阅读说明：本技术 一种磁性玩具用抗菌abs材料及其制备方法 (Antibacterial ABS material for magnetic 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性玩具用抗菌ABS材料及其制备方法,其技术方案要点是一种磁性玩具用抗菌ABS材料,以重量份数计,包括如下组分：ABS树脂70-80份、环保型增塑剂4-6份、润滑剂0.5-2份、抗氧剂0.5-1份以及复合抗菌剂1-3份；所述复合抗菌剂由重量比为1:(1-3)的聚六亚甲基胍和磷酸锆载银抗菌剂混合而成；所述磷酸锆载银抗菌剂在使用前经过表面处理,具体操作包括如下步骤：取磷酸锆载银抗菌剂,加入磷酸锆载银抗菌剂重量的4-6%的改性剂,搅拌后加入磷酸锆载银抗菌剂中的0.2-0.5wt%的硅烷偶联剂,经过研磨、干燥即可。本发明的ABS材料具有抗菌效果好、时效性长的优点。(The invention discloses an antibacterial ABS material for a magnetic toy and a preparation method thereof, and the technical scheme is that the antibacterial ABS material for the magnetic toy comprises the following components in parts by weight: 70-80 parts of ABS resin, 4-6 parts of environment-friendly plasticizer, 0.5-2 parts of lubricant, 0.5-1 part of antioxidant and 1-3 parts of composite antibacterial agent; the composite antibacterial agent is formed by mixing polyhexamethylene guanidine and zirconium phosphate silver-loaded antibacterial agent in a weight ratio of 1 (1-3); the zirconium phosphate silver-loaded antibacterial agent is subjected to surface treatment before use, and the specific operation comprises the following steps: adding a modifier which is 4-6% of the weight of the zirconium phosphate silver-loaded antibacterial agent into the zirconium phosphate silver-loaded antibacterial agent, stirring, adding a silane coupling agent which is 0.2-0.5wt% of the zirconium phosphate silver-loaded antibacterial agent, grinding and drying. The ABS material has the advantages of good antibacterial effect and long timeliness.)

1. An antibacterial ABS material for magnetic toys is characterized in that: the paint comprises the following components in parts by weight: 70-80 parts of ABS resin, 4-6 parts of environment-friendly plasticizer, 0.5-2 parts of lubricant, 0.5-1 part of antioxidant and 1-3 parts of composite antibacterial agent;

the composite antibacterial agent is formed by mixing polyhexamethylene guanidine and zirconium phosphate silver-loaded antibacterial agent in a weight ratio of 1 (1-3);

the zirconium phosphate silver-loaded antibacterial agent is subjected to surface treatment before use, and the specific operation comprises the following steps: adding a modifier which is 4-6% of the weight of the zirconium phosphate silver-loaded antibacterial agent into the zirconium phosphate silver-loaded antibacterial agent, stirring, adding a silane coupling agent which is 0.2-0.5wt% of the zirconium phosphate silver-loaded antibacterial agent, grinding and drying.

2. The antibacterial ABS material for magnetic toys according to claim 1, wherein: the modifier is prepared by adopting the following method: taking 10-20 parts of isothiazolinone, 2-4 parts of polyaspartic acid, 2-3 parts of itaconic anhydride and 20-30 parts of glycerol carbonate by weight parts, heating to 80-90 ℃, and stirring for 20-30min under heat preservation to obtain the modifier.

3. The antibacterial ABS material for magnetic toys according to claim 1, wherein: the polyhexamethylene guanidine is coated before use, and the specific operation comprises the following steps: taking 1 part of polyhexamethylene guanidine by weight, adding 2-2.5 parts of medical stone powder into the polyhexamethylene guanidine, and stirring at the speed of 800-; ② adding coating liquid with the weight of 2-4% of the polyhexamethylene guanidine-medical stone powder mixture, stirring for 20-40min at the temperature of 90-110 ℃, drying and cooling.

