WO2019127633A1 - 抗菌防螨防霉的再生纤维素纤维的制备方法及其应用 - Google Patents

抗菌防螨防霉的再生纤维素纤维的制备方法及其应用 Download PDF

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Publication number
WO2019127633A1
WO2019127633A1 PCT/CN2018/071364 CN2018071364W WO2019127633A1 WO 2019127633 A1 WO2019127633 A1 WO 2019127633A1 CN 2018071364 W CN2018071364 W CN 2018071364W WO 2019127633 A1 WO2019127633 A1 WO 2019127633A1
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Prior art keywords
mixed powder
spinning dope
extract
cellulose
slurry
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PCT/CN2018/071364
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English (en)
French (fr)
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吴娇
张晨
胡流云
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无限极（中国）有限公司
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Application filed by 无限极（中国）有限公司 filed Critical 无限极（中国）有限公司
Priority to KR1020187013163A priority Critical patent/KR102133237B1/ko
Priority to JP2018514903A priority patent/JP6797192B2/ja
Priority to EP18708897.6A priority patent/EP3524714A4/en
Priority to US15/760,845 priority patent/US10563322B2/en
Publication of WO2019127633A1 publication Critical patent/WO2019127633A1/zh

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A01N65/10—Apiaceae or Umbelliferae [Carrot family], e.g. parsley, caraway, dill, lovage, fennel or snakebed
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A01N65/22—Lamiaceae or Labiatae [Mint family], e.g. thyme, rosemary, skullcap, selfheal, lavender, perilla, pennyroyal, peppermint or spearmint
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
    • C08G12/12—Ureas; Thioureas
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/13—Physical properties anti-allergenic or anti-bacterial

Definitions

  • the invention belongs to the technical field of preparation of functional regenerated cellulose fibers, in particular to a method for preparing antibacterial, anti-mite and anti-mildew functions by using cumin extract, Litsea cubeba extract and thyme essential oil as raw materials.
  • locusts and human health are very close.
  • the harm to human body is mainly reflected in parasitic, stinging, poisonous phlegm, blood-sucking, allergic diseases and disease transmission.
  • Bacteria and molds are widely found in nature, and their presence can have many adverse effects on textiles, such as fiber degradation, unsightly color, and unpleasant odor. When people come into contact with moldy and textiles with a lot of bacteria, they can cause diseases and endanger human health.
  • Chinese Patent Application No. CN201610494383.1 discloses a regenerated cellulose fiber having antibacterial, antifungal and anti-mite functions and a preparation method thereof.
  • the preparation method comprises the following steps: 1) preparing a cassia seed-Houttuynia microcapsule; 2) preparing a viscose spinning stock solution: a mixture of bitter wood pulp and other pulp, and then making a glue to obtain a viscose spinning a raw liquid, the other pulp selected from the group consisting of: one or more of wood pulp, cotton pulp and bamboo pulp; 3) preparing a blend spinning dope; the cassia seed-Houttuynia microcapsule and the stick The rubber spinning dope is mixed to prepare a blend spinning dope; 4) Spinning and post-treatment: the blend spinning dope is spun into a bundle after being solidified, and the product is obtained after post-treatment.
  • the microcapsule preparation technology and the (bitter wood) pulp preparation technology are respectively used, the production process is complicated, the production efficiency is low, and the production cost is high, especially in the preparation of bitter wood pulp, the solvent method is used to extract cellulose. Not only is the production cost high, but the recovery of ionic liquids is difficult, further increasing the cost. At the same time, as the amount of functional component added increases, the physical and mechanical properties of the fiber are lowered.
  • the regenerated cellulose fiber also has a single function.
  • the improvement of anti-mite and anti-mildew effects with the improvement of people's living standards, regenerated cellulose fibers with antibacterial, anti-mite and anti-mildew functions have become the goal and direction pursued by fiber workers.
  • the fennel is spicy and warm, and has the effects of dispelling cold and relieving pain, and stomach and qi.
  • the active ingredient such as anisole in cumin has good antibacterial and sputum-repellent effects, and has a good inhibitory effect on Escherichia coli and Shigella, and has a good detachment effect on aphids.
  • Litsea cubeba is spicy, slightly bitter, aroma, non-toxic, and has anti-asthmatic, anti-allergic, anti-bacterial and anti-viral effects.
  • the main ingredient of plant thyme essential oil is thymol, which has strong sterilization, killing and fungicidal action. It kills germs and microorganisms.
  • the invention aims at the above deficiencies, and combines the excellent properties of cumin, Litsea cubeba, and thyme to provide a preparation method of functional regenerated cellulose fiber using thyme, cumin and Litsea cubeba as raw materials, and realizes the following technology. effect:
  • the preparation method of the invention has the advantages of reliable and simple operation, high production efficiency, low production cost, and high physical and mechanical properties of the fiber, and is harmless to human health.
  • the plant-based multifunctional regenerated cellulose fiber prepared by the invention has the versatility of antibacterial, anti-mildew and anti-mite: the fiber has a evasion rate of ⁇ 85% against aphids, and the inhibition rate is ⁇ 85% (GB/T24346-2009) "Evaluation of textile anti-mite performance”); anti-mold grade can reach level 0 and above (GB/T24346-2009 "Evaluation of textile mildew resistance”); antibacterial activity value 2.2-2.8, bactericidal activity value 0.3-0.7 .
  • the vegetable regenerated cellulose fiber prepared by the invention has excellent physical and mechanical properties, high strength, small coefficient of variation of strength, high wet modulus: fiber polymerization degree of 450-515, dry breaking strength of 3.89-4.52 cN/dtex, dry The coefficient of variation of state intensity is 11.2-13.6%, the wet rupture strength is 2.68-3.11cN/dtex, the hooking strength is 0.90-1.22cN/dtex, and the wet modulus is 0.48-0.75cN/dtex.
  • a preparation method of multi-plant regenerated cellulose fiber having antibacterial, anti-mite and anti-mildew functions comprising the following steps:
  • Step (1) preparation of a composite slurry
  • Step (2) blending the composite slurry with the denatured cellulose spinning dope to prepare a blend spinning dope
  • Step (3) blending spinning dope spinning and post-treatment.
  • the composite slurry is prepared by the following process:
  • the cumin extract and the extract of Litsea cubeba in the composite slurry preparation step i) are blended at a mass ratio of 1: (0.5-1.5), and the mixed powder has a particle diameter D90 ⁇ 1.568 ⁇ m.
  • the mass ratio of the mixed powder to the thyme essential oil in the composite slurry preparation step ii) is (5-10):1.
  • the emulsification in the composite slurry preparation step ii) is carried out by adding the above oily mixed powder slurry to an aqueous system of styrene maleic anhydride sodium salt content of 0.5-1.5%, and emulsification of the oily mixed powder slurry.
  • the mass ratio of the material to the aqueous system is 1: (2-5), and the emulsion particle size D90 ⁇ 2.038 ⁇ m.
  • the emulsion is stirred with the urea-formaldehyde resin prepolymer at 70-80 ° C, and the total mass of the cumin extract, the extract of Litsea cubeba and the essential oil of thyme in the emulsion is combined with urea formaldehyde.
  • the mass ratio of the resin prepolymer is (1-3): 1, the composite slurry has a particle diameter D90 ⁇ 2.562 ⁇ m, and a solid content of 20% to 40%.
