阅读说明：本技术 一种抗菌抗病毒聚氯乙烯人造革及其制备方法 (Antibacterial and antiviral polyvinyl chloride artificial leather and preparation method thereof ) 是由 赵建明 陆勤中 成峰 徐青 高卫忠 丁菊芳 于 2020-04-14 设计创作，主要内容包括：本发明公开了一种抗菌抗病毒聚氯乙烯人造革,包括基布层、抗菌PVC层和抗病毒涂饰层；所述抗菌PVC层的制备原料按质量份数包括以下组分：PVC树脂30～70份、增塑剂20～50份、稳定剂1～5份、改性剂1～5份、抗菌防霉剂0.5～10份、发泡剂0～2份；所述抗菌防霉剂为核壳结构的二氧化硅包覆银纳米颗粒与羧甲基壳聚糖复合而成的复合抗菌防霉剂；所述抗病毒涂饰层的制备原料包括丙烯酸酯乳液100份、中空氧化锌0.1～5份、氧化石墨烯0.1～5份、消泡剂0.1～1份、流平剂0.1～2份和去离子水20～30份。本发明制备的人造革透气性好,具有较优异的力学性能,产品档次高,且具有较持久和较优异的抗菌防霉效果以及抗病毒效果。(The invention discloses an antibacterial and antiviral polyvinyl chloride artificial leather, which comprises a base cloth layer, an antibacterial PVC layer and an antiviral coating layer; the antibacterial PVC layer is prepared from the following raw materials in parts by weight: 30-70 parts of PVC resin, 20-50 parts of plasticizer, 1-5 parts of stabilizer, 1-5 parts of modifier, 0.5-10 parts of antibacterial mildew preventive and 0-2 parts of foaming agent; the antibacterial mildew preventive is a composite antibacterial mildew preventive which is formed by compounding silicon dioxide coated silver nanoparticles with a core-shell structure and carboxymethyl chitosan; the preparation raw materials of the antiviral coating layer comprise 100 parts of acrylate emulsion, 0.1-5 parts of hollow zinc oxide, 0.1-5 parts of graphene oxide, 0.1-1 part of defoaming agent, 0.1-2 parts of flatting agent and 20-30 parts of deionized water. The artificial leather prepared by the invention has good air permeability, excellent mechanical property, high grade of products, and more lasting and excellent antibacterial and mildewproof effects and antiviral effects.)

1. An antibacterial and antiviral polyvinyl chloride artificial leather is characterized by comprising a base cloth layer, an antibacterial PVC layer and an antiviral coating layer;

the antibacterial PVC layer is prepared from the following raw materials in parts by weight: 30-70 parts of PVC resin, 20-50 parts of plasticizer, 1-5 parts of stabilizer, 1-5 parts of modifier, 0.5-10 parts of antibacterial mildew preventive and 0-2 parts of foaming agent;

the antibacterial mildew preventive is a composite antibacterial mildew preventive which is formed by compounding silicon dioxide coated silver nanoparticles with a core-shell structure and carboxymethyl chitosan;

wherein the shell of the silicon dioxide coated silver nano-particles is of a porous structure; the composite antibacterial mildew inhibitor is prepared by alkylating carboxymethyl chitosan and then loading silica-coated silver nanoparticles with a core-shell structure on the alkylated carboxymethyl chitosan;

the preparation raw materials of the antiviral coating layer comprise 100 parts of acrylate emulsion, 0.1-5 parts of hollow zinc oxide, 0.1-5 parts of graphene oxide, 0.1-1 part of defoaming agent, 0.1-2 parts of flatting agent and 20-30 parts of deionized water.

2. The antibacterial and antiviral polyvinyl chloride artificial leather according to claim 1, wherein: the plasticizer is selected from one or a combination of two or more of phthalate, phosphate and epoxy plasticizers.

3. The antibacterial and antiviral polyvinyl chloride artificial leather according to claim 1, wherein: the stabilizer is one or the combination of two or more of calcium and zinc, organic tin, lead salt, organic antimony, metal soap and rare earth stabilizer.

4. The antibacterial and antiviral polyvinyl chloride artificial leather according to claim 1, wherein: the modifier is a composite modifier formed by a styrene-like modifier and a CPE modifier.

5. The antibacterial and antiviral polyvinyl chloride artificial leather according to claim 1, wherein: the alkylated carboxymethyl chitosan is prepared by adopting 3-glycidyl ether trimethoxy silane to carry out alkylation treatment on carboxymethyl chitosan.

6. The antibacterial and antiviral polyvinyl chloride artificial leather according to claim 1, wherein: the silicon dioxide coated nano silver particle with the core-shell structure is prepared by reducing silver nitrate by hydrazine hydrate under the condition of taking CTAB as a surfactant and then coating a silicon dioxide layer by TEOS.

