the range of 68 to 72° C. The reaction time in the crosslinking reaction step is in the range of 150 to 240 minutes, more preferably in the range of 180 to 200 minutes.

[0042] The crosslinking reaction step a capsule cell material dispersion preparation step of dispersing nano-zinc oxide in a melamine-modified urea formaldehyde resin prepolymer to obtain a capsule cell material dispersion; It is preferable that the method further comprises a mixing step of mixing the capsule cell material dispersion liquid and the capsule core material emulsion liquid.

[0043] In the capsule cell material dispersion preparation step, the mass ratio of the nano zinc oxide to the total mass of melamine and urea is preferably in the range of 0.1 to 0.3:1, more preferably in the range of 0.16 to 0.25:1. The dispersion temperature in the capsule cell material dispersion preparation step is preferably in the range of 40 to 50° C., more preferably in the range of 43 to 47° C. The dispersion method is not particularly limited as long as it can achieve uniform dispersion.

[0044] In the present invention, the nano zinc oxide in the capsule cell material dispersion provides good antibacterial performance to the lyocell fiber.

[0045] In the mixing step, the mass ratio of the capsule core material to the melamine-modified urea-formaldehyde resin prepolymer is preferably in the range of 1.5 to 2.3:1, more preferably in the range of 1.8 to 2.1:1. In the present invention, the mixing temperature in the mixing step is preferably in the range of 40 to 50°C, more preferably in the range of 42 to 48°C. In the present invention, the mixing step is preferably carried out under stirring conditions. The rotation speed of the stirring is preferably in the range of 1800 to 2300 r / min, more preferably in the range of 1980 to 2150 r / min. The stirring time is not particularly limited as long as the mixture can be uniformly mixed.

[0046] In the present invention, it is preferable to carry out thermal evaporation after the crosslinking reaction step to remove a portion of the water. The microcapsule content in the microcapsule dispersion after the thermal evaporation is preferably in the range of 35 to 45% by mass, more preferably in the range of 38 to 42% by mass. There are no particular limitations on the conditions for the thermal evaporation, as long as the microcapsule content falls within the above-specified range.

[0047] In the present invention, it is preferable that the method further comprises, after the crosslinking reaction step, a solid-liquid separation step of subjecting the mixture obtained through the crosslinking reaction step to solid-liquid separation to obtain microcapsules. The means for the solid-liquid separation is not particularly limited as long as it can achieve solid-liquid separation.

[0048] In the present invention, it is preferable that the method further includes an activation step of activating cellulose pulp before the spinning dope preparation step. The activation step is preferably performed using cellulase. The pH value in the activation step is preferably in the range of 4 to 6, more preferably in the range of 5 to 5.5. The activation temperature in the activation step is preferably in the range of 40 to 55°C, more preferably in the range of 45 to 50°C. The activation time in the activation step is preferably in the range of 30 to 60 minutes, more preferably in the range of 40 to 50 minutes. The mass ratio of the dry weight of the cellulase to the dry weight of the cellulose pulp is preferably 500 to 6000 g:1000 kg, more preferably 2000 to 4000 g:1000 kg.

[0049] In the present invention, it is preferable that the activation step be followed by a pressing step in which the product obtained through the activation step is adjusted to a pH value in the range of 10 to 12 and pressed. The pH adjuster used to adjust the pH value is not particularly limited as long as it can achieve the desired pH value. After the pressing step, the moisture content of the cellulose pulp is preferably 30 to 60% by mass, more preferably 40 to 50% by mass.

[0050] In the present invention, in order to simplify the operating procedure, it is preferable to directly mix the microcapsule dispersion obtained through the crosslinking reaction step, the formalin catcher agent, the cellulose pulp and the N-methylmorpholine-N-oxide aqueous solution.

[0051] The phase change temperature regulating lyocell fibers of the present invention can be applied to clothing or bedding. [Example]

[0052] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0053] [Example 1] Paraffin was melted at 40°C and mixed with nano-zinc oxide having a particle size of 50 nm at a rotation speed of 600 r / min to obtain a capsule core material, where the mass ratio of paraffin to nano-zinc oxide was 0.2:10. Styrene maleic anhydride sodium salt was dispersed in distilled water to obtain an emulsifier dispersion. The capsule core material and the emulsifier dispersion were mixed at a temperature of 40°C and a rotation speed of 1800 r / min to obtain a capsule core material emulsion. In the capsule core material emulsion, the capsule core material content was 30% by mass, the styrene maleic anhydride sodium salt content was 2.5% by mass, and the particle size D90 was 0.892 μm.