  • the denatured cellulose spinning dope according to the step (2) is prepared by using a cellulose pulp having a polymerization degree of 800-1000 as a raw material to prepare a viscous collagen solution, and then adding a denaturant polyoxyethylene compound, wherein the denaturation is performed.
  • the amount of the agent added is 0.1-1.0% by mass of the cellulose A in the viscose collagen solution; the viscosity of the denatured cellulose spinning dope is 60-96 s, and the degree of esterification is 65-85.
  • the mass ratio of the composite slurry in the blend spinning dope described in the step (2) to the methyl cellulose in the denatured cellulose spinning dope is 4.0% to 10.0%.
  • the spinning in the step (3) uses a coagulation bath
  • the coagulation bath temperature is 20-40 ° C
  • the coagulation bath component comprises 5.0%-8.0% sulfuric acid, 0.5%-1.0% aluminum sulfate, and 10.0%-16.0 sodium sulfate. %, polyoxyethylene compound 0.1-0.5%, the balance is water.
  • the post-treatment of step (3) comprises desulfurization, oil bath, water washing and drying.
  • the prepared cumin extract and the extract of Litsea cubeba are extracted into 10 kg of fennel plant traditional Chinese medicine or Liriodendron chinense plant extract, respectively, and 1 kg of cumin extract and Litsea cubeba extract are extracted, wherein the total active ingredient content is ⁇ 30. %.
  • the thyme essential oil involved in the above steps is obtained by a technique known in the art such as steam distillation or solvent extraction.
  • the urea-formaldehyde resin prepolymer involved in the above steps is prepared by a known technique.
  • the conventional preparation method is as follows: urea, glutaraldehyde and distilled water are uniformly mixed, wherein the ratio of urea and glutaraldehyde is (2-3):1, and the pH is adjusted to 8-9 by adding triethanolamine or sodium hydroxide, and then the temperature is raised to The reaction is carried out at 60-70 ° C. After the solution becomes clear, PVA is added. The amount of PVA added is 2.0%-8.0% of the urea content, the temperature is lowered to 75-85 ° C, the temperature is reacted for 30-50 minutes, and then the pH of the system is adjusted with sodium hydroxide. Neutral and cool to 40-45 ° C for use.
  • the present invention also relates to the use of the regenerated cellulose fibers obtained by the above preparation method in antibacterial, anti-mite and mildew resistant fabrics.
  • the invention adopts the above technical solutions, and has the following beneficial effects compared with the prior art:
  • the preparation method of the invention has the advantages of reliable and simple operation, low production cost, aluminum sulfate instead of zinc sulfate in the preparation process, avoids environmental pollution, and the physical and mechanical properties of the fiber are relatively large. Improve, and achieve the plant versatility of the fiber composite, good durability, excellent water wash performance (> 50 times). At the same time, the functional components come from nature and are not harmful to human health.
  • the plant multi-functional regenerated cellulose fiber prepared by the invention has the versatility of antibacterial, anti-mildew and anti-mite: the repellent rate of the fiber to the aphid is ⁇ 85%, the inhibition rate is ⁇ 85%; It reaches the level of 0 and above; the bacteriostatic activity value is 2.2-2.8, and the bactericidal activity value is 0.3-0.7.
  • the plant-based multifunctional regenerated cellulose fiber prepared by the invention has excellent physical and mechanical properties, high strength, small coefficient of variation of strength, high wet modulus: fiber polymerization degree of 450-515, dry breaking strength of 2.89-3.52 cN/dtex
  • the dry state intensity coefficient is 11.2-13.6%
  • the wet state strength is 1.68-2.11 cN/dtex
  • the hooking strength is 0.90-1.22 cN/dtex
  • the wet modulus is 0.38-0.55 cN/dtex.
  • the invention also relates to the use of cumin, Litsea cubeba and plant thyme essential oil as functional modified addition components in the preparation of regenerated cellulose fibers having antibacterial, anti-mite, and anti-mildew functions.
  • the present invention finds that fennel, Litsea cubeba and thyme are used in combination as a raw material source to prepare regenerated cellulose fibers having antibacterial, anti-mite, and anti-mildew functions; thereby preparing regenerated cellulose fibers for aphids It has high repellent rate and inhibition rate, and the mildew resistance grade can reach 0 grade, and it also has excellent antibacterial and bactericidal activity against bacteria.
  • the regenerated cellulose fiber obtained by the invention has excellent physical and mechanical properties, high strength, small coefficient of variation of strength, and high wet modulus, and is of great significance to the development of the textile industry in China and the health of people.
  • a method for preparing regenerated cellulose fiber having an antibacterial, anti-mite and anti-mildew function with a specification of 1.11 dtex ⁇ 38 mm comprising the following steps:
  • the mixed powder prepared above is uniformly blended with the thyme essential oil, and the surface of the mixed powder is coated with a layer of thyme essential oil to prepare an oily mixed powder slurry, wherein the mass ratio of the mixed powder to the thyme essential oil is 5:1. .
  • the oily mixed powder slurry emulsion of the scorpion is a plant core
  • the urea-formaldehyde resin is a plant-based composite slurry of the capsule wall
  • the cumin extract the extract of Litsea cubeba and the thyme in the oil-mixed powder slurry emulsion
  • the mass ratio of the total mass of the essential oil to the urea-formaldehyde resin prepolymer is 1:1
  • the cellulose pulp is used as a raw material to obtain a viscous collagen solution through a viscose preparation process, and a denaturant is added to the viscous collagen solution for denaturation to prepare a denatured cellulose spinning dope.
  • the polymerization degree of the cellulose pulp is 800; the denaturing agent used is a polyoxyethylene compound, the added amount is 0.1% compared with the mass ratio of the cellulose A in the viscose collagen solution; and the viscosity of the denatured cellulose spinning dope is 60s.
  • the degree of esterification is 65.
  • the composite slurry prepared in the step 1 is added to the denatured cellulose spinning dope prepared in the step 2 by a pre-spinning injection system, wherein the pre-spinning injection system comprises a filtering device, a metering device and a mixing device to realize the botanical composite slurry. Filtration, precise metering and uniform mixing with denatured cellulose spinning stock. The mass ratio of the composite slurry to the cellulose A in the denatured cellulose spinning dope was 4.0%.
  • the pre-spinning injection system filtration device allowed the particle size of the particles to pass through 2.658 ⁇ m.
  • the mixing device consists of a dynamic mixer with a mixing time of 30 s.
  • the blended spinning dope is spun through an adjusted coagulation bath, and the primary tow is subjected to drawing to obtain a shaped tow.
  • the obtained tow is subjected to a scouring bath such as cutting, tempering desulfurization process, oiling bath, water washing, and drying to obtain a plant regenerated cellulose fiber having anti-mite, mildewproof and antibacterial functions.
  • the coagulation bath temperature was 20 ° C, and the coagulation bath component included 5.0% sulfuric acid, 0.5% aluminum sulfate, 10.0% sodium sulfate, 0.1% polyoxyethylene compound, and the balance was water.
  • the fiber has a repellent rate of 85% against aphids and an inhibition rate of 85%; the mildew resistance level can reach level 1; the antibacterial activity value is 2.2, and the bactericidal activity value is 0.3.