7. The antibacterial and antiviral polyvinyl chloride artificial leather according to claim 1, wherein: the preparation method comprises the steps of dispersing hollow zinc oxide and graphene oxide in deionized water in an ultrasonic mode to prepare suspension, and then mixing the suspension with acrylate emulsion.

8. The method for preparing polyvinyl chloride artificial leather having antibacterial and antiviral effects as claimed in any one of claims 1 to 7, comprising the steps of:

(1) preparation of antibacterial PVC (polyvinyl chloride) sheet

The preparation method comprises the following steps of putting the preparation raw materials of the antibacterial PVC layer into a high-speed stirrer according to the mass part ratio, mixing at a high speed, discharging into an internal mixer for mixing, wherein the mixing temperature is 100-150 ℃, discharging into an open mill after mixing is finished, plasticating at a temperature of 100-150 ℃ sequentially through two open mills, conveying to a calender for calendering into sheets, wherein the calendering temperature is 120-180 ℃, and calendering to obtain an antibacterial PVC layer sheet;

(2) bonding

Attaching the antibacterial PVC sheet to base cloth to prepare a semi-finished product, then sending the semi-finished product into a foaming embossing machine, and carrying out foaming embossing treatment at 160-210 ℃;

(3) anti-viral finish treatment

Ultrasonically dispersing hollow zinc oxide in deionized water to prepare a hollow zinc oxide suspension; ultrasonically dispersing graphene oxide in deionized water to prepare a graphene oxide solution; respectively adding the hollow zinc oxide suspension, the graphene oxide solution, the defoaming agent and the flatting agent into the acrylate emulsion for mixing to prepare an antiviral coating agent; and (3) rolling the antiviral coating agent on the antibacterial PVC layer in a rolling way, and drying to form the antiviral coating layer compounded on the antibacterial PVC layer.

Technical Field

The invention belongs to the technical field of artificial leather, and particularly relates to antibacterial and antiviral polyvinyl chloride artificial leather and a preparation method thereof.

Background

Since the last 90 s, the polyvinyl chloride (PVC) artificial leather product, which is the first generation artificial leather, is gradually replaced by Polyurethane (PU) artificial leather due to its disadvantages of poor air permeability and hygroscopicity, no recyclability, no environmental protection requirement, etc., and the PVC artificial leather is reduced to less than 40% from the initial almost 100% market share. However, in recent years, due to the rising price of raw materials of PU artificial leather and the poor performance of partial properties such as hydrolysis resistance and weather resistance, the advantages of hydrolysis resistance, wear resistance, scratch resistance, acid and alkali resistance, flame retardance and the like of PVC artificial leather are exerted, and in addition, the use of environment-friendly plasticizers and various processing aids, the improvement of PVC resin recycling technology and the improvement of waste gas recycling efficiency and the like, the main environmental protection problem is basically solved. Most importantly, the PVC artificial leather has the advantage of relatively low price, so that new vitality and vitality are revived in recent years.

The recent emergence of pathogenic E.coli, SARS virus, H7N9 virus, and recently emerging new coronavirus have caused social panic and seriously threatened the health and safety of people. In real life, people cannot avoid contacting microorganisms such as bacteria and fungi, and because the microorganisms have rapid reproductive capacity and diversified disease transmission ways, antibacterial and antiviral materials capable of effectively resisting pathogenic microorganisms and virus invasion are increasingly regarded.

In the production of PVC artificial leather, a plurality of auxiliary agents such as a stabilizer, a plasticizer and the like are added into PVC paste resin, the auxiliary agents can become a nutrient source of bacteria and mould, particularly, the plasticizer can become a food source of microorganisms more easily, and the microorganisms are propagated and eroded under proper conditions. The propagation and corrosion of bacteria, viruses and microorganisms not only threaten the health and safety of people, but also can cause the growth of mildew, discoloration, cracking and poor strength of the artificial leather material until the use value is lost; therefore, the antibacterial agent and the antiviral substance are added in the production process of the PVC artificial leather, so that the growth and the propagation of microorganisms can be effectively controlled, the use value of the artificial leather is improved, and the health and the safety of users are ensured.