[0054] Glutaraldehyde, a 37% by weight aqueous formaldehyde solution, melamine, and urea were mixed, the pH of the mixture was adjusted to 7.5 with triethanolamine, and the mixture was subjected to a polycondensation reaction at 60°C and a rotation speed of 400 r / min until a colorless, transparent solution was obtained, yielding a melamine-modified urea-formaldehyde resin prepolymer solution. The weight ratio of glutaraldehyde to formaldehyde in the aqueous formaldehyde solution was 1:1, the weight ratio of melamine to urea in the aqueous formaldehyde solution was 0.05:1, and the weight ratio of the total weight of formaldehyde in the aqueous glutaraldehyde and formaldehyde solution to the total weight of melamine and urea in the aqueous formaldehyde solution was 4:1.

[0055] Nano zinc oxide with a particle size of 50 nm was dispersed in a melamine-modified urea-formaldehyde resin prepolymer solution maintained at 40°C to obtain a capsule cell material dispersion, where the mass ratio of nano zinc oxide to the total mass of melamine and urea was 0.1:1.

[0056] The capsule core material emulsion and capsule cell material dispersion were mixed at 40°C and a rotation speed of 1800 r / min, and then a crosslinking reaction was carried out at 65°C for 240 minutes to obtain a microcapsule dispersion. Here, the mass ratio of capsule core material to melamine-modified urea-formaldehyde resin prepolymer was 1.5:1. The microcapsule dispersion was then heated and evaporated to obtain a microcapsule dispersion with a concentration of 35% by mass.

[0057] Cellulose pulp with an average degree of polymerization of 600 and an α-cellulose content of 92% by mass was activated with cellulase for 60 minutes at a pH of 4 and a temperature of 40°C. The mass ratio of the dry weight of cellulase to that of cellulose pulp was 500 g:1000 kg. After activation, the pH was adjusted to 10, and the pulp was pressed to obtain cellulose pulp with a moisture content of 30% by mass.

[0058] The microcapsule dispersion, an amide compound (RIKEN RESIN CHACHER C-40, manufactured by Miki Riken Co., Ltd., Japan), pressed cellulose pulp, and an 80% by mass aqueous solution of N-methylmorpholine-N-oxide were mixed, and then heated, vacuumed, dehydrated, dissolved, homogenized, degassed, and filtered to obtain a spinning solution. The mass ratio of the microcapsules, amide compound, and α-cellulose in the cellulose pulp was 50.6:2.53:100, and the α-cellulose content in the spinning solution was 10% by mass.

[0059] After spinning the spinning dope, the fibers were washed with water (deionized water, 20°C), bleached with a 1.0 g / L aqueous hydrogen peroxide solution at pH 8.5 and 45°C, and then coated with oil (oil bath with a 2.5 g / L oil bath at 50°C and pH 6.0). Microwave treatment at 1560 MHz was then performed for 36 minutes to obtain lyocell fibers. The spinning speed was 45 m / min, the coagulation bath concentration during spinning was 10%, and the coagulation bath temperature was 15°C. The resulting lyocell fibers had a moisture content of 8.5% by mass and a dimension of 2.22 dtex x 3 mm.

[0060] [Example 2] The capsule core material was obtained by melting n-octadecane at 42°C and mixing it with nano-zinc oxide having a particle size of 38 nm at a rotation speed of 680 r / min, where the mass ratio of paraffin to nano-zinc oxide was 0.25:1. Span-80 was dispersed in distilled water to obtain an emulsifier dispersion. The capsule core material and emulsifier dispersion were mixed at a temperature of 42°C and a rotation speed of 1980 r / min to obtain a capsule core material emulsion. The capsule core material content in the capsule core material emulsion was 32.5% by mass. The Span-80 content was 3.2% by mass, and the particle size D90 was 0.952 μm.

[0061] Glutaraldehyde, a 37% formaldehyde aqueous solution, melamine, and urea were mixed, and the pH was adjusted to 8.0 with triethanolamine. The mixture was then subjected to a polycondensation reaction at 70°C and a rotation speed of 320 rpm until the solution became transparent, yielding a melamine-modified urea-formaldehyde resin prepolymer solution. The mass ratio of glutaraldehyde to formaldehyde in the formaldehyde aqueous solution was 1:1.8, the mass ratio of melamine to urea was 0.08:1, and the mass ratio of the total mass of formaldehyde in the glutaraldehyde and formaldehyde aqueous solution to the total mass of melamine and urea was 3:1.

