Insect-proof antibacterial regenerated cellulose fiber containing cineole as well as preparation method and application of insect-proof antibacterial regenerated cellulose fiber

Abstract

The invention provides a cineole-containing insect-proof and antibacterial regenerated cellulose fiber and a preparation method and application thereof.The cineole-containing insect-proof and antibacterial regenerated cellulose fiber is prepared from viscose, cineole microcapsules and plant extract through a wet spinning technology after blending, the plant extract is a paper mulberry bark extract, and a core material of the microcapsule is high-purity cineole obtained by microwave-assisted steam distillation and purification. The insect-proof antibacterial regenerated cellulose fiber can continuously release cineole, has a repelling effect on common pests such as mosquitoes and mites, also can inhibit growth and reproduction of microorganisms such as bacteria and fungi, has small irritation to human skin, can be used for manufacturing textiles such as underwear and bedding articles which are in direct contact with a human body, and can be applied to the field of textile products. The current green and environment-friendly development trend is met.

Description

Technical Field

[0001] The present invention relates to the technical field of functional cellulose fibers, and particularly relates to an insect-proof and antibacterial regenerated cellulose fiber containing cineole and a preparation method thereof. Background Art

[0002] Artemisia argyi, also known as Artemisia princeps and sweet wormwood, contains chemical components such as volatile oils, flavonoids, and polysaccharides. Volatile oils are the main active ingredients. Analysis shows that the main components of the volatile oils of Artemisia argyi are cineole, camphor, borneol, α-caryophyllene, terpinene, and terpinolene, etc., among which cineole accounts for a relatively large proportion. Cineole is a natural monoterpene, which is a colorless and transparent liquid with a fresh camphor fragrance and a pungent taste. Research shows that cineole has various pharmacological effects such as insect repellent and antibacterial, and has broad application prospects in the fields of daily necessities, cosmetics, agriculture, etc.

[0003] Regenerated cellulose fibers are made from natural cellulose (such as cotton linters, wood, bamboo, etc.) through chemical treatment and mechanical processing. Due to its many advantages such as strong hygroscopicity, good air permeability, excellent dyeing performance, and soft handfeel, it is widely used in the fields of textiles, clothing, household items, etc. However, ordinary regenerated cellulose fibers do not have the functions of insect prevention and antibacterial themselves, and are easily eroded by pests and contaminated by microorganisms such as bacteria and fungi during use.

[0004] To solve the problem of insect prevention and antibacterial of textiles, at present, most methods on the market are to endow textiles with the effects of insect prevention and antibacterial by post-treatment. This method is to attach insect prevention and antibacterial agents to the surface of fibers or fabrics through processes such as impregnation and coating after the fibers or fabrics are made. This method has obvious defects: First, the combination of the insect prevention and antibacterial agent and the fiber is not firm enough, and it is easy to fall off during daily use such as washing and friction, and the insect prevention and antibacterial effect is difficult to last. Second, the post-treatment process may affect the original physical properties and handfeel of the fiber.

[0005] In addition, there are also some products that use the method of co-blending spinning to prepare insect-proof or antibacterial regenerated fibers, but most of the insect prevention and antibacterial agents used are chemically synthesized substances, and these substances may have problems such as biological toxicity and environmental unfriendliness. Long-term contact with chemically synthesized insect prevention and antibacterial agents may pose potential hazards to human health. For example, Chinese Patent CN 116121895 A provides a preparation method of a mosquito-proof viscose fiber, which adds permethrin during the manufacturing process of the viscose fiber spinning dope, and has a certain mosquito repellent effect, but it has potential safety hazards to human health and will also have an impact on the environment and organisms.

[0006] Chinese Patent CN 109825889 A provides a preparation method of regenerated cellulose fiber with a cooling and antibacterial function. By adding honeysuckle and mint ethanol extract into the spinning dope, the fiber is made to have the effects of cooling and antibacterial. However, it does not screen and protect the main functional components, and functional components such as menthol are easily volatile during use and have poor wash resistance. Summary of the Invention

[0007] In view of the above problems and deficiencies, the purpose of the present invention is to provide an insect-proof and antibacterial regenerated cellulose fiber containing cineole and its preparation method.

