阅读说明：本技术 一种磁力片玩具及其制备方法 (Magnetic sheet toy and preparation method thereof ) 是由 徐江洋 卢海卫 于 2020-06-15 设计创作，主要内容包括：本发明公开了一种磁力片玩具及其制备方法。磁力片玩具包括壳体、位于壳体内的磁铁和垫片,所述壳体包括以下重量份的原料：30-50份树脂基料、15-20份负离子改性聚酯纤维、10-20份PVC糊树脂/蛋白石复合材料、15-20份负离子粘胶纤维、7-13份相容剂、2-5份抗氧剂、5-10份硅烷偶联剂、6-12份有机抗菌剂、5-15份阻燃剂。本发明的磁力片玩具具有能净化空气,改善幼儿教学环境的空气质量,且抗菌率好,抗菌效果好,耐洗性好,经多次洗涤后,仍具有较高的负离子释放量和抗菌率的优点。(The invention discloses a magnetic sheet toy and a preparation method thereof. The magnetic sheet toy comprises a shell, a magnet and a gasket, wherein the magnet and the gasket are positioned in the shell, and the shell comprises the following raw materials in parts by weight: 30-50 parts of resin base material, 15-20 parts of anion modified polyester fiber, 10-20 parts of PVC paste resin/opal composite material, 15-20 parts of anion viscose fiber, 7-13 parts of compatilizer, 2-5 parts of antioxidant, 5-10 parts of silane coupling agent, 6-12 parts of organic antibacterial agent and 5-15 parts of flame retardant. The magnetic sheet toy has the advantages of purifying air, improving the air quality of the infant teaching environment, along with good antibacterial rate, good antibacterial effect and good washability, and still has higher negative ion release amount and antibacterial rate after being washed for many times.)

1. The magnetic force piece toy is characterized by comprising a shell, a magnet and a gasket, wherein the magnet and the gasket are positioned in the shell, and the shell comprises the following raw materials in parts by weight: 30-50 parts of resin base material, 15-20 parts of anion modified polyester fiber, 10-20 parts of PVC paste resin/opal composite material, 15-20 parts of anion viscose fiber, 7-13 parts of compatilizer, 2-5 parts of antioxidant, 5-10 parts of silane coupling agent, 6-12 parts of organic antibacterial agent and 5-15 parts of flame retardant;

the preparation method of the PVC paste resin/opal composite material comprises the following steps: (1) drying the loofah sponge and the opal at 70-80 ℃ for 1-2h, crushing, adding the opal powder into a triethanolamine solution, stirring for 1-2h, taking out, drying at 80-90 ℃, placing the loofah sponge powder into a trimethyl propyl mercaptan solution, heating at 180-200 ℃ for 1.5-2h, wherein the mass ratio of the loofah sponge powder to the opal powder to the trimethyl propyl mercaptan solution is 1:0.8-1:1.2-1.5, and the mass ratio of the opal powder to the triethanolamine solution is 1: 1-1.3;

(2) uniformly mixing PVC paste resin, kelp powder and seaweed powder, heating to the temperature of 160-175 ℃, stirring for 1-2h, cooling to the temperature of 100-120 ℃, adding the opal powder and the loofah sponge powder while stirring, continuously stirring for 20-60min, vacuumizing and defoaming, and cooling to room temperature, wherein the preparation ratio of the PVC paste resin, the kelp powder and the seaweed powder is 1:0.5-0.8:0.3-0.5, and the mass ratio of the PVC paste resin, the opal powder and the loofah sponge powder is 1:1.2-1.5: 2-3.

2. The magnetic sheet toy of claim 1, wherein the negative ion modified polyester fiber is made by the following method: (1) mixing the nano-copper/zinc oxide composite antibacterial agent, the graphene and the hexacyclic stone, adding polyamide resin, heating to 180-200 ℃, uniformly mixing, cooling to 40-60 ℃, curing, grinding to the particle size of 200-400nm, and preparing negative ion master batch, wherein the mass ratio of the nano-copper/zinc oxide composite antibacterial agent to the graphene to the hexacyclic stone to the polyamide resin is 0.4-0.5:0.2-0.4:0.5-0.7: 1;

(2) mixing the PET chips and the negative ion master batches according to the mass ratio of 7-9:1-3, and then carrying out melt spinning at the melting temperature of 275-290 ℃ to obtain the negative ion modified polyester fiber.