  • the degree of fiber polymerization is 515, the dry breaking strength is 3.52 cN/dtex, the coefficient of variation of dry strength is 11.2%, the strength of wet state is 2.11 cN/dtex, the hooking strength is 1.22 cN/dtex, and the wet modulus is 0.55 cN/dtex.
  • a method for preparing a plant regenerated cellulose fiber having an antibacterial, anti-mite, and anti-mildew function with a specification of 1.33 dtex ⁇ 38 mm comprising the following steps:
  • the mixed powder prepared above is uniformly blended with the thyme essential oil, and the surface of the mixed powder is coated with a layer of thyme essential oil to prepare an oily mixed powder slurry, wherein the mass ratio of the mixed powder to the thyme essential oil is 6:1. ;
  • the oily mixed powder slurry emulsion of the scorpion is a plant core
  • the urea-formaldehyde resin is a plant-based composite slurry of the capsule wall
  • the cumin extract the extract of Litsea cubeba and the thyme in the oil-mixed powder slurry emulsion
  • the cellulose pulp is used as a raw material to obtain a viscous collagen solution through a viscose preparation process, and a denaturant is added to the viscous collagen solution for denaturation to prepare a denatured cellulose spinning dope.
  • the polymerization degree of the cellulose pulp is 826; the denaturing agent used is a polyoxyethylene compound, the added amount is 0.26% compared with the mass ratio of the cellulose A in the viscose collagen solution; and the viscosity of the denatured cellulose spinning dope is 68s.
  • the degree of esterification was 73.
  • the composite slurry prepared in the step 1 is added to the denatured cellulose spinning dope prepared in the step 2 by a pre-spinning injection system, wherein the pre-spinning injection system comprises a filtering device, a metering device and a mixing device to realize the botanical composite slurry. Filtration, precise metering and uniform mixing with denatured cellulose spinning stock. The mass ratio of the composite slurry to the cellulose A in the denatured cellulose spinning dope was 5.8%.
  • the pre-spinning injection system filtration device allowed the particle size of the particles to pass through 2.756 ⁇ m.
  • the mixing device consisted of a static mixer with a mixing time of 78 s.
  • the blended spinning dope is spun through an adjusted coagulation bath, and the primary tow is subjected to drawing to obtain a shaped tow.
  • the obtained tow is subjected to a scouring bath such as cutting, tempering desulfurization process, oiling bath, water washing, and drying, thereby obtaining plant regenerated cellulose fibers having anti-mite, anti-mildew and anti-bacterial functions.
  • the coagulation bath temperature was 26 ° C, and the coagulation bath component included sulfuric acid 5.2%, aluminum sulfate 0.62%, sodium sulfate 10.0%, polyoxyethylene compound 0.15%, and the balance being water.
  • the fiber has a repellent rate of 88% against aphids and an inhibition rate of 87%; the mildew resistance level can reach level 1; the antibacterial activity value is 2.4, and the bactericidal activity value is 0.4.
  • the degree of fiber polymerization is 502, the dry rupture strength is 3.44 cN/dtex, the dry state strength coefficient is 12.1%, the wet state strength is 2.02 cN/dtex, the hooking strength is 1.15 cN/dtex, and the wet modulus is 0.52 cN/dtex.
  • a preparation method of a regenerated cellulose fiber having an antibacterial, anti-mite and anti-mildew function of 1.56 dtex ⁇ 38 mm comprising the following steps:
  • the mixed powder prepared above is uniformly blended with the thyme essential oil, and the surface of the mixed powder is coated with a layer of thyme essential oil to prepare an oily mixed powder slurry, wherein the mass ratio of the mixed powder to the thyme essential oil is 7:1. ;
  • the oily mixed powder slurry emulsion of the scorpion is a plant core
  • the urea-formaldehyde resin is a plant-based composite slurry of the capsule wall
  • the cumin extract the extract of Litsea cubeba and the thyme in the oil-mixed powder slurry emulsion
  • the cellulose pulp is used as a raw material to obtain a viscous collagen solution through a viscose preparation process, and a denaturant is added to the viscous collagen solution for denaturation to prepare a denatured cellulose spinning dope.
  • the polymerization degree of the cellulose pulp is 896; the denaturing agent used is a polyoxyethylene compound, and the added amount is 0.51% compared with the mass ratio of the cellulose A in the viscose collagen solution; the viscosity of the denatured cellulose spinning dope is 76s.
  • the degree of esterification is 78.
  • the botanical composite slurry prepared in the step 1 is added to the denatured cellulose spinning dope prepared in the step 2 by a pre-spinning injection system, wherein the pre-spinning injection system comprises a filtering device, a metering device and a mixing device to realize the botanical composite pulp. Filtration, precise metering and uniform mixing with denatured cellulose spinning stock. The mass ratio of the composite slurry to the cellulose A in the denatured cellulose spinning dope was 7.5%.
  • the pre-spinning injection system filtration device allows the particle size of the particles to pass through 2.632 ⁇ m.
  • the mixing device consists of two series of dynamic mixer and static mixer with a mixing time of 155s.
  • the blended spinning dope is spun through an adjusted coagulation bath, and the primary tow is subjected to drawing to obtain a shaped tow.
  • the obtained tow is subjected to a scouring bath such as cutting, tempering desulfurization process, oiling bath, water washing, and drying to obtain a plant regenerated cellulose fiber having anti-mite, mildewproof and antibacterial functions.
  • the coagulation bath temperature was 31 ° C, and the coagulation bath component included 6.5% sulfuric acid, 0.76% aluminum sulfate, 13.2% sodium sulfate, 0.25% polyoxyethylene compound, and the balance was water.
  • the fiber has a repellent rate of 92% against aphids and an inhibition rate of 92%; the mildew resistance level can reach level 0; the antibacterial activity value is 2.5, and the bactericidal activity value is 0.5.
  • the degree of fiber polymerization is 488, the dry rupture strength is 3.32 cN/dtex, the dry state strength coefficient is 12.5%, the wet state strength is 1.89 cN/dtex, the hooking strength is 1.07 cN/dtex, and the wet modulus is 0.45 cN/dtex.
  • a preparation method of a regenerated cellulose fiber having an antibacterial, anti-mite and anti-mildew function of 1.67 dtex ⁇ 38 mm comprising the following steps:
  • the mixed powder prepared above is uniformly blended with the thyme essential oil, and the surface of the mixed powder is coated with a layer of thyme essential oil to prepare an oily mixed powder slurry, wherein the mass ratio of the mixed powder to the thyme essential oil is 8.5:1. ;
  • the oily mixed powder slurry emulsion of the scorpion is a plant core
  • the urea-formaldehyde resin is a plant-based composite slurry of the capsule wall
  • the cumin extract the extract of Litsea cubeba and the thyme in the oil-mixed powder slurry emulsion
  • the mass ratio of the total mass of the essential oil to the urea-formaldehyde resin prepolymer is 2:1
  • the cellulose pulp is used as a raw material to obtain a viscous collagen solution through a viscose preparation process, and a denaturant is added to the viscous collagen solution for denaturation to prepare a denatured cellulose spinning dope.
  • the polymerization degree of the cellulose pulp is 937; the denaturing agent used is a polyoxyethylene compound, the added amount is 0.78% compared with the mass ratio of the cellulose in the viscose collagen solution; and the viscosity of the denatured cellulose spinning dope is 88s.