[0008] In order to achieve the above purpose, the present invention provides the following technical solutions:

[0009] An insect-proof and antibacterial regenerated cellulose fiber containing cineole, using viscose spinning solution, cineole microcapsules and plant extract (paper mulberry bark extract) as raw materials, preparing a blended spinning dope, and obtaining the insect-proof and antibacterial regenerated cellulose fiber through spinning;

[0010] Among them, using cellulose pulp with a degree of polymerization of 500 - 600 as the raw material, in the viscose solution prepared by the conventional viscose production process, the content of alpha-cellulose reaches 8% - 10% (w / w).

[0011] Among them, the cineole microcapsules account for 3wt% - 5wt% of the alpha-cellulose content of the viscose solution; the plant extract accounts for 2wt% - 4wt% of the alpha-cellulose content of the viscose solution.

[0012] Preferably, the preparation method of the cineole microcapsules is as follows:

[0013] Adding sodium dodecyl sulfate (SDS) into deionized water to prepare a 1% (mass fraction) SDS solution, stirring evenly as the aqueous phase; mixing toluene-2,4-diisocyanate (TDI) and cineole in a mass ratio of 2:1 as the oil phase; mixing the aqueous phase and the oil phase and pouring them into an ice-water bath, emulsifying with a shear emulsifier at 3000r / min for 20min to form an O / W type emulsion; placing the emulsion in a constant temperature water bath, dropwise adding polyethylene glycol-600 (PEG-600) while stirring, carrying out a prepolymerization reaction at 30°C at a rotation speed of 200r / min for 30min, finally heating to 60°C and adding the chain extender ethylene glycol and then reacting for 1h, filtering, washing, and drying at 60°C to obtain the cineole microcapsules.

[0014] The mixing volume ratio of the aqueous phase and the oil phase is 10:1; the mass ratio of the dosage of PEG-600 to the dosage of TDI is 1:1; the mass ratio of the dosage of ethylene glycol to the dosage of TDI is 1:5.

[0015] Further preferably, the particle size D90 of the cineole microcapsules ≤ 1.5μm.

[0016] Further preferably, the preparation method of cineole is as follows:

[0017] S1. Collect fresh wormwood, take the wormwood leaf part, wash it and dry it in a cool place. After the mass is constant, crush it and sieve it to obtain wormwood leaf powder;

[0018] S2. Put the wormwood leaf powder into a round-bottom flask, add distilled water and an auxiliary agent, connect an essential oil extractor and a reflux condenser, and apply microwave for extraction;

[0019] S3. After the extraction is completed, collect the upper oil phase of the essential oil analyzer, and dry it with anhydrous Na 2 SO 4 to obtain wormwood essential oil for standby;

[0020] S4. Carry out vacuum rectification on the collected wormwood essential oil, control the pressure at 0.073 - 0.078 MPa, collect the fraction at 68 - 78 °C, and obtain crude cineole with a purity greater than 85%;

[0021] S5. Place the crude cineole at -20 °C and freeze it for 48 - 36 h. After taking it out, centrifuge it at 3000 r / min for 10 - 15 min, and take the solid part to obtain high-purity cineole with a purity greater than 99%.

[0022] Furthermore, in S2, the microwave power is 150 - 200 W, the extraction time is 15 - 20 min, and the solid-liquid ratio is 1:8 - 1:15.

[0023] Furthermore, in S2, the auxiliary agent is sodium chloride; the dosage of the auxiliary agent is 5 wt% - 8 wt% of the distilled water.

[0024] Preferably, the preparation method of the insect-proof and bacteriostatic regenerated cellulose fiber containing cineole is as follows:

[0025] a) Add the cineole microcapsule aqueous solution and the plant extract into the spinning solution, stir to uniformly disperse the microcapsules and the extract in the viscose spinning solution, and after standing, filtering, defoaming and aging, obtain a blended spinning solution for standby;

[0026] b) Quantitatively transport the blended spinning solution to the spinneret through a spinning pump, and spray it into the coagulation bath from the capillary pores of the spinneret to form a thin stream and solidify the spinning solution into fibers;

[0027] c) Draw out the solidified fiber from the coagulation bath and stretch the fiber through a stretching device;

[0028] d) Further carry out post-treatment on the stretched fiber, and then dry it to obtain the insect-proof and bacteriostatic regenerated cellulose fiber containing cineole.