[0062] Nano zinc oxide with a particle size of 35 nm was dispersed in a melamine-modified urea-formaldehyde resin prepolymer solution at a temperature of 43°C to obtain a capsule cell material dispersion, where the mass ratio of nano zinc oxide to the total mass of melamine and urea was 0.16:1.

[0063] The capsule core material emulsion and capsule cell material dispersion were mixed at 42°C and a rotation speed of 1980 r / min, and then a crosslinking reaction was carried out at 68°C for 200 minutes to obtain a microcapsule dispersion. The mass ratio of the capsule core material to the melamine-modified urea-formaldehyde resin prepolymer was 1.8:1. The microcapsule dispersion was then heated and evaporated to obtain a microcapsule dispersion with a concentration of 38%.

[0064] Cellulose pulp with an average degree of polymerization of 680 and an α-cellulose content of 96% by mass was activated with cellulase for 50 minutes at a pH of 5 and a temperature of 45°C. The mass ratio of the dry weight of cellulase to that of cellulose pulp was 2000 g:1000 kg. After activation, the pH was adjusted to 10.5, and the pulp was pressed to obtain cellulose pulp with a moisture content of 40% by mass.

[0065] The microcapsule dispersion, an amide compound (RIKEN RESIN CHACHER C-40, manufactured by Miki Riken Co., Ltd., Japan), pressed cellulose pulp, and an 82% aqueous solution of N-methylmorpholine-N-oxide were mixed, followed by heating, evacuation, dehydration, dissolution, homogenization, degassing, and filtration to obtain a spinning solution. The mass ratio of the microcapsules, amide compound, and α-cellulose in the cellulose pulp was 68.5:3.4:100, and the α-cellulose content in the spinning solution was 12% by mass.

[0066] After spinning the spinning dope, the fibers were washed with water (deionized water, 30°C), bleached (1.5 g / L aqueous hydrogen peroxide solution, pH 9.0, temperature 41°C), and oiled (oil bath with 3.5 g / L oil, temperature 70°C, pH 7.0). Microwave treatment at 1650 MHz was then performed for 33 minutes to obtain lyocell fibers. The spinning speed was 40 m / min, the coagulation bath concentration during spinning was 13% by mass, and the coagulation bath temperature was 18°C. The resulting lyocell fibers had a moisture content of 9.7 and dimensions of 3.33 dtex x 42 mm.

[0067] [Example 3] The capsule core material was obtained by melting n-nonadecane at 48°C and mixing it with nano-zinc oxide having a particle size of 25 nm at a rotation speed of 800 r / min, where the mass ratio of paraffin to nano-zinc oxide was 0.28:1. Sodium lauryl sulfate was dispersed in distilled water to obtain an emulsifier dispersion. The capsule core material and emulsifier dispersion were mixed at a temperature of 46°C and a rotation speed of 21,150 r / min to obtain a capsule core material emulsion. The capsule core material content in the capsule core material emulsion was 36.8%. The sodium lauryl sulfate content was 3.75%, and the particle size D90 was 0.998 μm.

[0068] Glutaraldehyde, a 37% by weight aqueous formaldehyde solution, melamine, and urea were mixed, and the pH was adjusted to 8.0 using sodium hydroxide. The polycondensation reaction was carried out at 80°C and a rotation speed of 260 rpm until the solution became transparent, yielding a melamine-modified urea-formaldehyde resin prepolymer solution. The mass ratio of glutaraldehyde to formaldehyde in the aqueous formaldehyde solution was 1:2.5, the mass ratio of melamine to urea was 0.12:1, and the mass ratio of the total mass of formaldehyde in the aqueous glutaraldehyde and formaldehyde solution to the total mass of melamine and urea was 2.5:1.

[0069] Nano zinc oxide with a particle size of 20 nm was dispersed in a melamine-modified urea-formaldehyde resin prepolymer solution at 47°C to obtain a capsule cell material dispersion, where the mass ratio of nano zinc oxide to the total mass of melamine and urea was 0.25:1.

[0070] The capsule core material emulsion and capsule cell material dispersion were mixed at 48°C and a rotation speed of 2150 r / min, and then a crosslinking reaction was carried out at 72°C for 180 minutes to obtain a microcapsule dispersion. The mass ratio of the capsule core material to the melamine-modified urea-formaldehyde resin prepolymer was 2.1:1. The microcapsule dispersion was then heated and evaporated to obtain a microcapsule dispersion with a concentration of 42% by mass.