  • the degree of esterification is 81.
  • the composite slurry prepared in the step 1 is added to the denatured cellulose spinning dope prepared in the step 2 by a pre-spinning injection system, wherein the pre-spinning injection system comprises a filtering device, a metering device and a mixing device to realize the botanical composite slurry. Filtration, precise metering and uniform mixing with denatured cellulose spinning stock.
  • the mass ratio of the composite pulp to the cellulose A in the denatured cellulose spinning dope was 8.9%, and the particle size of the particles allowed to pass through the pre-spinning injection system filtration device was 2.852 ⁇ m.
  • the mixing device consists of two series of dynamic mixer and static mixer, mixing time 196s.
  • the blended spinning dope is spun through an adjusted coagulation bath, and the primary tow is subjected to drawing to obtain a shaped tow.
  • the obtained tow is subjected to a scouring bath such as cutting, tempering desulfurization process, oiling bath, water washing, and drying to obtain plant regenerated cellulose fibers having anti-mite, mildewproof and antibacterial functions.
  • the coagulation bath temperature was 36 ° C, and the coagulation bath component included sulfuric acid 7.2%, aluminum sulfate 0.78%, sodium sulfate 13.8%, polyoxyethylene compound 0.32%, and the balance was water.
  • the fiber has a repellent rate of 95% against aphids and a inhibition rate of 94%; the mildew resistance level can reach level 0; the bacteriostatic activity value is 2.7, and the bactericidal activity value is 0.6.
  • the fiber polymerization degree is 475, the dry rupture strength is 3.09 cN/dtex, the dry state intensity coefficient is 13.3%, the wet state strength is 1.75 cN/dtex, the hooking strength is 0.98 cN/dtex, and the wet modulus is 0.40 cN/dtex.
  • a preparation method of a regenerated cellulose fiber having an antibacterial, anti-mite and anti-mildew function of 2.22 dtex ⁇ 38 mm comprising the following steps:
  • the mixed powder prepared above is uniformly blended with the thyme essential oil, and the surface of the mixed powder is coated with a layer of thyme essential oil to prepare an oily mixed powder slurry, wherein the mass ratio of the mixed powder to the thyme essential oil is 10:1. ;
  • the oily mixed powder slurry emulsion of the scorpion is a plant core
  • the urea-formaldehyde resin is a plant-based composite slurry of the capsule wall
  • the cumin extract the extract of Litsea cubeba and the thyme in the oil-mixed powder slurry emulsion
  • the mass ratio of the total mass of the essential oil to the urea-formaldehyde resin prepolymer is 3:1
  • the cellulose pulp is used as a raw material to obtain a viscous collagen solution through a viscose preparation process, and a denaturant is added to the viscous collagen solution for denaturation to prepare a denatured cellulose spinning dope.
  • the polymerization degree of the cellulose pulp is 1000; the denaturing agent used is a polyoxyethylene compound, the added amount is 1.0% compared with the mass ratio of the cellulose A in the viscose collagen solution; and the viscosity of the denatured cellulose spinning dope is 96s.
  • the degree of esterification is 85.