3. The magnetic sheet toy of claim 2, wherein the nano copper/zinc oxide composite antibacterial agent is prepared by the following method: mixing and stirring zinc nitrate and copper nitrate, adding citric acid, mixing, adjusting the pH to 8-8.5 by using ammonia water, stirring at 80-85 ℃, drying at 85-90 ℃ to constant weight, calcining at 600 ℃ for 2h, cooling, grinding, wherein the mass ratio of zinc nitrate to copper nitrate to citric acid is 1: 0.02-0.1: 1.3-1.5.

4. The magnetic sheet toy of claim 1, wherein the negative ion viscose fiber is prepared by the following method: (1) mixing and grinding tourmaline powder and germanite powder, adding sodium polycarboxylate and cerium oxide, stirring at the rotating speed of 500r/min for 20-40min at 400-;

(2) mixing bamboo charcoal powder, mint extract and water according to the mass ratio of 1:0.8-1.2:3-5, and stirring at the rotating speed of 200-;

(3) and mixing the alkali cellulose, the negative ion slurry and the mixed slurry, filtering, defoaming and spinning to obtain the negative ion viscose, wherein the mass ratio of the alkali cellulose to the negative ion slurry to the mixed slurry is 1:0.6-0.8: 0.7-0.9.

5. The magnetic sheet toy of claim 1, wherein the resin base includes ABS resin, AS resin, and PC resin in a mass ratio of 1-2:0.5-1: 0.5-0.1.

6. The magnetic sheet toy of claim 1, wherein the organic antibacterial agent is prepared by mixing 3-methyl-4-isopropylphenol, paraben, polyhexamethylene guanidine in a mass ratio of 1:0.3-0.5: 0.5-0.7.

7. The magnetic sheet toy of claim 1, wherein the silane coupling agent is one or a combination of gamma-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane;

the antioxidant is one or a combination of more of antioxidant 1076, antioxidant 168 and antioxidant 1010.

8. The magnetic sheet toy of claim 1, wherein the compatibilizer is one or a combination of maleic anhydride grafted polyolefin, styrene-ethylene-propylene block copolymer, and maleic anhydride grafted PE;

the flame retardant is one or a combination of more of poly ammonium polyphosphate, melamine, aluminum hydroxide and zinc borate.

9. The magnetic sheet toy of claim 1, wherein the spacer is compounded from PE resin and PC resin in a mass ratio of 1: 0.5-2; the specification of the magnet is 4.3mm multiplied by 9 mm.

10. A method of making a magnetic sheet toy according to any one of claims 1 to 9, comprising the steps of:

s1, ultrasonically dispersing the negative ion modified polyester fiber, the negative ion viscose fiber and the PVC paste resin/opal composite material for 20-50min, adding a resin base material, a compatilizer and a silane coupling agent, stirring at the temperature of 175-190 ℃ for 20-40min, adding an antioxidant, an organic antibacterial agent and a flame retardant, mixing at the temperature of 180-200 ℃ for 5-10min, extruding by a double-screw extruder, and then injecting and molding to obtain the magnetic piece toy shell;

s2, placing the gasket and the magnet between the two magnetic force piece toy shells, then pressing the two magnetic force piece toy shells, softening the edges of the two magnetic force piece toys by using the heating plate, and enabling the joint parts of the two magnetic force piece toys to be tightly connected.

Technical Field

The invention relates to the technical field of plastic products, in particular to a magnetic sheet toy and a preparation method thereof.

Background

In recent years, with the continuous improvement of living standard of people, the requirements on living quality are higher and higher, the cultivation of infants is more and more emphasized, and most families are mainly concerned about the development of intelligence of the infants of low ages. For developing the intelligence of children, the market is full of various intelligence-developing toys, such as magnetic sheet toys. Magnetic force piece toy forms different molding through assembling the magnetic force piece with various magnetic forces, and the infant can exert latent imagination according to the shape of different magnetic force pieces, assembles into the model that oneself likes, for example: houses, cars, etc.