[0071] Cellulose pulp with an average degree of polymerization of 750 and an α-cellulose content of 98% was activated with cellulase for 40 minutes at a pH of 5.5 and a temperature of 50°C. The mass ratio of the dry weight of cellulase to that of cellulose pulp was 4000 g:1000 kg. After activation, the pH was adjusted to 11.5, and the pulp was pressed to obtain cellulose pulp with a moisture content of 50% by weight.

[0072] The microcapsule dispersion, an amide compound (RIKEN RESIN CHACHERC-40, manufactured by Miki Riken Co., Ltd., Japan), pressed cellulose pulp, and an 85% aqueous solution of N-methylmorpholine-N-oxide were mixed, followed by heating, vacuuming, dehydration, dissolution, homogenization, degassing, and filtration to obtain a spinning solution. The mass ratio of the microcapsules, amide compound, and α-cellulose in the cellulose pulp was 91.0:4.55:100, and the α-cellulose content in the spinning solution was 16%.

[0073] After spinning the spinning dope, the fibers were washed with water (deionized water, 40°C), bleached (1.8 g / L aqueous hydrogen peroxide solution, pH 9.5, temperature 36°C), and oiled (oil bath with 5.0 g / L oil, temperature 65°C, pH 8.0). Microwave treatment at 1720 MHz was then performed for 26 minutes to obtain lyocell fibers. The spinning speed was 32 m / min, the coagulation bath concentration during spinning was 18% by mass, and the coagulation bath temperature was 22°C. The resulting lyocell fibers had a moisture content of 10.2% by mass and dimensions of 5.56 dtex x 60 mm.

[0074] [Example 4] The capsule core material was obtained by melting n-eicosane at 50°C and mixing it with nano-zinc oxide having a particle size of 15 nm at a rotation speed of 850 r / min, where the mass ratio of paraffin to nano-zinc oxide was 0.3:1. Polysorbate-80 was dispersed in distilled water to obtain an emulsifier dispersion. The capsule core material and emulsifier dispersion were mixed at a temperature of 50°C and a rotation speed of 2300 r / min to obtain a capsule core material emulsion. The capsule core material content in the capsule core material emulsion was 40% by mass. The polysorbate-80 content was 4% by mass, and the particle size D90 was 1.055 μm.

[0075] Glutaraldehyde, a 37% formaldehyde aqueous solution, melamine, and urea were mixed, and the pH was adjusted to 8.5 using sodium hydroxide. The mixture was then subjected to a polycondensation reaction at 90°C and a rotation speed of 200 rpm until the solution became transparent, yielding a melamine-modified urea-formaldehyde resin prepolymer solution. The weight ratio of glutaraldehyde to formaldehyde in the formaldehyde aqueous solution was 1:3, the weight ratio of melamine to urea was 0.15:1, and the weight ratio of the total weight of formaldehyde in the glutaraldehyde and formaldehyde aqueous solution to the total weight of melamine and urea was 2:1.

[0076] Nano zinc oxide with a particle size of 15 nm was dispersed in a melamine-modified urea-formaldehyde resin prepolymer solution at 50°C to obtain a capsule cell material dispersion, where the mass ratio of nano zinc oxide to the total mass of melamine and urea was 0.3:1.

[0077] The capsule core material emulsion and capsule cell material dispersion were mixed at 50°C and a rotation speed of 2300 r / min, and then a crosslinking reaction was carried out at 75°C for 150 minutes to obtain a microcapsule dispersion. The mass ratio of the capsule core material to the melamine-modified urea-formaldehyde resin prepolymer was 2.3:1. The microcapsule dispersion was then heated and evaporated to obtain a microcapsule dispersion with a concentration of 45% by mass.

[0078] Cellulose pulp with an average degree of polymerization of 800 and an α-cellulose content of 99% was activated with cellulase for 30 minutes at a pH of 6 and a temperature of 55°C. The mass ratio of the dry weight of cellulase to that of cellulose pulp was 6000 g:1000 kg. After activation, the pH was adjusted to 12, and the pulp was pressed to obtain cellulose pulp with a moisture content of 60% by mass.