4. The antibacterial ABS material for magnetic toys according to claim 3, wherein: the coating solution is prepared by the following method: taking 10-20 parts of zinc oxide, 20-25 parts of zein, 3-5 parts of lauric acid monoglyceride, 2-3 parts of calcium stearate, 0.2-0.4 part of silane coupling agent and 40-50 parts of ethanol solution with volume fraction of 80% -92% by weight, and stirring for 20-40min at the temperature of 70-80 ℃ to obtain the coating solution.

5. The antibacterial ABS material for magnetic toys according to claim 1, wherein: the environment-friendly plasticizer is prepared by mixing acetyl tributyl citrate and epoxy soybean oil in a weight ratio of 1: 1.

6. The antibacterial ABS material for magnetic toys according to claim 1, wherein: the antioxidant is prepared by mixing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate and tris [2, 4-di-tert-butylphenyl ] phosphite in a weight ratio of 3: 1.

7. The antibacterial ABS material for magnetic toys according to claim 1, wherein: the lubricant is one of pentaerythritol stearate and ethylene bis-stearamide or a compound of the pentaerythritol stearate and the ethylene bis-stearamide.

8. A preparation method of an antibacterial ABS material for magnetic toys is characterized by comprising the following steps: the method comprises the following steps:

s1, mixing materials: weighing the pre-dried ABS resin, the environment-friendly plasticizer, the lubricant, the antioxidant and the composite antibacterial agent according to the proportion, and mixing for 10-30min at the speed of 1000-2000r/min to obtain a mixture;

s2, melting and blending the mixture at the temperature of 160-200 ℃, extruding and granulating.

9. The preparation method of the antibacterial ABS material for the magnetic toy according to claim 8, characterized in that: the pre-dried ABS resin in S1 refers to: and (3) drying the ABS resin for 2-4h by hot air at the temperature of 70-80 ℃.

10. The preparation method of the antibacterial ABS material for the magnetic toy according to claim 8, characterized in that: s2, placing the mixture in a double-screw extruder for melt blending, wherein the temperatures of the zones are as follows: the temperature of the first zone is 160-170 ℃, the temperature of the second zone is 170-180 ℃, the temperature of the third zone is 180-190 ℃, the temperature of the fourth zone is 190-200 ℃, the temperature of the fifth zone is 185-195 ℃, the temperature of the sixth zone is 180-190 ℃ and the temperature of the die head is 180-190 ℃.

Technical Field

The invention relates to the technical field of high polymer materials, in particular to an antibacterial ABS material for a magnetic toy and a preparation method thereof.

Background

The magnetic toy is a spliced intelligence toy composed of a plurality of magnetic sheets, is similar to the traditional building blocks, is spliced into the shapes of houses, vehicles, animals and the like through different arrangement combinations, and is beneficial to training the hand-eye coordination ability of children and developing the intelligence of the children. Different from the traditional building blocks, because the magnetic force piece is composed of a plastic sheet and a magnet, in the prior art, a Chinese patent with an authorization publication number of CN201823320U discloses a polygonal magnetic splicing toy which is composed of a magnet and a body, wherein the body is polygonal, the magnet is arranged at the edge of each edge of the body, the body and the magnet are fixedly connected through a magnet sleeve, a middle shaft of the magnet is parallel to the edge of the magnet, and the body is further provided with a steel ball hole. After a plurality of magnetic force pieces are spliced with each other, the connection device can be accurately positioned and is not easy to move after being connected and firm in connection through attraction of the magnets, the connection device is convenient to split and rich in color, and therefore the connection device has a very wide market space.