The antibacterial agent mainly comprises inorganic antibacterial agent, synthetic organic antibacterial agent, and natural organic antibacterial agent. The inorganic antibacterial agent has many kinds, and the inorganic antibacterial agent is widely applied and is represented by metal or metal ion antibacterial agents such as silver, copper, zinc and the like and metal oxides (such as TiO)₂ZnO, etc.) inorganic nano antibacterial agents. Inorganic antibacterial agents have many advantages such as safety in use, heat resistance, good persistence, broad antibacterial spectrum, etc., and thus have become a research hotspot in the field of antibacterial agents. Among them, the silver-based antibacterial agent is an inorganic antibacterial agent having the highest antibacterial efficiency. However, silver-based antibacterial agents are liable to be discolored, and are difficult to produce and complicated in the process of using them in materials. Generally, silver ions of a silver-based antibacterial agent need to be loaded on an inorganic carrier, but the silver ions are easily discolored under illumination, and the silver ions are released too fast to realize the long-lasting antibacterial effect. Synthetic organic antibacterial agents used in artificial leather are mainly compounds such as quaternary ammonium salts, biguanides, alcohols, phenols, aldehydes, organic acids, peroxides, halogens, imidazoles, thiophenes, pyridines, and the like. The organic antibacterial agent has the advantages of high sterilization speed, strong sterilization capability, no toxicity of partial antibacterial agents, convenient processing, good color stability and poor heat resistance. The natural organic antibacterial agent mainly comprises chitosan, serum protein, cassia oil, thujoram oil, garlicin, natural phenols and the like, and most of the antibacterial agents are refined from animals and plants; the natural antibacterial agent has advantages of environmental friendliness and better biocompatibility unlike other antibacterial agents, and has disadvantages of poor stability and heat resistance.

At present, most of antibacterial agents are used independently in PVC artificial leather, and the antibacterial effect has certain limitation, such as narrow bactericidal spectrum of single component, larger dosage, short time effect, higher cost, poorer biodegradability of some antibacterial agents, poor use safety and larger influence on environment. If different antibacterial agents are compounded according to the antibacterial characteristics of the different antibacterial agents, the respective advantages can be exerted, and the cost for developing new antibacterial agents is saved.

In addition, in the prior art, few researches on the antiviral property of artificial leather are carried out, and in order to solve various viral problems, the development of an artificial leather product with good antibacterial property and antiviral property is urgently needed.

Disclosure of Invention

In order to solve the above technical problems, the present invention aims to provide an antibacterial and antiviral polyvinyl chloride artificial leather and a preparation method thereof, wherein the prepared artificial leather has good air permeability, excellent mechanical properties, high product grade, and relatively durable and excellent antibacterial and antifungal effects and antiviral effects.

In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:

an antibacterial and antiviral polyvinyl chloride artificial leather comprises a base cloth layer, an antibacterial PVC layer and an antiviral coating layer;

the antibacterial PVC layer is prepared from the following raw materials in parts by weight: 30-70 parts of PVC resin, 20-50 parts of plasticizer, 1-5 parts of stabilizer, 1-5 parts of modifier, 0.5-10 parts of antibacterial mildew preventive and 0-2 parts of foaming agent;

the antibacterial mildew preventive is a composite antibacterial mildew preventive which is formed by compounding silicon dioxide coated silver nanoparticles with a core-shell structure and carboxymethyl chitosan;

wherein the shell of the silicon dioxide coated silver nano-particles is of a porous structure; the composite antibacterial mildew inhibitor is prepared by alkylating carboxymethyl chitosan and then loading silica-coated silver nanoparticles with a core-shell structure on the alkylated carboxymethyl chitosan;

the preparation raw material of the antiviral coating layer comprises 100 parts of acrylate emulsion, 0.1-5 parts of hollow zinc oxide, 0.1-5 parts of graphene oxide, 0.1-1 part of defoaming agent, 0.1-2 parts of flatting agent and 20-30 parts of deionized water.

Further, the plasticizer is selected from one or a combination of two or more of phthalate, phosphate and epoxy plasticizers.

Further, the stabilizer is one or a combination of two or more of calcium and zinc, organic tin, lead salt, organic antimony, metal soap and rare earth stabilizer.

Further, the modifier is a composite modifier formed by a styrene-like modifier and a CPE modifier.

Furthermore, the alkylated carboxymethyl chitosan is prepared by alkylating the carboxymethyl chitosan by using 3-glycidyl ether trimethoxy silane.

Further, the silica-coated nano silver particles with the core-shell structure are prepared by reducing silver nitrate by hydrazine hydrate under the condition that CTAB is taken as a surfactant, and then coating a silica layer by TEOS.

Further, the hollow zinc oxide and the graphene oxide in the raw materials are respectively dispersed in deionized water in an ultrasonic mode to prepare a suspension, and then the suspension is mixed with the acrylate emulsion.