One magnetic sheet is composed of three parts: 1. shell (i.e. the final shape presented to us for the magnetic sheet); 2. an inner gasket (fixed and provided with a space for the magnet to rotate freely inside); 3. the strong magnet (core component) is characterized in that the magnetic sheet shell is made of food-grade ABS materials, so that even if an infant is bitten in the mouth, the infant cannot be hurt.

Disclosure of Invention

In view of the shortcomings of the prior art, the first object of the present invention is to provide a magnetic sheet toy, which has the advantages of purifying air and improving the air quality of the infant teaching environment.

The second purpose of the invention is to provide a preparation method of the magnetic sheet toy, which has the advantages of simple preparation process and easy operation.

In order to achieve the first object, the invention provides the following technical scheme: the magnetic force sheet toy comprises a shell, a magnet and a gasket, wherein the magnet and the gasket are positioned in the shell, and the shell comprises the following raw materials in parts by weight: 30-50 parts of resin base material, 15-20 parts of anion modified polyester fiber, 10-20 parts of PVC paste resin/opal composite material, 15-20 parts of anion viscose fiber, 7-13 parts of compatilizer, 2-5 parts of antioxidant, 5-10 parts of silane coupling agent, 6-12 parts of organic antibacterial agent and 5-15 parts of flame retardant;

the preparation method of the PVC paste resin/opal composite material comprises the following steps: (1) drying the loofah sponge and the opal at 70-80 ℃ for 1-2h, crushing, adding the opal powder into a triethanolamine solution, stirring for 1-2h, taking out, drying at 80-90 ℃, placing the loofah sponge powder into a trimethyl propyl mercaptan solution, heating at 180-200 ℃ for 1.5-2h, wherein the mass ratio of the loofah sponge powder to the opal powder to the trimethyl propyl mercaptan solution is 1:0.8-1:1.2-1.5, and the mass ratio of the opal powder to the triethanolamine solution is 1: 1-1.3;

(2) uniformly mixing PVC paste resin, kelp powder and seaweed powder, heating to the temperature of 160-175 ℃, stirring for 1-2h, cooling to the temperature of 100-120 ℃, adding the opal powder and the loofah sponge powder while stirring, continuously stirring for 20-60min, vacuumizing and defoaming, and cooling to room temperature, wherein the preparation ratio of the PVC paste resin, the kelp powder and the seaweed powder is 1:0.5-0.8:0.3-0.5, and the mass ratio of the PVC paste resin, the opal powder and the loofah sponge powder is 1:1.2-1.5: 2-3.

By adopting the technical scheme, the magnetic toy shell is prepared by adopting the PVC paste resin/opal composite material, the anion viscose fiber, the anion modified polyester fiber and other substances, the anion modified polyester fiber is melted and extruded by the polyester slices and the anion powder, the anion modified polyester fiber has the effect of releasing anions, and the anions are combined with harmful substances such as air positive ions, dust, fine impurities and the like to be settled on the ground, so that the effect of purifying air is achieved, the propagation of various viruses is inhibited, the antibacterial and bacteriostatic effects are achieved, meanwhile, the cortical function and the brain activity are enhanced, the spirit of infants is stimulated, the teaching quality is improved, the hygroscopicity of the anion viscose fiber is good, the anions can be released, the flexibility and the strength are good, the magnetic toy can be prevented from generating static electricity, and dust is adsorbed; the interface combination of the opal and the loofah sponge powder subjected to surface treatment and the PVC paste resin is good, the dispersion is uniform, the agglomeration is avoided, the loofah sponge is used as a reinforcing material of the PVC paste resin, the softness of the loofah sponge subjected to trimethyl propanethiol treatment is improved, the loofah sponge and the PVC paste resin have strong interface adhesion, the kelp powder and the seaweed powder have strong inhibition effect on bacteria, and the PVC paste resin, the kelp powder and the seaweed powder are mixed and then mixed with the opal powder and the loofah sponge powder, so that the PVC paste resin/opal composite material with high anion release amount and good antibacterial effect can be prepared.