Because the magnetic toys are mostly used by children of 3-12 years old, plastic sheets for the magnetic toys are required to be safe and non-toxic, have high impact resistance and falling resistance, have good luster and bright colors, and ABS plastics are mostly adopted as the plastic sheets for the magnetic toys at present for the reasons. The ABS plastic is a terpolymer of three monomers of acrylonitrile (A), butadiene (B) and styrene (S), and integrates the performances of three components, wherein the acrylonitrile has high hardness and strength, heat resistance and corrosion resistance; butadiene has impact resistance and toughness; the styrene has high surface gloss, easy coloring and easy processing, and the characteristics of the three components enable the ABS plastic to become a thermoplastic plastic with good comprehensive performance of toughness, hardness and rigidity.

As children are contacted with different toys for a long time and may carry partial bacteria when touching the toys, parents can regularly disinfect and sterilize the toys, the generally adopted disinfection method is to boil the toys in boiling water for a period of time to kill worm eggs and bacteria, but as the heat-resistant temperature of ABS plastic is generally 80-90 ℃, the ABS plastic is easy to deform when disinfected at high temperature, the mechanical property of the ABS plastic is reduced, and the service life of the ABS plastic is influenced.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide the antibacterial ABS material for the magnetic toy, which has the advantages of good antibacterial effect and long timeliness.

The second purpose of the invention is to provide a preparation method of the antibacterial ABS material for the magnetic toy, which has the advantages of simple operation and easy processing.

In order to achieve the first object, the invention provides the following technical scheme: an antibacterial ABS material for magnetic toys comprises the following components in parts by weight: 70-80 parts of ABS resin, 4-6 parts of environment-friendly plasticizer, 0.5-2 parts of lubricant, 0.5-1 part of antioxidant and 1-3 parts of composite antibacterial agent; the composite antibacterial agent is formed by mixing polyhexamethylene guanidine and zirconium phosphate silver-loaded antibacterial agent in a weight ratio of 1 (1-3); the zirconium phosphate silver-loaded antibacterial agent is subjected to surface treatment before use, and the specific operation comprises the following steps: adding a modifier which is 4-6% of the weight of the zirconium phosphate silver-loaded antibacterial agent into the zirconium phosphate silver-loaded antibacterial agent, stirring, adding a silane coupling agent which is 0.2-0.5wt% of the zirconium phosphate silver-loaded antibacterial agent, grinding and drying.

By adopting the technical scheme, the zirconium phosphate silver-carrying antibacterial agent belongs to an inorganic antibacterial agent, is a broad-spectrum antibacterial agent, is harmless to human bodies, has no irritation to skin, and belongs to a safe and non-toxic product; after the surface treatment, the compatibility of the ABS resin with the ABS resin can be improved; the composite antibacterial agent obtained by compounding the polyhexamethylene guanidine and the zirconium phosphate silver-loaded antibacterial agent is safe and non-toxic, has no stimulation to skin, and has good dispersibility in ABS resin; the composite antibacterial agent not only has good antibacterial effect, but also has good hydrolysis resistance, and still has good antibacterial performance after being washed by the surfactant for multiple times, so that the ABS material has long-acting and lasting antibacterial effect.

Further, the modifier is prepared by adopting the following method: taking 10-20 parts of isothiazolinone, 2-4 parts of polyaspartic acid, 2-3 parts of itaconic anhydride and 20-30 parts of glycerol carbonate by weight parts, heating to 80-90 ℃, and stirring for 20-30min under heat preservation to obtain the modifier.

By adopting the technical scheme, the isothiazolinone is a broad-spectrum, high-efficiency and low-toxicity bactericide and has the advantage of low toxicity, the modifier prepared by mixing the isothiazolinone with polyaspartic acid, itaconic anhydride and glycerol carbonate has a certain antibacterial effect, and after the zirconium phosphate silver-carrying antibacterial agent is treated by the modifier, on one hand, the antibacterial durability of the zirconium phosphate silver-carrying antibacterial agent can be improved, on the other hand, the zirconium phosphate silver-carrying antibacterial agent is subjected to modification treatment in advance and then the surface of the zirconium phosphate silver-carrying antibacterial agent is treated by the silane coupling agent, so that the zirconium phosphate silver-carrying antibacterial agent can be prevented from being agglomerated in a polymer, the dispersibility of the zirconium phosphate silver-carrying antibacterial agent in the polymer is improved, and the defect of reduction of the mechanical property of the polymer caused by.