[0079] The microcapsule dispersion, an amide compound (RIKEN RESIN CHACHERC-40, manufactured by Miki Riken Co., Ltd., Japan), pressed cellulose pulp, and an 87% by mass aqueous solution of N-methylmorpholine-N-oxide were mixed, and then heated, vacuumed, dehydrated, dissolved, homogenized, degassed, and filtered to obtain a spinning solution. The mass ratio of the microcapsules, amide compound, and α-cellulose in the cellulose pulp was 101.8:5.1:100, and the α-cellulose content in the spinning solution was 20% by mass.

[0080] After spinning the spinning dope, the fibers were washed with deionized water (50°C), bleached with a 2.0 g / L aqueous hydrogen peroxide solution at pH 10.0 and 30°C, and then coated with oil (6.0 g / L oil bath at 65°C and pH 9.0). Microwave treatment at 1800 MHz was then performed for 20 minutes to obtain lyocell fibers. The spinning speed was 25 m / min, the coagulation bath concentration during spinning was 20% by mass, and the coagulation bath temperature was 25°C. The resulting lyocell fibers had a moisture content of 11.6% and a size of 6.67 dtex x 60 mm.

[0081] In the examples and comparative examples, various physical properties were measured or calculated as follows.

[0082] According to GB / T14337-2008 "Testing method for tensile properties of chemical staple fibers," the dry breaking strength, wet breaking strength, and transverse swelling ratio of the lyocell fibers produced in Examples 1 to 4 were measured. The results are shown in Table 1.

[0083] According to the oscillation method in Part 3 of GB / T20944.3-2008 "Evaluation of antibacterial performance of textile products," the inhibition rates of Staphylococcus aureus, Escherichia coli, and Candida albicans of the lyocell fibers produced in Examples 1 to 4 were determined. The results are shown in Table 1.

[0084] According to GB / T19466.3-2004 "Plastics Differential Scanning Calorimetry (DSC) Part 3: Measurement of Melting and Crystallization Temperature and Enthalpy," the phase change melting temperature, melting phase change enthalpy, phase change crystallization temperature, and crystallization phase change enthalpy of the lyocell fibers produced in Examples 1 to 4 were measured. The results are shown in Table 1.

[0085] The formalin measurement method was a test to measure the amount of free formaldehyde extracted in the liquid phase from textile products. The results are shown in Table 1.

[0086] The amount of formaldehyde in the lyocell fibers produced in Examples 1 to 4 was measured according to the Ministry of Health, Labor and Welfare Ordinance No. 34, "Enforcement Regulations of the Law Concerning the Control of Household Products Containing Harmful Substances," or JIS L1041, "Testing Methods for Resin-Finished Woven and Knitted Fabrics." The results are shown in Table 1.

[0087] According to the washing method in Appendix C4. Simple washing conditions and program of Standard FZ / T73023-2006, the lyocell fibers produced in Examples 1 to 4 were washed 50 times and then subjected to performance tests. The results are shown in Table 2.

[0088] [Table 1]

[0089] Table 1 shows the performance parameters of the lyocell fibers produced in Examples 1 to 4. As shown in Table 1, the lyocell fibers of the present invention have good tensile properties and antibacterial properties, as well as highly efficient energy storage and temperature regulating properties. The lyocell fibers of the present invention were also found to have a formalin absorption effect. Furthermore, the lyocell fibers of the present invention were found to have an enthalpy value of more than 40 J / g. The higher the enthalpy value, the better the temperature regulating effect of the lyocell fibers.

[0090] [Table 2]

[0091] Table 2 shows the performance parameters after 50 washes of the lyocell fibers prepared in Examples 1 to 4. As can be seen from comparing Tables 1 and 2, the lyocell fibers of the present invention were able to maintain good tensile properties, antibacterial properties, and highly efficient energy storage and temperature regulation properties even after 50 washes.

[0092] Although the present invention has been described in detail based on the above examples, these are only a part of the embodiments of the present invention, and are not all of the embodiments, and it should be understood that other embodiments can be obtained based on these embodiments, and all of these embodiments fall within the scope of protection of the present invention. [Explanation of symbols]

[0093] 1···Microcapsule, 2···Lyocell fiber matrix, 3···Formalin scavenger, 4···Microcapsule core, 5···Microcapsule cell.

Claims

1. A lyocell fiber comprising cellulose, microcapsules having a core-cell structure, and a formalin scavenger, the microcapsules are crosslinked with the cellulose and the formalin scavenger; the microcapsule core comprises a phase change material and a nano-nucleating agent; The cells of the microcapsules contain a melamine-modified urea-formaldehyde resin prepolymer.