  • the composite slurry prepared in the step 1 is added to the denatured cellulose spinning dope prepared in the step 2 by a pre-spinning injection system, wherein the pre-spinning injection system comprises a filtering device, a metering device and a mixing device to realize the botanical composite slurry. Filtration, precise metering and uniform mixing with denatured cellulose spinning stock. The mass ratio of the composite slurry to the cellulose A in the denatured cellulose spinning dope was 10.0%.
  • the pre-spinning injection system filtration device allowed the particle size of the particles to pass through 2.968 ⁇ m.
  • the mixing device consists of two series of dynamic mixers and static mixers with a mixing time of 300 s.
  • the blended spinning dope is spun through an adjusted coagulation bath, and the primary tow is subjected to drawing to obtain a shaped tow.
  • the obtained tow is subjected to a scouring bath such as cutting, tempering desulfurization process, oiling bath, water washing, and drying to obtain a plant regenerated cellulose fiber having anti-mite, mildewproof and antibacterial functions.
  • the coagulation bath temperature was 40 ° C, and the coagulation bath component included sulfuric acid 8.0%, aluminum sulfate 1.0%, sodium sulfate 16.0%, polyoxyethylene compound 0.5%, and the balance was water.
  • the fiber has a repellent rate of 98% against aphids and an inhibition rate of 98%; the mildew resistance level can reach level 0; the bacteriostatic activity value is 2.8, and the bactericidal activity value is 0.7.
  • the fiber polymerization degree is 450, the dry rupture strength is 2.89 cN/dtex, the dry state intensity coefficient is 13.6%, the wet state strength is 1.68 cN/dtex, the hooking strength is 0.90 cN/dtex, and the wet modulus is 0.38 cN/dtex.

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Abstract

本发明提供了由小茴香提取物、山苍子提取物以及百里香精油制备具有抗菌防螨防霉功能的再生纤维素纤维的方法。本发明还涉及利用上述方法所制备的再生纤维素纤维在抗菌、防螨和防霉织物领域中的应用。本发明解决了现有技术中再生纤维素纤维功能单一、防螨和防霉效果差的技术缺陷。

Description

抗菌防螨防霉的再生纤维素纤维的制备方法及其应用 技术领域
本发明属于功能性再生纤维素纤维的制备技术领域，具体而言，涉及一种以小茴香提取物、山苍子提取物以及百里香精油为原料制备具有抗菌、防螨、和防霉功能的再生纤维素纤维的方法。
背景技术
我国再生纤维素纤维多数是普通品种，随着人民生活水平的提高和健康、环保意识的不断增强，大力推进开发健康、环保产品和绿色的功能性再生纤维素纤维已经成为大势所趋。
螨虫与人的健康关系非常密切，对人体危害主要体现在寄生、叮刺、毒蛰、吸血、过敏性疾病、传播疾病等方面。
细菌和霉菌广泛存在于自然界，它的存在会对纺织品产生很多不利影响，如纤维发生降解、产生难看的色泽、散发出难闻的气味等。人接触发霉和带有大量细菌的纺织品后，会诱发疾病，危害人类健康。
申请号为CN201610494383.1的中国专利公开了一种具有抗菌、防霉、防螨功能的再生纤维素纤维及其制备方法。在该专利技术中，所述制备方法为：1)制备决明子-鱼腥草微胶囊；2)制备黏胶纺丝原液：苦木浆粕和其它浆粕混合后制胶，得黏胶纺丝原液，所述其它浆粕选自：木浆粕、棉浆粕和竹浆粕中的一种或多种；3)制备共混纺丝原液；所述决明子-鱼腥草微胶囊和所述黏胶纺丝原液混合，制得共混纺丝原液；4)纺丝及后处理：所述共混纺丝原液经凝固浴后纺丝成束，经后处理得产品。该技术中分别用到了微胶囊制备技术和(苦木)浆粕制备技术，生产工艺复杂，生产效率低，生产成本较高，尤其是在制备苦木浆粕时用到溶剂法提取纤维素，不仅生产成本较高，而且离子液体回收较困难，进一步提高成本。同时，随着功能性组份添加量的增加，使得纤维的物理机械性能降低。
现有技术中，如申请号为CN200710190764.1、CN200710014654.X、CN200510044541.5、CN200610022614.5、CN201410187341.4、CN201510663207.1、CN201510998349.3、CN201510109483.3、再生纤维素 纤维还存在功能单一、防螨和防霉效果差等问题，随着人们生活水平的提高，具有抗菌、防螨、和防霉功能的再生纤维素纤维已成为纤维工作者追求的目标与方向。
小茴香味辛、性温，具有散寒止痛、和胃理气的功效。小茴香中的茴香醚等有效成分具有很好的抗菌、驱螨功效，对大肠杆菌、痢疾杆菌等都有很好的抑制作用，对螨虫有很好的驱离作用。山苍子性味辛、微苦，有香气，无毒，具有平喘、抗过敏、抗菌、抗病毒作用。植物性百里香精油的主要成分是百里香酚，具有很强的杀菌、杀螨、杀霉菌作用，分子杀灭病菌及微生物，进入人体精油分子能增强人体的免疫力，对皮肤系统具有杀菌、抗炎、愈合、除臭、驱虫作用；对免疫系统具有抗细菌、抗病毒、抗霉菌作用和驱虫作用。
发明内容
本发明针对以上不足，结合小茴香、山苍子、和百里香的优异性能，提供了一种以百里香、小茴香以及山苍子为原料来源的功能性再生纤维素纤维的制备方法，实现以下技术效果：
(1)本发明的制备方法较现有技术来说，生产工艺运行可靠简单，生产效率高，生产成本低，而且纤维的物理机械性能得到较大提高，对人体健康无害。