The invention also provides a preparation method of the antibacterial and antiviral polyvinyl chloride artificial leather, which comprises the following steps:

(1) preparation of antibacterial PVC (polyvinyl chloride) sheet

The preparation method comprises the following steps of putting the preparation raw materials of the antibacterial PVC layer into a high-speed stirrer according to the mass part ratio, mixing at a high speed, discharging into an internal mixer for mixing, wherein the mixing temperature is 100-150 ℃, discharging into an open mill after mixing is finished, plasticating at a temperature of 100-150 ℃ sequentially through two open mills, conveying to a calender for calendering into sheets, wherein the calendering temperature is 120-180 ℃, and calendering to obtain an antibacterial PVC layer sheet;

(2) bonding

Attaching the antibacterial PVC sheet to base cloth to prepare a semi-finished product, then sending the semi-finished product into a foaming embossing machine, and carrying out foaming embossing treatment at 160-210 ℃;

(3) anti-viral finish treatment

Ultrasonically dispersing hollow zinc oxide in deionized water to prepare a hollow zinc oxide suspension; ultrasonically dispersing graphene oxide in deionized water to prepare a graphene oxide solution; respectively adding the hollow zinc oxide suspension, the graphene oxide solution, the defoaming agent and the flatting agent into the acrylate emulsion for mixing to prepare an antiviral coating agent; and (3) rolling the antiviral coating agent on the antibacterial PVC layer in a rolling way, and drying to form the antiviral coating layer compounded on the antibacterial PVC layer.

The invention has the beneficial effects that:

(1) the antibacterial and mildewproof effects are as follows:

the antibacterial mildew inhibitor in the raw materials for preparing the polyvinyl chloride artificial leather is a composite antibacterial mildew inhibitor formed by compounding silicon dioxide-coated silver nanoparticles with a core-shell structure and carboxymethyl chitosan; the silicon dioxide coated silver nano-particles with the core-shell structure are prepared by reducing silver nitrate by hydrazine hydrate under the condition of taking CTAB as a surfactant and then coating a silicon dioxide layer by TEOS. The prepared silicon dioxide coated silver nano-particle is of a core-shell structure with a silicon dioxide layer as a shell and nano silver as a core, and the silicon dioxide shell is of a porous structure, so that silver ions can be released through holes of the silicon dioxide shell to realize an antibacterial effect; the silver particles are coated in the silicon dioxide shell layer, so that the silver particles can be prevented from falling off quickly, and the silver ions can be prevented from discoloring under illumination, thereby ensuring the durability of the antibacterial effect; the invention selects chitosan as the organic antibacterial agent, which has better biocompatibility, biological nontoxicity and biodegradability, and the carboxymethyl chitosan adopted by the invention is obtained by utilizing the reaction of chitosan and monochloroacetic acid under the alkaline condition, compared with the conventional chitosan, the carboxymethyl chitosan has enhanced water solubility, enhanced antibacterial activity and enlarged antibacterial range; according to the invention, 3-glycidyl ether trimethoxy silane is adopted to carry out alkylation treatment on carboxymethyl chitosan to prepare alkylated carboxymethyl chitosan, and then silicon dioxide coated silver nanoparticles are loaded on the alkylated carboxymethyl chitosan to prepare the composite antibacterial mildew preventive, so that the composite antibacterial mildew preventive has the advantages of an organic antibacterial agent and an inorganic antibacterial agent, overcomes the defect of a single antibacterial component, produces a synergistic effect of the organic component and the inorganic component, enhances the antibacterial effect, improves the antibacterial stability and the long-acting property, and can enable the antibacterial mildew preventive effect to have the same period and the same service life as that of an artificial leather product.

(2) The antiviral effect is as follows:

the invention adopts an antiviral finishing agent to form an antiviral finishing layer on the surface of the antibacterial PVC layer; the hollow zinc oxide in the antiviral finishing agent is of a hollow structure, the specific surface area, the cavity volume and the surface roughness of the hollow zinc oxide are large, more ultraviolet light is absorbed, and more active oxygen is generated, so that the hollow zinc oxide can perform oxidation reaction with organic matters in bacteria and viruses to kill the bacteria and the viruses; the graphene oxide in the antiviral coating agent is of a two-dimensional structure and high in oxygen content, can enable DNA damage in bacteria and viruses to break under the action of oxidative stress, and can also be combined with the viruses through electrostatic interaction to damage the viruses, so that the antiviral effect is finally achieved. The hollow zinc oxide is matched with the graphene oxide, so that the antiviral effect can be more remarkably improved.

(3) Other effects are as follows:

the modifier in the invention adopts a composite modifier formed by a styrene-like modifier and a CPE modifier; the styrene-like modifier and CPE (chlorinated polyvinyl chloride) are used together to generate a good synergistic effect, can improve the processing performance of PVC, improve the melt fluidity, play roles in plasticization, toughening and lubrication, and improve the heat resistance, electrical insulation and impact resistance of products. In addition, the hollow structure and the larger specific surface area of the hollow zinc oxide can improve the air permeability and the water resistance of the artificial leather; the graphene oxide can improve the mechanical property and the water resistance of the artificial leather.

Detailed Description

The technical solutions in the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.