[0029] Further preferably, the coagulation bath is composed of 100 - 120 g / L of sulfuric acid, 250 - 300 g / L of sodium sulfate, 12 - 15 g / L of zinc sulfate, and the temperature of the coagulation bath is 50 - 60 °C.

[0030] Further preferably, the post-treatment steps are conventional bunching drawing, cutting, water washing, desulfurization, bleaching, pickling, and oiling.

[0031] Further preferably, the drying temperature is 105 - 120 °C.

[0032] The beneficial effects of the present invention are as follows:

[0033] 1. Cineole itself has natural insect-proof and antibacterial properties. It is made into microcapsules and added to the cellulose fiber spinning solution, and the extract of Broussonetia papyrifera is added to prepare regenerated cellulose fibers, enabling the fibers to continuously release cineole, which has a repellent effect on common pests such as mosquitoes and mites, and can also inhibit the growth and reproduction of microorganisms such as bacteria and fungi.

[0034] 2. The volatile oil in Artemisia argyi is extracted by microwave-assisted steam distillation method, and further purified by a pure physical method to prepare high-purity cineole without introducing any chemical reagents. Moreover, cineole is a natural ingredient extracted from Artemisia argyi. Compared with some chemically synthesized insect-proof and antibacterial agents, it has higher safety, less irritation to human skin, and can be used to make textiles that directly contact the human body such as underwear and bedding, meeting the current development trend of green environmental protection.

[0035] 3. While endowing the fibers with insect-proof and antibacterial functions, this preparation method will not damage the excellent properties of the regenerated cellulose fibers themselves. The regenerated cellulose fibers have the characteristics of strong hygroscopicity, good air permeability, and excellent dyeing performance, and the textiles made are comfortable to wear. The regenerated cellulose fibers containing cineole still retain these characteristics, making the product both functional and having a good user experience. Specific Embodiments

[0036] The present invention will be further described below. The following examples are only used to illustrate the technical solution of the present invention more clearly, and cannot be used to limit the protection scope of the present invention.

[0037] Example 1

[0038] (1) Extraction of Cineole

[0039] 1) Extraction of Artemisia argyi essential oil

[0040] Collect fresh Artemisia argyi, take the Artemisia argyi leaves, wash them and dry them in a cool place. After the mass is constant, crush them and pass through a 40-mesh sieve to obtain Artemisia argyi powder; take 50 parts of Artemisia argyi powder and add it to a round-bottom flask, add 500 parts of distilled water and 25 parts of NaCl, connect a volatile oil extractor and a reflux condenser, and assist in extraction with 180 W of microwave for 16 min; after the extraction is completed, collect the upper oil phase of the volatile oil analyzer, and use anhydrous Na 2 SO 4 dry to obtain Artemisia argyi essential oil for standby.

[0041] 2) Purification of eucalyptol

[0042] Perform vacuum rectification on the collected Artemisia argyi essential oil, control the pressure at 0.073 - 0.078 MPa, collect the fraction at 68 - 78 °C to obtain crude eucalyptol with a purity greater than 85%; place the crude eucalyptol in a freezer at -20 °C for 48 h, take it out and centrifuge at 3000 r / min for 15 min, take the solid part to obtain high-purity eucalyptol, and its purity is determined to be 99.4% by gas chromatography-mass spectrometry.

[0043] (2) Preparation of eucalyptol microcapsules

[0044] Add SDS to deionized water to prepare a 1% SDS solution, stir evenly as the aqueous phase; mix TDI and eucalyptol in a mass ratio of 2:1 as the oil phase; mix the aqueous phase and the oil phase and pour them into an ice-water bath, and emulsify with a shear emulsifier at 3000 r / min for 20 min to form an O / W emulsion; place the emulsion in a constant temperature water bath, dropwise add PEG-600 while stirring, and carry out a prepolymerization reaction at 30 °C at a rotation speed of 200 r / min for 30 min, and finally raise the temperature to 60 °C and add the chain extender ethylene glycol and then react for 1 h, filter, wash, and dry at 60 °C to obtain eucalyptol microcapsules. After determination by a particle size analyzer, it is determined that D90 ≤ 1.5 μm.

[0045] The mixing volume ratio of the aqueous phase to the oil phase is 10:1; the mass ratio of the dosage of PEG-600 to the dosage of TDI is 1:1; the mass ratio of the dosage of ethylene glycol to the dosage of TDI is 1:5.