(2)本发明制备的植物性多功能再生纤维素纤维具有抗菌、防霉和防螨虫等多功能性：该纤维对螨虫的趋避率≥85％，抑制率≥85％(GB/T24346-2009《纺织品防螨性能的评价》)；防霉等级可达到0级及以上水平(GB/T24346-2009《纺织品防霉性能的评价》)；抑菌活性值2.2-2.8，杀菌活性值0.3-0.7。
(3)本发明制备的植物性再生纤维素纤维物理机械性能优良，强度高，强度变异系数小，湿模量高：纤维聚合度450-515，干态断裂强度3.89-4.52cN/dtex，干态强度变异系数11.2-13.6％，湿态断裂强度2.68-3.11cN/dtex，钩接强度0.90-1.22cN/dtex，湿模量0.48-0.75cN/dtex。
为解决上述技术问题，采用以下技术方案：
一种具有抗菌、防螨、防霉功能的多植物性再生纤维素纤维的的制备方法，包括以下步骤：
步骤(1)：复合浆料的制备；
步骤(2)：复合浆料与变性纤维素纺丝原液共混制备共混纺丝原液；
步骤(3)：共混纺丝原液纺丝及后处理。
优选地，所述的复合浆料通过以下过程制备：
i)共混小茴香提取物和山苍子提取物获得混合粉体；
ii)将步骤i)获得的混合粉体与百里香精油混合，制备油性混合粉体浆料，并进一步乳化得乳化液；
iii)将步骤ii)获得的乳化液与脲醛树脂预聚体反应，获得复合浆料。
更为优选地，复合浆料制备步骤i)中小茴香提取物和山苍子提取物以1:(0.5-1.5)的质量比进行共混，混合粉体粒径D90≤1.568μm。
更为优选地，复合浆料制备步骤ii)中所述混合粉体与所述百里香精油的混合质量比为(5-10)：1。
更为优选地，复合浆料制备步骤ii)中所述乳化为将上述油性混合粉体浆料加入到苯乙烯马来酸酐钠盐含量0.5-1.5％的水性体系中乳化，油性混合粉体浆料与水性体系的质量比为1:(2-5)，乳化液粒径D90≤2.038μm。
更为优选地，复合浆料制备步骤iii)所述乳化液与脲醛树脂预聚体在70-80℃搅拌反应，乳化液中小茴香提取物、山苍子提取物以及百里香精油的总质量与脲醛树脂预聚体的质量之比为(1-3)：1，复合浆料粒径D90≤2.562μm，固含量20％-40％。
优选地，步骤(2)所述的变性纤维素纺丝原液以聚合度为800-1000的纤维素浆粕为原料先制得粘胶原液，再添加变性剂聚氧乙烯类化合物制得，其中变性剂的添加量相较粘胶原液中甲种纤维素质量比为0.1-1.0％；所述变性纤维素纺丝原液粘度为60-96s，酯化度为65-85。
优选地，步骤(2)所述的共混纺丝原液中所述复合浆料相较变性纤维素纺丝原液中甲种纤维素质量比为4.0％～10.0％。
优选地，步骤(3)所述纺丝使用凝固浴，凝固浴温度为20-40℃，凝固浴组份包括硫酸5.0％-8.0％、硫酸铝0.5％-1.0％、硫酸钠10.0％-16.0％，聚氧乙烯类化合物0.1-0.5％，余量为水。
优选地，步骤(3)所述后处理包括脱硫、油浴、水洗及烘干。
上述步骤中所涉及的小茴香提取物和山苍子提取物，由市场购买或采用公知技术制备，常规制备方法为：
1)取小茴香或山苍子植物的有效部位，除杂、水洗，90-110℃烘干；
2)将烘干物粉碎，加8-10倍质量水90-100℃提取2-4小时；
3)过滤，提取液进造粒机喷雾干燥得提取物颗粒。
制备获得的小茴香提取物和山苍子提取物的规格为10公斤小茴香植物中药或山苍子植物中药分别提取1公斤小茴香提取物和山苍子提取物，其中总有效成分含量≥30％。
上述步骤中所涉及的百里香精油，采用本领域公知的技术如水蒸气蒸馏法、溶剂萃取法等技术提取获得。
上述步骤中所涉及的脲醛树脂预聚体，其采用公知技术制备。常规制备方法如下：将尿素、戊二醛和蒸馏水混合均匀，其中尿素、戊二醛的比例为(2-3):1，并加入三乙醇胺或氢氧化钠调节pH至8-9后升温至60-70℃进行反应，待溶液变澄清后加入PVA，PVA加入量为尿素含量的2.0％-8.0％，温度降至75-85℃，恒温反应30～50min，然后用氢氧化钠调节体系pH至中性，并降温至40-45℃备用。
本发明还涉及上述制备方法获得的再生纤维素纤维在抗菌、防螨和防霉织物中的应用。
本发明采用上述技术方案，与现有技术相比，具有以下有益效果：
(1)本发明的制备方法较现有技术来说，生产工艺运行可靠简单，生产成本较低，制备工艺中用硫酸铝代替硫酸锌，避免了环境污染，而且纤维的物理机械性能得到较大提高，并实现了纤维的植物多功能性复合，持久性好，耐水洗性能优良(＞50次)。同时，功能性组份来自于自然界，对人体健康无害。
(2)本发明制备的植物性多功能再生纤维素纤维具有抗菌、防霉和防螨虫等多功能性：该纤维对螨虫的驱避率≥85％，抑制率≥85％；防霉等级可达到0级及以上水平；抑菌活性值2.2-2.8，杀菌活性值0.3-0.7。
(3)本发明制备的植物性多功能再生纤维素纤维物理机械性能优异，强度高，强度变异系数小，湿模量高：纤维聚合度450-515，干态断裂强度2.89-3.52cN/dtex，干态强度变异系数11.2-13.6％，湿态强度1.68-2.11cN/dtex，钩接强度0.90-1.22cN/dtex，湿模量达0.38-0.55cN/dtex。
抗菌、防霉、防螨评价简介：
Figure PCTCN2018071364-appb-000001
Figure PCTCN2018071364-appb-000002
本发明还涉及小茴香、山苍子和植物性百里香精油作为功能性改性添加组份，在制备具有抗菌、防螨、和防霉功能的再生纤维素纤维中的用途。
本发明发现，组合利用小茴香、山苍子和百里香，将其作为原料来源，制备具有抗菌、防螨、和防霉多功能的再生纤维素纤维；由此制备获得的再生纤维素纤维对螨虫具有高的驱避率和抑制率，防霉等级可达到0级，同时对细菌也具有优良的抑菌和杀菌活性。此外，本发明获得的再生纤维素纤维物理机械性能优异，强度高，强度变异系数小，湿模量高，对我国纺织产业的发展及人们的身体健康具有十分重要的意义。
具体实施方式
以下对本发明的优选实施例进行说明，应当理解，此处所描述的优选实施例仅用于说明和解释本发明，并不用于限定本发明。
实施例1：
一种规格为1.11dtex×38mm的具有抗菌防螨防霉功能的再生纤维素纤维的制备方法，包括以下步骤：
1、复合浆料的制备步骤
1)将小茴香提取物和山苍子提取物进行混合、粉碎、研磨，得到两者的混合粉体，混合粉体中小茴香提取物和山苍子提取物的质量比为1:0.5，粉体粒径D90＝1.256μm，备用。
2)将上述制备的混合粉体与百里香精油共混均匀，使混合粉体表面包覆一层百里香精油，制备油性混合粉体浆料，其中混合粉体与百里香精油的 质量比为5:1。
将上述油性混合粉体浆料加入乳化剂苯乙烯马来酸酐钠盐含量为0.5％的苯乙烯马来酸酐钠盐水性体系中充分乳化，油性混合粉体浆料与水性体系的质量比为1:5，形成O/W型乳化液，乳化后的乳液粒径为D90＝1.565μm。
3)复合浆料的制备：将油性混合粉体浆料乳化液加入脲醛树脂预聚体中，70-80℃充分搅拌反应，使得脲醛树脂预聚体交联，制备以百里香、小茴香和山苍子为植物来源的油性混合粉体浆料乳化液为囊芯，脲醛树脂为囊壁的植物性复合浆料，油性混合粉体浆料乳化液中小茴香提取物、山苍子提取物以及百里香精油的总质量与脲醛树脂预聚体的质量比为1：1，多功能复合浆料的粒径为D90＝2.216μm，固含量20.1％。
2、复合浆料与变性纤维素纺丝原液共混制备共混纺丝原液步骤
1)变性纤维素纺丝原液的制备步骤
以纤维素浆粕为原料，经过粘胶制备工艺制得粘胶原液，并在粘胶原液中加入变性剂进行变性，制备变性纤维素纺丝原液。所述纤维素浆粕的聚合度为800；所用变性剂为聚氧乙烯类化合物，添加量相较粘胶原液中甲种纤维素质量比为0.1％；变性纤维素纺丝原液的粘度为60s，酯化度为65。
2)共混制备共混纺丝原液步骤