Further, the anion modified polyester fiber is prepared by the following method: (1) mixing the nano-copper/zinc oxide composite antibacterial agent, the graphene and the hexacyclic stone, adding polyamide resin, heating to 180-200 ℃, uniformly mixing, cooling to 40-60 ℃, curing, grinding to the particle size of 200-400nm, and preparing negative ion master batch, wherein the mass ratio of the nano-copper/zinc oxide composite antibacterial agent to the graphene to the hexacyclic stone to the polyamide resin is 0.4-0.5:0.2-0.4:0.5-0.7: 1;

(2) mixing the PET chips and the negative ion master batches according to the mass ratio of 7-9:1-3, and then carrying out melt spinning at the melting temperature of 275-290 ℃ to obtain the negative ion modified polyester fiber.

By adopting the technical scheme, the nano-copper/zinc oxide composite antibacterial agent, the graphene, the hexacyclic stone and the polyamide resin are blended to prepare the anion master batch, when the PET slice and the anion master batch are subjected to melt spinning, the polyamide resin and the PET slice are melted, the nano-copper/zinc oxide composite antibacterial agent can improve the thermal stability and the antibacterial washability of the anion modified polyester fiber, and the graphene and the hexacyclic stone can improve the anion releasing performance and the anion releasing stability of the polyester fiber, so that the modified polyester fiber has a better washability effect, and still has higher anion releasing amount and antibacterial effect after being washed for multiple times; anion modified polyester fiber can also increase magnetic force piece toy moisture absorption, antistatic effect, prevents that the infant from holding when magnetic force piece toy, and the palm of the hand is perspired, glues on magnetic force piece toy surface, leads to the dust adhesion, can increase antistatic effect simultaneously, promotes dust adhesion effect.

Further, the preparation method of the nano-copper/zinc oxide composite antibacterial agent comprises the following steps: mixing and stirring zinc nitrate and copper nitrate, adding citric acid, mixing, adjusting the pH to 8-8.5 by using ammonia water, stirring at 80-85 ℃, drying at 85-90 ℃ to constant weight, calcining at 600 ℃ for 2h, cooling, grinding, wherein the mass ratio of zinc nitrate to copper nitrate to citric acid is 1: 0.02-0.1: 1.3-1.5.

By adopting the technical scheme, the copper ion doped zinc oxide can enhance the expansion degree and the absorption strength of the zinc oxide in the range of visible light, so that the visible light activity of the zinc oxide is improved, and the antibacterial performance is improved.

Further, the preparation method of the negative ion viscose fiber comprises the following steps: (1) mixing and grinding tourmaline powder and germanite powder, adding sodium polycarboxylate and cerium oxide, stirring at the rotating speed of 500r/min for 20-40min at 400-;

(2) mixing bamboo charcoal powder, mint extract and water according to the mass ratio of 1:0.8-1.2:3-5, and stirring at the rotating speed of 200-;

(3) and mixing the alkali cellulose, the negative ion slurry and the mixed slurry, filtering, defoaming and spinning to obtain the negative ion viscose, wherein the mass ratio of the alkali cellulose to the negative ion slurry to the mixed slurry is 1:0.6-0.8: 0.7-0.9.

By adopting the technical scheme, the tourmaline powder and the germanite powder have a strong negative ion releasing effect, the bamboo charcoal powder and the mint extract can enhance the antibacterial effect and the negative ion releasing amount of the negative ion viscose fiber, the cerium oxide can be matched with the tourmaline powder and the germanite powder, and after the fusion spinning with the alkali cellulose, the tourmaline powder, the germanite powder, the cerium oxide, the bamboo charcoal powder and the mint extract can be fully fused in the viscose fiber, so that the magnetic sheet toy has a relatively lasting air purifying and antibacterial effect, more negative ions can still be released after the magnetic sheet toy is washed for many times, and the antibacterial effect is good; hydroxyl groups in the mint extract and metal ions of tourmaline are beneficial to improving the ripening speed of cellulose and the crystallization of the cellulose, and crystals can be formed in agglomerated small particles of the tourmaline and the mint extract and filled in non-crystals of the cellulose, so that the crystallinity and the orientation degree of the whole fiber are improved.

Further, the resin base material comprises ABS resin, AS resin and PC resin in a mass ratio of 1-2:0.5-1: 0.5-0.1.