[0046] (3) Preparation of regenerated cellulose fiber

[0047] 1) Add an aqueous solution of eucalyptol microcapsules with a mass concentration of 10% and bark extract (Shaanxi Sinuote Biotechnology Co., Ltd.) to a viscose solution with a cellulose xanthate content of 8.9% (a viscose solution prepared from cellulose pulp with a polymerization degree of 500 - 600 through a conventional viscose production process), stir to make the microcapsules and the extract evenly disperse in the spinning solution, and obtain a blended spinning solution after standing, filtering, degassing, and aging for standby; the eucalyptol microcapsules account for 4 wt% of the cellulose xanthate content in the viscose solution, and the bark extract accounts for 3 wt% of the cellulose xanthate content in the viscose solution;

[0048] 2) The blended spinning solution is quantitatively delivered to the spinneret through a spinning pump, extruded from the capillary holes of the spinneret to form a thin stream, and enters the coagulation bath, where the spinning solution solidifies into fibers. The spinning speed is 20 m / min. The composition of the coagulation bath is 110 g / L sulfuric acid, 270 g / L sodium sulfate, and 13 g / L zinc sulfate, and the temperature of the coagulation bath is 60 °C.

[0049] 3) The solidified fibers are drawn out from the coagulation bath and stretched by a stretching device.

[0050] 4) The stretched fibers are further subjected to bunch drawing, cutting, washing, desulfurization, bleaching, pickling, oiling, and drying at 110 °C to obtain insect-repellent and bacteriostatic regenerated cellulose fibers containing cineole.

[0051] Example 2

[0052] (1) Extraction of cineole

[0053] 1) Extraction of Artemisia argyi essential oil

[0054] Collect fresh Artemisia argyi, take the leaf part, wash it and dry it in a cool place. After the mass is constant, it is crushed and sieved through a 40-mesh sieve to obtain Artemisia argyi powder. Take 50 parts of Artemisia argyi powder and add it to a round-bottom flask, add 450 parts of distilled water and 30 parts of NaCl, connect the volatile oil extractor and the reflux condenser, and assist in extraction with 200 W of microwave for 15 min. After the extraction is completed, collect the upper oil phase of the volatile oil analyzer and dry it with anhydrous Na 2 SO 4 to obtain Artemisia argyi essential oil for standby.

[0055] 2) Purification of cineole

[0056] Same as Example 1.

[0057] (2) Preparation of cineole microcapsules

[0058] Same as Example 1. After determination by a particle size analyzer, it is determined that D90 ≤ 1.5 μm.

[0059] (3) Preparation of regenerated cellulose fibers

[0060] 1) Add an aqueous solution of cineole microcapsules with a mass concentration of 10% and the extract of Broussonetia papyrifera bark to a viscose solution with a cellulose xanthate content of 8.9%, stir to uniformly disperse the microcapsules and the extract in the viscose solution, and let it stand, filter, defoam, and age before use to obtain a blended spinning solution. The cineole microcapsules account for 5 wt% of the cellulose xanthate content in the viscose solution, and the extract of Broussonetia papyrifera bark accounts for 4 wt% of the cellulose xanthate content in the viscose solution.

[0061] 2) The blended spinning solution is quantitatively delivered to the spinneret through a spinning pump, extruded from the capillary holes of the spinneret to form a thin stream, which enters the coagulation bath, causing the spinning solution to solidify into fibers. The spinning speed is 25 m / min. The composition of the coagulation bath is 100 g / L sulfuric acid, 250 g / L sodium sulfate, and 14 g / L zinc sulfate, and the temperature of the coagulation bath is 50 °C.

[0062] 3) The solidified fibers are drawn out from the coagulation bath and stretched by a stretching device.

[0063] 4) The stretched fibers are further subjected to bunch drawing, cutting, washing, desulfurization, bleaching, pickling, oiling, and drying at 105 °C to obtain the insect-repellent and bacteriostatic regenerated cellulose fibers containing cineole.

[0064] Example 3

[0065] (1) Extraction of cineole

[0066] 1) Extraction of Artemisia argyi essential oil

[0067] Collect fresh Artemisia argyi, take the leaf part, wash it and dry it in a cool place. After the mass is constant, it is pulverized and passed through a 40-mesh sieve to obtain Artemisia argyi powder. Take 50 parts of Artemisia argyi powder and add it to a round-bottom flask, add 750 parts of distilled water and 60 parts of NaCl, connect the volatile oil extractor and the reflux condenser, and assist in extraction with 200 W of microwave for 20 min. After the extraction is completed, collect the upper oil phase of the volatile oil analyzer and dry it with anhydrous Na 2 SO 4 to obtain the prepared Artemisia argyi essential oil for standby.