将步骤1制备的复合浆料通过纺前注射系统加入到步骤2制备的变性纤维素纺丝原液中，其中纺前注射系统包括过滤装置、计量装置以及混合装置，以实现植物性复合浆料的过滤、精确计量以及与变性纤维素纺丝原液的均匀混合。复合浆料相较变性纤维素纺丝原液中甲种纤维素质量比为4.0％。纺前注射系统过滤装置允许通过的粒子粒径为2.658μm。混合装置由动态混合器组成，混合时间30s。
3、纺丝及后处理
将所述共混纺丝原液通过调整好的凝固浴进行纺丝，初生丝束经过牵伸后得到成型丝束。所得丝束经过切断、缓和脱硫工艺、上油浴、水洗等精练浴以及烘干后，得到具有防螨、防霉和抗菌功能的植物性再生纤维素纤维。
凝固浴温度为20℃，凝固浴组份包括硫酸5.0％、硫酸铝0.5％、硫酸钠10.0％，聚氧乙烯类化合物0.1％，余量为水。
该纤维对螨虫的驱避率为85％，抑制率为85％；防霉等级可达到1级；抑菌活性值2.2，杀菌活性值0.3。纤维聚合度515，干态断裂强度3.52cN/dtex， 干态强度变异系数11.2％，湿态强度2.11cN/dtex，钩接强度1.22cN/dtex，湿模量达0.55cN/dtex。
实施例2：
一种规格为1.33dtex×38mm的具有抗菌、防螨、和防霉功能的植物性再生纤维素纤维的的制备方法，包括以下步骤：
1、复合浆料的制备步骤
1)将小茴香提取物和山苍子提取物进行混合、粉碎、研磨，得到两者的混合粉体，混合粉体中小茴香提取物和山苍子提取物的质量比为1:0.75，混合粉体粒径D90＝1.321μm，备用；
2)将上述制备的混合粉体与百里香精油共混均匀，使混合粉体表面包覆一层百里香精油，制备油性混合粉体浆料，其中混合粉体与百里香精油的质量比为6:1；
将上述油性混合粉体浆料加入乳化剂苯乙烯马来酸酐钠盐含量为0.65％的苯乙烯马来酸酐钠盐水性体系中充分乳化，油性混合粉体浆料与水性体系的质量比为1:4，形成O/W型乳化液，乳化后的乳液粒径为D90＝1.663μm；
3)复合浆料的制备：将油性混合粉体浆料乳化液加入脲醛树脂预聚体中，70-80℃充分搅拌反应，使得脲醛树脂预聚体交联，制备以百里香、小茴香和山苍子为植物来源的油性混合粉体浆料乳化液为囊芯，脲醛树脂为囊壁的植物性复合浆料，油性混合粉体浆料乳化液中小茴香提取物、山苍子提取物以及百里香精油的总质量与脲醛树脂预聚体的质量比为1.2：1，多功能复合浆料的粒径为D90＝2.312μm，固含量26.7％。
2、复合浆料与变性纤维素纺丝原液共混制备共混纺丝原液步骤
1)变性纤维素纺丝原液的制备步骤
以纤维素浆粕为原料，经过粘胶制备工艺制得粘胶原液，并在粘胶原液中加入变性剂进行变性，制备变性纤维素纺丝原液。所述纤维素浆粕的聚合度为826；所用变性剂为聚氧乙烯类化合物，添加量相较粘胶原液中甲种纤维素质量比为0.26％；变性纤维素纺丝原液的粘度为68s，酯化度为73。
2)共混制备共混纺丝原液步骤
将步骤1制备的复合浆料通过纺前注射系统加入到步骤2制备的变性纤维素纺丝原液中，其中纺前注射系统包括过滤装置、计量装置以及混合装置， 以实现植物性复合浆料的过滤、精确计量以及与变性纤维素纺丝原液的均匀混合。复合浆料相较变性纤维素纺丝原液中甲种纤维素质量比为5.8％。纺前注射系统过滤装置允许通过的粒子粒径为2.756μm。混合装置由静态混合器组成，混合时间78s。
3、纺丝及后处理
将所述共混纺丝原液通过调整好的凝固浴进行纺丝，初生丝束经过牵伸后得到成型丝束。所得丝束经过切断、缓和脱硫工艺、上油浴、水洗等精练浴以及烘干后，得到具有防螨、防霉、抗菌功能的植物性再生纤维素纤维。
所述凝固浴温度为26℃，凝固浴组份包括硫酸5.2％、硫酸铝0.62％、硫酸钠10.0％，聚氧乙烯类化合物0.15％，余量为水。
该纤维对螨虫的驱避率为88％，抑制率87％；防霉等级可达到1级；抑菌活性值2.4，杀菌活性值0.4。纤维聚合度502，干态断裂强度3.44cN/dtex，干态强度变异系数12.1％，湿态强度2.02cN/dtex，钩接强度1.15cN/dtex，湿模量达0.52cN/dtex。
实施例3：
一种规格为1.56dtex×38mm的具有抗菌防螨防霉功能的再生纤维素纤维的的制备方法，包括以下步骤：
1、复合浆料的制备步骤
1)将小茴香提取物和山苍子提取物进行混合、粉碎、研磨，得到两者的混合粉体，混合粉体中小茴香提取物和山苍子提取物的质量比为1:1，混合粉体粒径D90＝1.412μm，备用；
2)将上述制备的混合粉体与百里香精油共混均匀，使混合粉体表面包覆一层百里香精油，制备油性混合粉体浆料，其中混合粉体与百里香精油的质量比为7:1；
将上述油性混合粉体浆料加入乳化剂苯乙烯马来酸酐钠盐含量为0.89％的苯乙烯马来酸酐钠盐水性体系中充分乳化，油性混合粉体浆料与水性体系的质量比为1:3，形成O/W型乳化液，乳化后的乳液粒径为D90＝1.782μm；
3)复合浆料的制备：将油性混合粉体浆料乳化液加入脲醛树脂预聚体中，70-80℃充分搅拌反应，使得脲醛树脂预聚体交联，制备以百里香、小茴香和山苍子为植物来源的油性混合粉体浆料乳化液为囊芯，脲醛树脂为囊 壁的植物性复合浆料，油性混合粉体浆料乳化液中小茴香提取物、山苍子提取物以及百里香精油的总质量与脲醛树脂预聚体的质量比为1.5:1，多功能复合浆料的粒径为D90＝2.396μm，固含量32.5％。
2、复合浆料与变性纤维素纺丝原液共混制备共混纺丝原液步骤
1)变性纤维素纺丝原液的制备步骤
以纤维素浆粕为原料，经过粘胶制备工艺制得粘胶原液，并在粘胶原液中加入变性剂进行变性，制备变性纤维素纺丝原液。所述纤维素浆粕的聚合度为896；所用变性剂为聚氧乙烯类化合物，添加量相较粘胶原液中甲种纤维素质量比为0.51％；变性纤维素纺丝原液的粘度为76s，酯化度为78。
2)共混制备共混纺丝原液步骤
将步骤1制备的植物性复合浆料通过纺前注射系统加入到步骤2制备的变性纤维素纺丝原液中，其中纺前注射系统包括过滤装置、计量装置以及混合装置，以实现植物性复合浆料的过滤、精确计量以及与变性纤维素纺丝原液的均匀混合。复合浆料相较变性纤维素纺丝原液中甲种纤维素质量比为7.5％。纺前注射系统过滤装置允许通过的粒子粒径2.632μm。混合装置由动态混合器和静态混合器两种串联组成，混合时间155s。
3、纺丝及后处理
将所述共混纺丝原液通过调整好的凝固浴进行纺丝，初生丝束经过牵伸后得到成型丝束。所得丝束经过切断、缓和脱硫工艺、上油浴、水洗等精练浴以及烘干后，得到具有防螨、防霉和抗菌功能的植物性再生纤维素纤维。
凝固浴温度为31℃，凝固浴组份包括硫酸6.5％、硫酸铝0.76％、硫酸钠13.2％，聚氧乙烯类化合物0.25％，余量为水。
该纤维对螨虫的驱避率92％，抑制率92％；防霉等级可达到0级水平；抑菌活性值2.5，杀菌活性值0.5。纤维聚合度488，干态断裂强度3.32cN/dtex，干态强度变异系数12.5％，湿态强度1.89cN/dtex，钩接强度1.07cN/dtex，湿模量达0.45cN/dtex。
实施例4：
一种规格为1.67dtex×38mm的具有抗菌防螨防霉功能的再生纤维素纤维的制备方法，包括以下步骤：
1、复合浆料的制备步骤
1)将小茴香提取物和山苍子提取物进行混合、粉碎、研磨，得到两者的混合粉体，混合粉体中小茴香提取物和山苍子提取物的质量比为1:1.25，混合粉体粒径D90＝1.523μm，备用；
2)将上述制备的混合粉体与百里香精油共混均匀，使混合粉体表面包覆一层百里香精油，制备油性混合粉体浆料，其中混合粉体与百里香精油的质量比为8.5:1；
将上述油性混合粉体浆料加入乳化剂苯乙烯马来酸酐钠盐含量为0.5％的苯乙烯马来酸酐钠盐水性体系中充分乳化，油性混合粉体浆料与水性体系的质量比为1:2，形成O/W型乳化液，乳化后的乳液粒径为D90＝1.905μm；