Further, the polyhexamethylene guanidine is coated before use, and the specific operation comprises the following steps: taking 1 part of polyhexamethylene guanidine by weight, adding 2-2.5 parts of medical stone powder into the polyhexamethylene guanidine, and stirring at the speed of 800-; ② adding coating liquid with the weight of 2-4% of the polyhexamethylene guanidine-medical stone powder mixture, stirring for 20-40min at the temperature of 90-110 ℃, drying and cooling.

By adopting the technical scheme, the medical stone has strong adsorption effect, and the medical stone is mixed with the polyhexamethylene guanidine to adsorb the polyhexamethylene guanidine so as to disperse the polyhexamethylene guanidine in pores of the medical stone powder; after the polyhexamethylene guanidine-medical stone powder mixture is coated, a coating film can be formed on the surface of the medical stone powder, so that the compatibility of the medical stone powder and ABS resin can be improved, the dispersion uniformity of the medical stone powder in a polymer can be improved, and the effect of protecting the polyhexamethylene guanidine can be improved through the coating film with a certain antibacterial effect, so that the defect of easy hydrolysis of the polyhexamethylene guanidine can be relieved, and the long-acting antibacterial performance of the polyhexamethylene guanidine can be effectively prolonged.

Further, the coating solution is prepared by the following method: by weight, 10-20 parts of zinc oxide, 20-25 parts of zein, 3-5 parts of lauric acid monoglyceride, 2-3 parts of calcium stearate, 0.2-0.4 part of silane coupling agent and 40-50 parts of

Stirring 80-92% ethanol solution at 70-80 deg.C for 20-40min to obtain coating solution.

By adopting the technical scheme, the lauric acid monoglyceride, also known as lauric acid monoglyceride, is a lipophilic nonionic surfactant, and the coating liquid is prepared by mixing isothiazolinone, zein, lauric acid monoglyceride, calcium stearate and a silane coupling agent, so that the compatibility of the medical stone powder and ABS resin can be improved on one hand, the dispersion uniformity of the medical stone powder and ABS resin in a polymer is improved, and the effect of protecting polyhexamethylene guanidine can be improved through a coating film with a certain antibacterial effect on the other hand, the defect of easy hydrolysis of polyhexamethylene guanidine is relieved, and the long-acting antibacterial performance of the polyhexamethylene guanidine can be effectively prolonged.

Further, the environment-friendly plasticizer is formed by mixing acetyl tributyl citrate and epoxy soybean oil in a weight ratio of 1: 1.

By adopting the technical scheme, the acetyl tributyl citrate belongs to a citrate plasticizer, is safe and non-toxic, and the epoxidized soybean oil belongs to an epoxy plasticizer, is a plasticizer prepared by performing epoxidation reaction on natural oil and organic peroxyacid, and has the advantages of no toxicity and good light resistance and stability; the environment-friendly plasticizer obtained by mixing the epoxidized soybean oil and the acetyl tributyl citrate has the advantages of safety and low toxicity, and has a good plasticizing effect on ABS materials.

Further, the antioxidant is prepared by mixing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester and tris [2, 4-di-tert-butylphenyl ] phosphite in a weight ratio of 3: 1.

By adopting the technical scheme, the n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate is also called as an antioxidant 1076, and the tris [2, 4-di-tert-butylphenyl ] phosphite is also called as an antioxidant 168, so that when the antioxidant 1076 and the antioxidant 168 are compounded, a remarkable synergistic effect is achieved, the thermal degradation and oxidative degradation of ABS resin can be effectively inhibited, and the mechanical strength of the polymer is improved.