[0068] 2) Purification of cineole

[0069] Same as Example 1.

[0070] (2) Preparation of cineole microcapsules

[0071] Same as Example 1. After determination by a particle size analyzer, it is determined that D90 ≤ 1.5 μm.

[0072] (3) Preparation of regenerated cellulose fibers

[0073] 1) Add an aqueous solution of cineole microcapsules with a mass concentration of 10% and the extract of Broussonetia papyrifera bark to the viscose solution with a cellulose xanthate content of 8.9%, stir to uniformly disperse the microcapsules and the extract in the viscose solution, and let it stand, filter, defoam, and age for standby. The cineole microcapsules account for 4 wt% of the cellulose xanthate content in the viscose solution, and the extract of Broussonetia papyrifera bark accounts for 3 wt% of the cellulose xanthate content in the viscose solution.

[0074] 2) The blended spinning solution is quantitatively delivered to the spinneret through a spinning pump, extruded from the capillary holes of the spinneret to form a thin stream, which enters the coagulation bath, causing the spinning solution to solidify into fibers. The spinning speed is 23 m / min. The composition of the coagulation bath is 120 g / L sulfuric acid, 300 g / L sodium sulfate, and 15 g / L zinc sulfate, and the temperature of the coagulation bath is 55 °C.

[0075] 3) The solidified fibers are drawn out from the coagulation bath and stretched by a stretching device.

[0076] 4) The stretched fibers are further subjected to bunch drawing, cutting, washing, desulfurization, bleaching, pickling, oiling, and drying at 120 °C to obtain insect - repellent and antibacterial regenerated cellulose fibers containing cineole.

[0077] Example 4

[0078] (1) Extraction of cineole

[0079] 1) Extraction of Artemisia argyi essential oil

[0080] Collect fresh Artemisia argyi, take the leaf part, wash it and dry it in a cool place. After the mass is constant, crush it and pass through a 40 - mesh sieve to obtain Artemisia argyi powder. Take 50 parts of Artemisia argyi powder and add it to a round - bottom flask, add 400 parts of distilled water and 20 parts of NaCl, connect the volatile oil extractor and the reflux condenser, and assist the extraction with 150 W of microwave for 18 min. After the extraction is completed, collect the upper oil phase of the volatile oil analyzer and dry it with anhydrous Na 2 SO 4 to obtain Artemisia argyi essential oil for standby.

[0081] 2) Purification of cineole

[0082] Same as Example 1.

[0083] (2) Preparation of cineole microcapsules

[0084] Same as Example 1. After determination by a particle size analyzer, it is determined that D90 ≤ 1.5 μm.

[0085] (3) Preparation of regenerated cellulose fibers

[0086] 1) Add an aqueous solution of cineole microcapsules with a mass concentration of 10% and the extract of Broussonetia papyrifera bark to a viscose solution with a cellulose xanthate content of 8.9%, stir to uniformly disperse the microcapsules in the viscose solution, and set aside after standing, filtering, degassing, and aging. The cineole microcapsules account for 3 wt% of the cellulose xanthate content in the viscose solution, and the extract of Broussonetia papyrifera bark accounts for 2 wt% of the cellulose xanthate content in the viscose solution.

[0087] 2) The blended spinning solution is quantitatively delivered to the spinneret through a spinning pump, extruded from the capillary holes of the spinneret to form a thin stream, which enters the coagulation bath, causing the spinning solution to solidify into fibers. The spinning speed is 20 m / min.

[0088] 3) The coagulated fiber is drawn out from the coagulation bath and stretched by a stretching device; the composition of the coagulation bath is 105 g / L sulfuric acid, 280 g / L sodium sulfate, 12 g / L zinc sulfate, and the coagulation bath temperature is 55°C.

[0089] 4) The stretched fibers are further subjected to bundle drawing, cutting, water washing, desulfurization, bleaching, pickling, oiling, and drying at 110° C. to obtain insect-proof and antibacterial regenerated cellulose fibers containing eucalyptol.