3)复合浆料的制备：将油性混合粉体浆料乳化液加入脲醛树脂预聚体中，70-80℃充分搅拌反应，使得脲醛树脂预聚体交联，制备以百里香、小茴香和山苍子为植物来源的油性混合粉体浆料乳化液为囊芯，脲醛树脂为囊壁的植物性复合浆料，油性混合粉体浆料乳化液中小茴香提取物、山苍子提取物以及百里香精油的总质量与脲醛树脂预聚体的质量比为2:1，多功能复合浆料的粒径D90＝2.443μm，固含量36.8％。
2、复合浆料与变性纤维素纺丝原液共混制备共混纺丝原液步骤
1)变性纤维素纺丝原液的制备步骤
以纤维素浆粕为原料，经过粘胶制备工艺制得粘胶原液，并在粘胶原液中加入变性剂进行变性，制备变性纤维素纺丝原液。所述纤维素浆粕的聚合度为937；所用变性剂为聚氧乙烯类化合物，添加量相较粘胶原液中甲种纤维素质量比为0.78％；变性纤维素纺丝原液的粘度为88s，酯化度为81。
2)共混制备共混纺丝原液步骤
将步骤1制备的复合浆料通过纺前注射系统加入到步骤2制备的变性纤维素纺丝原液中，其中纺前注射系统包括过滤装置、计量装置以及混合装置，以实现植物性复合浆料的过滤、精确计量以及与变性纤维素纺丝原液的均匀混合。复合浆料相较变性纤维素纺丝原液中甲种纤维素质量比为8.9％，纺前注射系统过滤装置允许通过的粒子粒径2.852μm。混合装置由动态混合器和静态混合器两种串联组成，混合时间196s。
3、纺丝及后处理
将所述共混纺丝原液通过调整好的凝固浴进行纺丝，初生丝束经过牵伸后得到成型丝束。所得丝束经过切断、缓和脱硫工艺、上油浴、水洗等精练 浴以及烘干后，得到具有防螨、防霉和抗菌功能的植物性再生纤维素纤维。
凝固浴温度为36℃，凝固浴组份包括硫酸7.2％、硫酸铝0.78％、硫酸钠13.8％，聚氧乙烯类化合物0.32％，余量为水。
该纤维对螨虫的驱避率95％，抑制率94％；防霉等级可达到0级水平；抑菌活性值2.7，杀菌活性值0.6。纤维聚合度475，干态断裂强度3.09cN/dtex，干态强度变异系数13.3％，湿态强度1.75cN/dtex，钩接强度0.98cN/dtex，湿模量达0.40cN/dtex。
实施例5：
一种规格为2.22dtex×38mm的具有抗菌防螨防霉功能的再生纤维素纤维的的制备方法，包括以下步骤：
1、复合浆料的制备步骤
1)将小茴香提取物和山苍子提取物进行混合、粉碎、研磨，得到两者的混合粉体，混合粉体中小茴香提取物和山苍子提取物的质量比为1:1.5，混合粉体粒径D90＝1.568μm，备用；
2)将上述制备的混合粉体与百里香精油共混均匀，使混合粉体表面包覆一层百里香精油，制备油性混合粉体浆料，其中混合粉体与百里香精油的质量比为10:1；
将上述油性混合粉体浆料加入乳化剂苯乙烯马来酸酐钠盐含量为0.5％的苯乙烯马来酸酐钠盐水性体系中充分乳化，油性混合粉体浆料与水性体系的质量比为1:5，形成O/W型乳化液，乳化后的乳液粒径为D90＝2.038μm；
3)复合浆料的制备：将油性混合粉体浆料乳化液加入脲醛树脂预聚体中，70-80℃充分搅拌反应，使得脲醛树脂预聚体交联，制备以百里香、小茴香和山苍子为植物来源的油性混合粉体浆料乳化液为囊芯，脲醛树脂为囊壁的植物性复合浆料，油性混合粉体浆料乳化液中小茴香提取物、山苍子提取物以及百里香精油的总质量与脲醛树脂预聚体的质量比为3：1，多功能复合浆料的粒径D90＝2.562μm，固含量39.9％。
2、复合浆料与变性纤维素纺丝原液共混制备共混纺丝原液步骤
1)变性纤维素纺丝原液的制备步骤
以纤维素浆粕为原料，经过粘胶制备工艺制得粘胶原液，并在粘胶原液中加入变性剂进行变性，制备变性纤维素纺丝原液。所述纤维素浆粕的聚合 度为1000；所用变性剂为聚氧乙烯类化合物，添加量相较粘胶原液中甲种纤维素质量比为1.0％；变性纤维素纺丝原液的粘度为96s，酯化度为85。
2)共混制备共混纺丝原液步骤
将步骤1制备的复合浆料通过纺前注射系统加入到步骤2制备的变性纤维素纺丝原液中，其中纺前注射系统包括过滤装置、计量装置以及混合装置，以实现植物性复合浆料的过滤、精确计量以及与变性纤维素纺丝原液的均匀混合。复合浆料相较变性纤维素纺丝原液中甲种纤维素质量比为10.0％。纺前注射系统过滤装置允许通过的粒子粒径为2.968μm。混合装置由动态混合器和静态混合器两种串联组成，混合时间300s。
3、纺丝及后处理
将所述共混纺丝原液通过调整好的凝固浴进行纺丝，初生丝束经过牵伸后得到成型丝束。所得丝束经过切断、缓和脱硫工艺、上油浴、水洗等精练浴以及烘干后，得到具有防螨、防霉和抗菌功能的植物性再生纤维素纤维。
凝固浴温度为40℃，凝固浴组份包括硫酸8.0％、硫酸铝1.0％、硫酸钠16.0％，聚氧乙烯类化合物0.5％，余量为水。
该纤维对螨虫的驱避率98％，抑制率98％；防霉等级可达到0级水平；抑菌活性值2.8，杀菌活性值0.7。纤维聚合度450，干态断裂强度2.89cN/dtex，干态强度变异系数13.6％，湿态强度1.68cN/dtex，钩接强度0.90cN/dtex，湿模量达0.38cN/dtex。
最后应说明的是：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (11)

  1. 一种具有抗菌、防螨、和防霉功能的再生纤维素纤维的制备方法，其包括如下步骤：
    步骤(1)：复合浆料的制备；
    步骤(2)：复合浆料与变性纤维素纺丝原液共混制备共混纺丝原液；
    步骤(3)：共混纺丝原液纺丝及后处理。
  2. 权利要求1中所述的方法，其中所述的复合浆料通过以下过程制备：
    i)共混小茴香提取物和山苍子提取物获得混合粉体；
    ii)将步骤i)获得的混合粉体与百里香精油混合，制备油性混合粉体浆料，并进一步乳化得乳化液；
    iii)将步骤ii)获得的乳化液与脲醛树脂预聚体反应，获得复合浆料。
  3. 权利要求2所述的方法，其中步骤i)中小茴香提取物和山苍子提取物以1:(0.5-1.5)的质量比进行共混，混合粉体粒径D90≤1.568μm。
  4. 权利要求2所述的方法，其中步骤ii)中所述混合粉体与所述百里香精油的混合质量比为(5-10)：1。
  5. 权利要求2所述的方法，其中步骤ii)中所述乳化为将上述油性混合粉体浆料加入到苯乙烯马来酸酐钠盐含量0.5-1.5％的水性体系中乳化，油性混合粉体浆料与水性体系的质量比为1:(2-5)，乳化液粒径D90≤2.038μm。
  6. 权利要求2所述的方法，其中步骤iii)所述乳化液与脲醛树脂预聚体在70-80℃搅拌反应，乳化液中小茴香提取物、山苍子提取物以及百里香精油的总质量与脲醛树脂预聚体的质量之比为(1-3)：1，复合浆料粒径D90≤2.562μm，固含量20％-40％。
  7. 权利要求1所述的方法，其中步骤(2)所述的变性纤维素纺丝原液以聚合度为800-1000的纤维素浆粕为原料先制得粘胶原液，再添加变性剂聚氧乙烯类化合物制得，其中变性剂的添加量相较粘胶原液中甲种纤维素质量比为0.1-1.0％；所述变性纤维素纺丝原液粘度为60-96s，酯化度为65-85。
  8. 权利要求1所述的方法，其中步骤(2)所述的共混纺丝原液中所述复合浆料相较变性纤维素纺丝原液中甲种纤维素质量比为4.0％～10.0％。
  9. 权利要求1所述的方法，其中步骤(3)所述纺丝使用凝固浴，凝固 浴温度为20-40℃，凝固浴组份包括硫酸5.0％-8.0％、硫酸铝0.5％-1.0％、硫酸钠10.0％-16.0％，聚氧乙烯类化合物0.1-0.5％，余量为水。
  10. 权利要求1所述的方法，其中步骤(3)所述后处理包括脱硫、油浴、水洗及烘干。
  11. 一种使用权利要求1-10任一项所述的制备方法获得的再生纤维素纤维在抗菌、防螨和防霉织物中的应用。
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