2. The lyocell fiber according to claim 1, characterized in that the mass ratio of the cellulose, microcapsules, and formalin scavenger is in the range of 100:49.8-99.7:2.5-5.

3. 2. The lyocell fiber of claim 1, wherein the cells of the microcapsules further contain nano zinc oxide particles.

4. the phase change material includes at least one selected from the group consisting of paraffin, n-octadecane, n-nonadecane, and n-eicosane; the nano-nucleating agent comprises at least one selected from the group consisting of nano-zinc oxide, nano-titanium dioxide, nano-calcium carbonate, and nano-silica; The particle size of the nano-nucleating agent is in the range of 15 to 50 nm; The lyocell fiber according to any one of claims 1 to 3, characterized in that the mass ratio of the content of the nano-nucleating agent to the content of the phase change material is in the range of 0.2-0.3:

10.

5. 2. The lyocell fiber according to claim 1, wherein the mass ratio of the content of the formalin scavenger to the content of the microcapsules is in the range of 1 to 1.5:

20.

6. The lyocell fiber according to claim 3, characterized in that the mass ratio of the nano zinc oxide particles in the cells of the microcapsules to the content of the melamine-modified urea formaldehyde resin prepolymer is in the range of 0.1 to 0.3:

1.

7. The lyocell fiber according to any one of claims 1 to 6, wherein the formalin scavenger is an amide compound.

8. a spinning dope preparation step in which cellulose pulp, N-methylmorpholine-N-oxide, microcapsules having a core-cell structure, and a formalin scavenger are mixed and post-treated; a spinning step of spinning the spinning dope obtained through the spinning dope preparation step; and The method for producing lyocell fiber includes a microwave treatment step in which the yarn obtained through the spinning step is subjected to a microwave treatment step.

9. The method for producing lyocell fiber according to claim 8, characterized in that the frequency of the microwave irradiated in the microwave treatment step is in the range of 1560 to 1800 MHz, and the treatment time of the microwave treatment step is in the range of 20 to 36 minutes.

10. the cellulose pulp contains an α-cellulose content of 92 to 99% by mass, The method for producing lyocell fiber according to claim 8, characterized in that the ratio of the content of the microcapsules, the content of the formalin scavenger, and the content of the α-cellulose contained in the cellulose pulp is 50.6 to 101.8:2.5 to 5:100 by mass ratio.

11. The method further includes a microcapsule production step of producing microcapsules having the core-cell structure, The microcapsule manufacturing process includes: an emulsion preparation step of mixing a phase change material, a nano-nucleating agent, an emulsifier, and water to obtain an emulsion for capsule cores; a prepolymer preparation step of mixing glutaraldehyde, formaldehyde, melamine, urea, and water to carry out a polycondensation reaction to obtain a melamine-modified urea-formaldehyde resin prepolymer; and 9. The method for producing lyocell fiber according to claim 8, further comprising a crosslinking reaction step of crosslinking the capsule core emulsion obtained through the emulsion preparation step, the melamine-modified urea-formaldehyde resin prepolymer obtained through the prepolymer preparation step, and nano-zinc oxide.

12. The emulsion preparation step includes: a capsule core material preparation step of mixing the molten phase change material and the nano-nucleating agent to obtain a capsule core material; The method for producing lyocell fiber according to claim 11, further comprising a capsule core material emulsion preparation step of mixing the capsule core material, an emulsifier, and water to obtain a capsule core material emulsion.

13. The crosslinking reaction step a capsule cell material dispersion preparation step of dispersing nano-zinc oxide in a melamine-modified urea-formaldehyde resin prepolymer to obtain a capsule cell material dispersion; The method for producing lyocell fiber according to claim 11, further comprising a mixing step of mixing the capsule cell material dispersion with the capsule core material emulsion.

14. the reaction temperature of the polycondensation reaction in the prepolymer preparation step is in the range of 40 to 50°C; The method for producing lyocell fiber according to claim 11, characterized in that the reaction temperature of the crosslinking reaction in the crosslinking reaction step is in the range of 65 to 75°C and the reaction time is in the range of 150 to 240 minutes.

15. The method for producing lyocell fiber according to any one of claims 8 to 14, characterized in that the post-treatment includes at least one selected from the group consisting of heating, vacuuming, dehydration, dissolving, homogenizing, degassing, and filtration processes.

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