[0090] Example 5

[0091] The preparation method of eucalyptol microcapsules is the same as that of Example 1;

[0092] In this example, eucalyptus microcapsules accounted for 2wt% of the methyl cellulose content in the viscose solution, and paper mulberry bark extract accounted for 2wt% of the methyl cellulose content in the viscose solution. Wet spinning was carried out in the same way as in Example 1 to prepare regenerated cellulose fibers.

[0093] Example 6

[0094] The preparation method of eucalyptol microcapsules is the same as that of Example 1;

[0095] In this example, the added eucalyptol microcapsules accounted for 6wt% of the methyl cellulose content in the viscose solution, and the paper mulberry bark extract accounted for 4wt% of the methyl cellulose content in the viscose solution. The wet spinning method was carried out in the same way as in Example 1 to prepare regenerated cellulose fibers.

[0096] Example 7

[0097] The preparation method of eucalyptol microcapsules is the same as that of Example 1;

[0098] In this example, the added eucalyptol microcapsules accounted for 3wt% of the methyl cellulose content in the viscose solution, and the paper mulberry bark extract accounted for 1wt% of the methyl cellulose content in the viscose solution. The wet spinning method was carried out in the same way as in Example 1 to prepare regenerated cellulose fibers.

[0099] Example 8

[0100] The preparation method of eucalyptol microcapsules is the same as that of Example 1;

[0101] In this example, eucalyptus microcapsules accounted for 5wt% of the methyl cellulose content in the viscose solution, and paper mulberry bark extract accounted for 5wt% of the methyl cellulose content in the viscose solution. Wet spinning was carried out in the same way as in Example 1 to prepare regenerated cellulose fibers.

[0102] Comparative Example 1

[0103] In this example, no paper mulberry bark extract and eucalyptol microcapsules were added, and wet spinning was carried out in the same manner as in Example 1 to prepare ordinary regenerated cellulose fibers.

[0104] Comparative Example 2

[0105] In this example, eucalyptol microcapsules are not added, and they are replaced with an equal amount of Broussonetia papyrifera bark extract. Wet spinning is carried out with Example 1 to prepare regenerated cellulose fibers.

[0106] Comparative Example 3

[0107] The preparation method of eucalyptol microcapsules is the same as that in Example 1;

[0108] In this example, Broussonetia papyrifera bark extract is not added, and it is replaced with an equal amount of eucalyptol microcapsules. Wet spinning is carried out with Example 1 to prepare regenerated cellulose fibers.

[0109] Performance Test

[0110] Fiber mechanical properties: The test is carried out with reference to GB / T14337-2008 "Test Method for Tensile Properties of Chemical Fiber Staple Fibers".

[0111] Fiber mosquito repellent effect: With reference to the repellent method of GB / T 30126—2013 "Detection and Evaluation of Mosquito Repellent Properties of Textiles", the mosquito repellent performance of the fabric is evaluated by the repellent rate: P>70% is rated as Grade A (with extremely strong repellent effect); 50%<P<70 is rated as Grade B (with good repellent effect), and 30%<P<50% is rated as Grade C (with repellent effect).

[0112] Fiber acarid-proof performance: The test is carried out with reference to GB / T 24253-2009 "Evaluation of Acarid-proof Properties of Textiles".

[0113] Bacteriostatic performance: The test is carried out with reference to GB / T 20944.3-2008 "Evaluation of Antibacterial Properties of Textiles - Part 3: Oscillation Method". The bacteriostatic performances against Staphylococcus aureus (ATCC 6538) Gram-positive bacteria, Escherichia coli (ATCC 11229) Gram-negative bacteria and Candida albicans (ATCC 10231) are tested respectively.

[0114] Washing method: Washing is carried out according to GB / T 12490-2007 "Textiles - Tests for Colour Fastness - Colour Fastness to Home and Commercial Laundering".

[0115] Table 1 Mechanical Properties of Regenerated Cellulose Fibers

[0116]

[0117] As can be seen from Table 1, for the prepared eucalyptol-containing insect-repellent and antibacterial regenerated cellulose fibers, although the breaking strength and elongation at break are both lower than those of ordinary regenerated cellulose fibers in both wet and dry states, their mechanical properties are not much different from those of ordinary regenerated cellulose fibers, and it does not affect their wearability. In Comparative Example 3 and Example 6, due to the large addition amount of microcapsules, the continuity of cellulose molecular chains becomes poor, resulting in an increase in stress concentration points and a significant decrease in the mechanical properties of the fibers. In Example 8, after further increasing the addition amount of Broussonetia papyrifera extract, the breaking strength and elongation at break of the fibers also decreased significantly.