By adopting the technical scheme, the AS resin has high gloss, high transparency, high impact, good heat resistance and mechanical property, high rigidity, higher chemical stability, water resistance, oil resistance, acid resistance, alkali resistance and alcohol resistance, the PC resin has good impact resistance, good toughness, good optical property, thermal stability and bacteria inhibition property, and the PC resin, the AS resin and the ABS resin are blended to be used AS base materials, so that the magnetic sheet toy has excellent heat resistance, dimensional stability and impact resistance and also has excellent processing fluidity.

Further, the organic antibacterial agent is prepared by mixing 3-methyl-4-isopropyl phenol, p-hydroxybenzoate and polyhexamethylene guanidine according to a mass ratio of 1:0.3-0.5: 0.5-0.7.

By adopting the technical scheme, the 3-methyl-4-isopropyl phenol has very strong sterilization and antibiosis benefits, inhibits oxidation and degradation of the magnetic sheet toy, inhibits various moulds, yeasts and bacteria from being affected by the paraben, has the characteristics of sterilization spectrum, high action speed, long-term bacteriostasis and no corrosivity, and can improve the antibacterial durability of the magnetic sheet toy by cooperatively using the three.

Further, the silane coupling agent is one or a combination of a plurality of gamma-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane;

the antioxidant is one or a combination of more of antioxidant 1076, antioxidant 168 and antioxidant 1010.

Further, the compatilizer is one or a combination of more of maleic anhydride grafted polyolefin, styrene-ethylene-propylene block copolymer and maleic anhydride grafted PE.

The flame retardant is one or a combination of more of poly ammonium polyphosphate, melamine, aluminum hydroxide and zinc borate.

The gasket is prepared by compounding PE resin and PC resin according to the mass ratio of 1: 0.5-2; the specification of the magnet is 4.3mm multiplied by 9 mm.

By adopting the technical scheme, the PC resin has good impact resistance, good toughness, good optical performance, good thermal stability and bacteria inhibiting property, and the PE resin has the advantages of good impact resistance and high chemical stability, and the PE resin are matched for use, so that the gasket has good bacteriostasis, impact resistance and thermal stability.

In order to achieve the second object, the invention provides the following technical scheme: a preparation method of a magnetic sheet toy comprises the following steps:

s1, ultrasonically dispersing the negative ion modified polyester fiber, the negative ion viscose fiber and the PVC paste resin/opal composite material for 20-50min, adding a resin base material, a compatilizer and a silane coupling agent, stirring at the temperature of 175-190 ℃ for 20-40min, adding an antioxidant, an organic antibacterial agent and a flame retardant, mixing at the temperature of 180-200 ℃ for 5-10min, extruding by a double-screw extruder, and then injecting and molding to obtain the magnetic piece toy shell;

s2, placing the gasket and the magnet between the two magnetic force piece toy shells, then pressing the two magnetic force piece toy shells, softening the edges of the two magnetic force piece toys by using the heating plate, and enabling the joint parts of the two magnetic force piece toys to be tightly connected.

In conclusion, the invention has the following beneficial effects:

firstly, because the invention adopts PVC paste resin/opal composite material, anion viscose fiber and anion modified polyester fiber and other raw materials to prepare the magnetic sheet toy, because the PVC paste resin uses opal powder and loofah sponge powder, and is doped with kelp powder and seaweed powder, the negative ion release amount of the magnetic sheet toy is high, the magnetic sheet toy can purify air, improve air quality, has good antibacterial effect, prevents children from infecting germs when playing, and simultaneously is matched with the anion modified polyester fiber and the anion viscose fiber, so that the magnetic sheet toy has better water absorption and antistatic effects, can absorb sweat stains on palms of the children when playing, and reduces dust adhesion amount.

Secondly, the anion modified polyester fiber is prepared by preferentially adopting the nano-copper/zinc oxide composite antibacterial agent, the graphene, the hexacyclic stone and the PET slice for melt spinning, the hexacyclic stone reaches the level of people after being ground, the hexacyclic stone can be better dispersed in the polyester fiber, the graphene can enhance the antibacterial effect of the polyester fiber, and the nano-copper/zinc oxide composite antibacterial agent can improve the thermal stability and the antibacterial washability of the anion modified polyester fiber, so that the supported anion modified polyester fiber has higher anion release amount and better antibacterial effect.