Further, the lubricant is one of pentaerythritol stearate and ethylene bis-stearic acid amide or a compound of the pentaerythritol stearate and the ethylene bis-stearic acid amide.

By adopting the technical scheme, the pentaerythritol stearate is safe, non-toxic, good in internal and external lubricity, good in compatibility with ABS resin, and capable of improving the thermal stability and the demolding property of a product; the erucamide is safe and non-toxic, and the ethylene bis-stearamide also has good internal and external lubricity, so that the fluidity of the resin is improved, the demolding performance is improved, and the surface glossiness of the product is improved.

In order to achieve the second object, the invention provides the following technical scheme:

a preparation method of an antibacterial ABS material for magnetic toys is characterized by comprising the following steps: the method comprises the following steps:

s1, mixing materials: weighing the pre-dried ABS resin, the environment-friendly plasticizer, the lubricant, the antioxidant and the composite antibacterial agent according to the proportion, and mixing for 10-30min at the speed of 1000-2000r/min to obtain a mixture;

s2, melting and blending the mixture at the temperature of 160-200 ℃, extruding and granulating.

Further, the ABS resin predried in S1 means: and (3) drying the ABS resin for 2-4h by hot air at the temperature of 70-80 ℃.

By adopting the technical scheme, the water absorption of the ABS is generally 0.2-0.5%, and the ABS resin is dried before processing to reduce the water content to be below 0.1%, so that appearance defects such as bubbles, silver wires and the like on the surface of a product can be reduced, and the quality of the product is improved.

Further, S2, the mixture is put into a double-screw extruder for melt blending, and the temperature of each zone is as follows: the temperature of the first zone is 160-170 ℃, the temperature of the second zone is 170-180 ℃, the temperature of the third zone is 180-190 ℃, the temperature of the fourth zone is 190-200 ℃, the temperature of the fifth zone is 185-195 ℃, the temperature of the sixth zone is 180-190 ℃ and the temperature of the die head is 180-190 ℃.

In summary, compared with the prior art, the invention has the following beneficial effects:

1. the zirconium phosphate silver-carrying antibacterial agent belongs to an inorganic antibacterial agent, is a broad-spectrum antibacterial agent, is harmless to human bodies, has no irritation to skins, and belongs to a safe and non-toxic product; after the surface treatment, the compatibility of the ABS resin with the ABS resin can be improved; the composite antibacterial agent obtained by compounding the polyhexamethylene guanidine and the zirconium phosphate silver-loaded antibacterial agent is safe and non-toxic, has no stimulation to skin, and has good dispersibility in ABS resin; the composite antibacterial agent not only has good antibacterial effect, but also has good hydrolysis resistance, and still has good antibacterial performance after being washed by the surfactant for multiple times, so that the ABS material has long-acting and lasting antibacterial effect;

2. isothiazolinone is a broad-spectrum, high-efficient, low-toxicity fungicide, the advantage with low toxicity, the modifier made by mixing isothiazolinone, poly aspartic acid, itaconic anhydride and carbonic acid glyceride, have certain antibacterial effects, after adopting modifier to carry on the treatment to silver-carrying antiseptic of zirconium phosphate, on the one hand can improve its antibacterial persistence, on the other hand after modifying it in advance, process its surface through silane coupling agent, can prevent silver-carrying antiseptic of zirconium phosphate from agglomerating in the polymer, in order to improve its dispersibility in polymer, thus reduce the defect that the mechanical property of the polymer is reduced because of adding the inorganic antiseptic;

3. the medical stone has strong adsorption effect, and the medical stone can be mixed with polyhexamethylene guanidine to adsorb the polyhexamethylene guanidine so as to disperse the polyhexamethylene guanidine in pores of the medical stone powder; after the polyhexamethylene guanidine-medical stone powder mixture is coated, a coating film can be formed on the surface of the medical stone powder, so that the compatibility of the medical stone powder and ABS resin can be improved, the dispersion uniformity of the medical stone powder in a polymer can be improved, and the effect of protecting the polyhexamethylene guanidine can be improved through the coating film with a certain antibacterial effect, so that the defect of easy hydrolysis of the polyhexamethylene guanidine can be relieved, and the long-acting antibacterial performance of the polyhexamethylene guanidine can be effectively prolonged.