[0118] Table 2 Mosquito Repellent Effect of Regenerated Cellulose Fibers

[0119] Example Repellency rate without washing (%) Repellency rate after 10 washes (%) Repellency rate after 20 washes (%) Example 1 93％ 90％ 86％ Example 2 95％ 92％ 89％ Example 3 92％ 89％ 86％ Example 4 91％ 87％ 83％ Comparative Example 1 / / / Comparative Example 2 65％ 60％ 54％ Comparative Example 3 89％ 86％ 83％ Example 5 84％ 81％ 78％ Example 6 96％ 93％ 90％ Example 7 86％ 83％ 80％ Example 8 93％ 90％ 87％

[0120] As can be seen from Table 2, the prepared eucalyptol-containing insect-repellent and antibacterial regenerated cellulose fibers have excellent mosquito repellent effects and good wash resistance. After 20 washes, the mosquito repellent rate of the fibers is still above 80%. The regenerated cellulose fibers without adding eucalyptol microcapsules and Broussonetia papyrifera extract or those adding only one of them have no repellent effect or a weak repellent effect, indicating that the two have a synergistic effect. In Example 5 and Example 7, when the addition amounts of microcapsules and Broussonetia papyrifera extract are reduced respectively, the mosquito repellent effect decreases significantly; in Example 6 and Example 8, when the addition amounts of microcapsules and Broussonetia papyrifera extract are increased respectively, the mosquito repellent effect does not increase significantly, and combined with Table 1, it can be seen that it will lead to a decrease in the mechanical properties of the fibers.

[0121] Table 3 Mite Repellent Effect of Regenerated Cellulose Fibers

[0122] Example Repellency rate without washing (%) Repellency rate after 10 washes (%) Repellency rate after 20 washes (%) Example 1 95％ 92％ 90％ Example 2 96％ 93％ 90％ Example 3 95％ 92％ 89％ Example 4 94％ 91％ 88％ Comparative Example 1 / / / Comparative Example 2 68％ 63％ 59％ Comparative Example 3 91％ 88％ 85％ Example 5 86％ 83％ 80％ Example 6 96％ 93％ 91％ Example 7 88％ 85％ 82％ Example 8 95％ 92％ 89％

[0123] As can be seen from Table 3, the prepared eucalyptol-containing insect-repellent and antibacterial regenerated cellulose fibers also have excellent mite repellent effects and good wash resistance. After 20 washes, the mite repellent rate of the fibers is still at 88% and above. The regenerated cellulose fibers without adding eucalyptol microcapsules and Broussonetia papyrifera extract or those adding only one of them have no repellent effect or a weaker repellent effect compared with those adding both, indicating that the two have a synergistic effect. In Example 5 and Example 7, when the addition amounts of microcapsules and Broussonetia papyrifera extract are reduced respectively, the mite prevention effect decreases significantly; in Example 6 and Example 8, when the addition amounts of microcapsules and Broussonetia papyrifera extract are increased respectively, the mite prevention effect does not increase significantly, and combined with Table 1, it can be seen that it will lead to a decrease in the mechanical properties of the fibers.

[0124] Table 4 Antibacterial Test Results

[0125]

[0126]

[0127] As can be seen from Table 4, the prepared eucalyptol-containing insecticidal and bacteriostatic regenerated cellulose fibers have inhibitory effects on Escherichia coli, Staphylococcus aureus and Candida albicans. After 10 times of washing, the bacteriostatic performance only slightly decreases. The regenerated cellulose fibers without eucalyptol microcapsules and Broussonetia papyrifera extracts or those with only one of them added alone have no bacteriostatic effect or slightly weaker bacteriostatic performance compared with those with both added, indicating that the two have a synergistic effect. In Examples 5 and 7, the addition amounts of the microcapsules and Broussonetia papyrifera extracts are reduced respectively, and the bacteriostatic effect significantly decreases; in Examples 6 and 8, the addition amounts of the microcapsules and Broussonetia papyrifera extracts are increased respectively, and the bacteriostatic effect does not increase significantly.