Thirdly, tourmaline powder, germanite powder and cerium oxide are preferably mixed to prepare negative ion slurry, the cerium oxide can be matched with the tourmaline powder and the germanite powder to enable the tourmaline powder and the germanite powder to continuously release negative ions, then the slurry prepared by mixing bamboo charcoal powder and mint extract is melt-spun with the negative ion slurry and alkali lignin to prepare negative ion viscose, and the bamboo charcoal, the mint extract, the tourmaline powder and the germanite powder are fully fused in the viscose, so that the magnetic sheet toy has relatively lasting air purifying and antibacterial effects.

Detailed Description

The present invention will be described in further detail with reference to examples.

Preparation examples 1 to 3 of PVC paste resin/opal composite Material

The PVC paste resin in preparation examples 1 to 3 was selected from the PVC paste resin sold under the trade designation P450 by Rong Bei (Shanghai) chemical science and technology Limited, the kelp powder was selected from the kelp powder sold under the trade designation 094 by Jiangsu Jinjie food Limited, and the kelp powder was selected from the kelp powder sold under the trade designation 002 by Shenzhen Hensheng Biotech Limited.

Preparation example 1: (1) drying the loofah sponge and the opal at 70 ℃ for 2h, crushing, adding the opal powder into a triethanolamine solution, stirring for 1h, taking out, drying at 80 ℃, placing the loofah sponge powder into a trimethyl propyl mercaptan solution, heating at 180 ℃ for 2h, wherein the mass ratio of the loofah sponge powder to the opal powder to the trimethyl propyl mercaptan solution is 1:0.8:1.2, and the mass ratio of the opal powder to the triethanolamine solution is 1: 1;

(2) uniformly mixing PVC paste resin, kelp powder and seaweed powder, heating to 160 ℃, stirring for 2 hours, cooling to 100 ℃, adding the opal powder and the loofah sponge powder while stirring, continuously stirring for 20 minutes, vacuumizing, defoaming, and cooling to room temperature, wherein the preparation ratio of the PVC paste resin to the opal powder to the loofah sponge powder is 1:0.5:0.3, the mass ratio of the PVC paste resin to the opal powder to the loofah sponge powder is 1:1.2:2, and the particle size of the kelp powder to the seaweed powder is 200 nm.

Preparation example 2: (1) drying the loofah sponge and the opal at 75 ℃ for 1.5h, crushing, adding the opal powder into a triethanolamine solution, stirring for 1.5h, taking out, drying at 85 ℃, placing the loofah sponge powder into a trimethyl propyl mercaptan solution, heating at 190 ℃ for 1.8h, wherein the mass ratio of the loofah sponge powder to the opal powder to the trimethyl propyl mercaptan solution is 1:0.9:1.3, and the mass ratio of the opal powder to the triethanolamine solution is 1: 1.2;

(2) uniformly mixing PVC paste resin, kelp powder and seaweed powder, heating to 170 ℃, stirring for 1.5h, cooling to 150 ℃, adding the opal powder and the loofah sponge powder while stirring, continuously stirring for 40min, vacuumizing, defoaming, and cooling to room temperature, wherein the preparation ratio of the PVC paste resin to the opal powder to the loofah sponge powder is 1:0.7:0.4, the mass ratio of the PVC paste resin to the opal powder to the loofah sponge powder is 1:1.3:2.5, and the particle size of the kelp powder to the seaweed powder is 200 nm.

Preparation example 3: (1) drying the loofah sponge and the opal at 80 ℃ for 1h, crushing, adding the opal powder into a triethanolamine solution, stirring for 1h, taking out, drying at 90 ℃, placing the loofah sponge powder into a trimethyl propyl mercaptan solution, heating at 200 ℃ for 1.5h, wherein the mass ratio of the loofah sponge powder to the opal powder to the trimethyl propyl mercaptan solution is 1:1:1.5, and the mass ratio of the opal powder to the triethanolamine solution is 1: 1.3;

(2) uniformly mixing PVC paste resin, kelp powder and seaweed powder, heating to 175 ℃, stirring for 1h, cooling to 200 ℃, adding the opal powder and the loofah sponge powder while stirring, continuously stirring for 60min, vacuumizing, defoaming, and cooling to room temperature, wherein the mass ratio of the PVC paste resin to the opal powder to the loofah sponge powder is 1:0.8:0.5, the particle size of the kelp powder to the seaweed powder is 200nm, and the mass ratio of the PVC paste resin to the opal powder to the loofah sponge powder is 1:1.5: 3.