Detailed Description

The present invention will be described in further detail below.

Examples of preparation of composite antimicrobial the silver-loaded zirconium phosphate antimicrobial agent of the following examples was selected from the silver-loaded zirconium phosphate antimicrobial agent available from xiamen xindakang inorganic materials ltd under model number XDK-201.

Preparation example 1: the composite antibacterial agent is prepared by the following method:

(1) pretreatment of polyhexamethylene guanidine: 1kg of polyhexamethylene guanidine is taken, 2kg of medical stone powder is added into the polyhexamethylene guanidine, and the mixture is stirred for 10min at the speed of 800r/min to obtain a polyhexamethylene guanidine-medical stone powder mixture;

secondly, stirring 10kg of zinc oxide, 20kg of zein, 3kg of lauric acid monoglyceride, 2kg of calcium stearate, 0.2kg of silane coupling agent KH5500.2kg and 40kg of ethanol solution with the volume fraction of 80% at the temperature of 70 ℃ for 20min to obtain a coating solution;

③ adding 2 percent of coating liquid of the weight of the mixture of polyhexamethylene guanidine and medical stone powder into the mixture, stirring the mixture for 20min at the temperature of 90 ℃ at the speed of 400r/min, then drying the mixture for 10h at the temperature of 80 ℃, and cooling the mixture to the normal temperature.

(2) Pretreatment of the zirconium phosphate silver-loaded antibacterial agent: heating 10kg of isothiazolinone, 2kg of polyaspartic acid, 2kg of itaconic anhydride and 20kg of glycerol carbonate to 80 ℃, and stirring for 20min under the condition of heat preservation to obtain a modifier;

secondly, stirring 1kg of zirconium phosphate silver-loaded antibacterial agent and 0.04kg of modifier at the speed of 1000r/min for 30min, adding 0.002kg of silane coupling agent KH550, and performing ball milling at the speed of 100r/min for 2h to obtain a ball-milled substance; and then drying the ball-milled material for 8 hours at the temperature of 120 ℃.

(3) Mixing: and (3) stirring the polyhexamethylene guanidine pretreated in the step (1) and the zirconium phosphate silver-loaded antibacterial agent pretreated in the step (2) at the speed of 200r/min for 10min to obtain the composite antibacterial agent.

Preparation example 2: the composite antibacterial agent is prepared by the following method:

(1) pretreatment of polyhexamethylene guanidine: 1kg of polyhexamethylene guanidine is taken, 2.25kg of medical stone powder is added into the polyhexamethylene guanidine, and the mixture is stirred for 15min at the speed of 1500r/min to obtain a polyhexamethylene guanidine-medical stone powder mixture;

15kg of zinc oxide, 22.5kg of zein, 4kg of lauric acid monoglyceride, 2.5kg of calcium stearate, 0.3kg of silane coupling agent KH550and 45kg of ethanol solution with the volume fraction of 85 percent are stirred for 30min at the temperature of 75 ℃ to obtain coating liquid; ③ adding coating liquid accounting for 3 percent of the weight of the mixture of the polyhexamethylene guanidine and the medical stone powder into the mixture, stirring the mixture for 30min at the temperature of 100 ℃ at the speed of 400r/min, then drying the mixture for 10h at the temperature of 80 ℃, and cooling the mixture to the normal temperature.