[0128] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and its concept of the present invention, making equivalent substitutions or changes should be covered within the protection scope of the present invention.

Claims

1. An insect-proof and antibacterial regenerated cellulose fiber containing eucalyptol, characterized in that: Viscose solution, eucalyptol microcapsules and plant extracts are used as raw materials to prepare a blended spinning solution, and insect-proof and antibacterial regenerated cellulose fibers are obtained through spinning; the eucalyptol microcapsules account for 3wt% to 5wt% of the methylcellulose content in the viscose solution, and the plant extracts account for 2wt% to 4wt% of the methylcellulose content in the viscose solution; the plant extracts are paper mulberry bark extracts.

2. The insect-proof and antibacterial regenerated cellulose fiber containing eucalyptol according to claim 1, characterized in that: The particle size D90 of the eucalyptus microcapsule is ≤1.5 μm; the core material is eucalyptus.

3. The insect-proof and antibacterial regenerated cellulose fiber containing eucalyptol according to claim 1, characterized in that: The viscose liquid is prepared from cellulose pulp with a polymerization degree of 500-600 as a raw material, and the mass content of methyl cellulose in the viscose liquid reaches 8%-10%.

4. The insect-proof and antibacterial regenerated cellulose fiber containing eucalyptol according to claim 1, characterized in that: The eucalyptol is high-purity eucalyptol, and its preparation method is as follows: S1. Collect fresh wormwood, take wormwood leaves, wash and dry in a cool place, crush and sieve after the mass is constant to obtain wormwood leaf powder; S2. Take the wormwood powder and the additives and add them to distilled water, and perform microwave extraction under microwave conditions; S3. After the extraction, the upper oil phase was collected from the volatile oil analyzer and dried with anhydrous Na2SO4 to obtain wormwood essential oil for later use; S4. The collected wormwood essential oil was subjected to vacuum distillation, the pressure was controlled at 0.073-0.078 MPa, and the 68-78 ° C fraction was collected to obtain a crude eucalyptol with a purity greater than 85%; S5. Freeze the crude eucalyptol at -20°C for 36 to 48 hours, take it out and centrifuge it to collect the solid to obtain high-purity eucalyptol.

5. The insect-proof and antibacterial regenerated cellulose fiber containing eucalyptol according to claim 4, characterized in that: The microwave power in S2 microwave extraction is 150-200 W, the extraction time is 15-20 min, and the solid-liquid ratio is 1:8-1:

15.

6. The insect-proof and antibacterial regenerated cellulose fiber containing eucalyptol according to claim 4, characterized in that: The auxiliary agent in S2 is sodium chloride; the amount of the auxiliary agent is 5wt% to 8wt% of distilled water.

7. The method for preparing the insect-proof and antibacterial regenerated cellulose fiber containing eucalyptol as claimed in claim 4, characterized in that: The preparation method is: a) adding eucalyptol microcapsule aqueous solution and paper mulberry bark extract to viscose solution, stirring to make the microcapsules and extract uniformly dispersed in spinning, and obtaining a blended spinning solution after standing, filtering, degassing and ripening for standby use; b) quantitatively transporting the blended spinning solution to a spinneret through a spinning pump, and spinning the fibers into the spinneret through the capillary holes to form a thin stream that enters a coagulation bath, so that the spinning solution is coagulated into fibers; c) drawing the coagulated fiber out of the coagulation bath and stretching the fiber by a stretching device; d) further post-treating the stretched fiber and drying it to obtain an insect-proof and antibacterial regenerated cellulose fiber containing eucalyptol.

8. The method for preparing the insect-proof and antibacterial regenerated cellulose fiber containing eucalyptol according to claim 7, characterized in that: The composition of the coagulation bath in step (b) is 100-120 g / L sulfuric acid, 250-300 g / L sodium sulfate, and 12-15 g / L zinc sulfate, and the coagulation bath temperature is 50-60°C.

9. The method for preparing the insect-proof and antibacterial regenerated cellulose fiber containing eucalyptol according to claim 7, characterized in that: The post-treatment steps include bunching and drawing, cutting, washing, desulfurization, bleaching, pickling and oiling; the drying temperature after post-treatment is 105-120°C.

10. Use of the insect-proof and antibacterial regenerated cellulose fiber containing eucalyptol according to claim 1 in the preparation of insect-proof and antibacterial textile products.

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