Preparation examples 4-6 of composite antibacterial agent of nano copper/zinc oxide

Preparation example 4: mixing and stirring zinc nitrate and copper nitrate, adding citric acid, mixing, adjusting the pH to 8 by using ammonia water, stirring at 80 ℃, drying at 85 ℃ to constant weight, calcining at 600 ℃ for 2 hours, cooling, grinding, wherein the mass ratio of the zinc nitrate to the copper nitrate to the citric acid is 1:0.02: 1.3.

Preparation example 5: mixing and stirring zinc nitrate and copper nitrate, adding citric acid, mixing, adjusting the pH to 8.3 by using ammonia water, stirring at 83 ℃, drying at 88 ℃ to constant weight, calcining at 600 ℃ for 2 hours, cooling and grinding, wherein the mass ratio of the zinc nitrate to the copper nitrate to the citric acid is 1:0.06: 1.4.

Preparation example 6: mixing and stirring zinc nitrate and copper nitrate, adding citric acid, mixing, adjusting the pH to 8.5 by using ammonia water, stirring at 85 ℃, drying at 90 ℃ to constant weight, calcining at 600 ℃ for 2 hours, cooling and grinding, wherein the mass ratio of the zinc nitrate to the copper nitrate to the citric acid is 1:0.1: 1.5.

Preparation examples 7 to 9 of anion viscose fibers

Preparation example 7: (1) mixing and grinding tourmaline powder and germanite powder, adding sodium polycarboxylate and cerium oxide, stirring at the rotating speed of 400r/min for 40min to prepare negative ion slurry, wherein the mass ratio of the tourmaline powder to the germanite powder to the sodium polycarboxylate to the cerium oxide is 0.8:0.7:1: 1;

(2) mixing bamboo charcoal powder, herba Menthae extract and water at a mass ratio of 1:0.8:3, stirring at a rotation speed of 200r/min for 50min to obtain mixed slurry;

(3) and mixing the alkali cellulose, the negative ion slurry and the mixed slurry, filtering, defoaming and spinning to obtain the negative ion viscose, wherein the mass ratio of the alkali cellulose to the negative ion slurry to the mixed slurry is 1:0.6: 0.7.

Preparation example 8: (1) mixing and grinding tourmaline powder and germanite powder, adding sodium polycarboxylate and cerium oxide, stirring at the rotating speed of 450r/min for 30min to prepare negative ion slurry, wherein the mass ratio of the tourmaline powder to the germanite powder to the sodium polycarboxylate to the cerium oxide is 0.9:0.8:1.5: 1.3;

(2) mixing bamboo charcoal powder, herba Menthae extract and water at a mass ratio of 1:1:4, stirring at 250r/min for 40min to obtain mixed slurry;

(3) and mixing the alkali cellulose, the negative ion slurry and the mixed slurry, filtering, defoaming and spinning to obtain the negative ion viscose, wherein the mass ratio of the alkali cellulose to the negative ion slurry to the mixed slurry is 1:0.7: 0.8.

Preparation example 9: (1) mixing and grinding tourmaline powder and germanite powder, adding sodium polycarboxylate and cerium oxide, stirring at the rotating speed of 500r/min for 20min to prepare negative ion slurry, wherein the mass ratio of the tourmaline powder to the germanite powder to the sodium polycarboxylate to the cerium oxide is 1:0.9:2: 1.5;

(2) mixing bamboo charcoal powder, herba Menthae extract and water at a mass ratio of 1:1.2:5, stirring at 300r/min for 50min to obtain mixed slurry;

(3) and mixing the alkali cellulose, the negative ion slurry and the mixed slurry, filtering, defoaming and spinning to obtain the negative ion viscose, wherein the mass ratio of the alkali cellulose to the negative ion slurry to the mixed slurry is 1:0.8: 0.9.