(2) Pretreatment of the zirconium phosphate silver-loaded antibacterial agent: firstly, heating 15kg of isothiazolinone, 3kg of polyaspartic acid, 2.5kg of itaconic anhydride and 25kg of glycerol carbonate to 85 ℃, and stirring for 25min under the condition of heat preservation to obtain a modifier;

adding 0.1kg of modifier into 2kg of zirconium phosphate silver-loaded antibacterial agent, stirring for 30min at the speed of 1000r/min, adding 0.006kg of silane coupling agent KH550, and ball-milling for 2h at the speed of 100r/min to obtain a ball-milled substance; and then drying the ball-milled material for 8 hours at the temperature of 120 ℃.

(3) Mixing: and (3) stirring the polyhexamethylene guanidine pretreated in the step (1) and the zirconium phosphate silver-loaded antibacterial agent pretreated in the step (2) at the speed of 200r/min for 10min to obtain the composite antibacterial agent.

Preparation example 3: the composite antibacterial agent is prepared by the following method:

(1) pretreatment of polyhexamethylene guanidine: 1kg of polyhexamethylene guanidine is taken, 2.5kg of medical stone powder is added into the polyhexamethylene guanidine, and the mixture is stirred for 20min at the speed of 2000r/min to obtain a polyhexamethylene guanidine-medical stone powder mixture;

② 20kg of zinc oxide, 25kg of zein, 5kg of lauric acid monoglyceride, 3kg of calcium stearate, 0.4kg of silane coupling agent KH550and 50kg of ethanol solution with the volume fraction of 92 percent are taken and stirred for 40min at the temperature of 80 ℃ to obtain coating liquid;

③ adding 4 percent of coating liquid of the weight of the mixture of polyhexamethylene guanidine and medical stone powder into the mixture, stirring the mixture for 40min at the temperature of 110 ℃ at the speed of 400r/min, then drying the mixture for 10h at the temperature of 80 ℃, and cooling the mixture to the normal temperature.

(2) Pretreatment of the zirconium phosphate silver-loaded antibacterial agent: heating 20kg of isothiazolinone, 4kg of polyaspartic acid, 3kg of itaconic anhydride and 30kg of glycerol carbonate to 90 ℃, and stirring for 30min under the condition of heat preservation to obtain a modifier;

adding 0.18kg of modifier into 3kg of zirconium phosphate silver-loaded antibacterial agent, stirring for 30min at the speed of 1000r/min, adding 0.015kg of silane coupling agent KH550, and performing ball milling for 2h at the speed of 100r/min to obtain a ball-milled substance; and then drying the ball-milled material for 8 hours at the temperature of 120 ℃.

(3) Mixing: and (3) stirring the polyhexamethylene guanidine pretreated in the step (1) and the zirconium phosphate silver-loaded antibacterial agent pretreated in the step (2) at the speed of 200r/min for 10min to obtain the composite antibacterial agent.

Preparation example 4: this preparation example differs from preparation example 1 in that neither polyhexamethylene guanidine nor the silver-loaded zirconium phosphate antimicrobial agent was pretreated prior to mixing.

Preparation example 5: this preparation differs from preparation 1 in that polyhexamethylene guanidine has not been pretreated before mixing.

Preparation example 6: this production example is different from production example 1 in that zinc oxide, zein, monoglycerol laurate and calcium stearate in the coating solution are replaced by an equal amount of an ethanol solution having a volume fraction of 80% in the case of the polyhexamethylene guanidine pretreatment.

Preparation example 7: the difference between the preparation example and the preparation example 1 is that no modifier is added in the step (II) when the zirconium phosphate silver-loaded antibacterial agent is pretreated.

Preparation example 8: the difference between the preparation example and the preparation example 1 is that the dosage of the zirconium phosphate silver-loaded antibacterial agent in the step (2) is 4kg, the dosage of the modifier is 0.16kg, and the dosage of the silane coupling agent KH550 is 0.008 kg.

Preparation example 9: the difference between the preparation example and the preparation example 1 is that the dosage of the silver-loaded zirconium phosphate antibacterial agent in the step (2) is 0.5kg, the dosage of the modifier is 0.02kg, and the dosage of the silane coupling agent KH550 is 0.001 kg.