CN114347594A - Antibacterial PVC floor and preparation method thereof - Google Patents
Antibacterial PVC floor and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an antibacterial PVC floor, which comprises an antibacterial substrate layer, wherein the surface layer of the antibacterial substrate layer is an antibacterial wear-resistant layer, and an antibacterial binding layer and an antibacterial UV layer which are sequentially laminated are arranged on the surface of the antibacterial wear-resistant layer from bottom to top; the main components of the antibacterial UV layer comprise an organic antibacterial agent and/or an inorganic antibacterial agent and urethane acrylate; the main components of the antibacterial binding layer comprise an inorganic antibacterial agent, an organic antibacterial agent and PVC resin; the main components of the antibacterial wear-resistant layer comprise an inorganic antibacterial agent and PVC paste resin; the inorganic antibacterial agent is a silver-zinc-copper ion compound antibacterial agent; the organic antibacterial agent is benzisothiazolinone organic antibacterial agent. The antibacterial PVC floor is characterized in that the antibacterial base material layer is combined with the antibacterial binding layer and the antibacterial UV layer to achieve synergistic effect, the antibacterial binding layer improves antibacterial continuity and antibacterial stability of the antibacterial PVC floor, and the zinc-silver-copper ion compound antibacterial agent and the benzisothiazolinone organic antibacterial agent are combined to achieve synergistic effect to further improve antibacterial performance.
Description
Technical Field
The invention relates to the technical field of floors, in particular to an antibacterial PVC floor and a preparation method thereof.
Background
PVC materials have no antibacterial property, and products, particularly PVC floors, have dirty surfaces after a period of time, and various harmful microorganisms such as bacteria, mold, fungi and the like are bred. Particularly, when objective conditions such as temperature, humidity and the like are suitable, harmful microorganisms are more easily propagated and spread, and cross infection can be caused by contact of different people, so that the microorganisms become a bacterial pollution source and a disease transmission source, and harm is brought to the body health of people. In order to make the PVC floor have antibacterial effect, some antibacterial agents are usually required to be added, and the following defects are often existed: on one hand, the existing PVC floor has precipitation phenomenon after the antibacterial agent is added, and the antibacterial effect is reduced; on the other hand, the antibacterial agent added to the PVC floor has poor antibacterial persistence.
Therefore, there is a need to improve the antibacterial performance of the PVC flooring in the prior art.
Disclosure of Invention
One of the purposes of the invention is to overcome the defects in the prior art and provide an antibacterial PVC floor, wherein an antibacterial base material layer is combined with an antibacterial bonding layer and an antibacterial UV layer to have a synergistic effect, the antibacterial bonding layer improves the antibacterial stability and antibacterial continuity of the antibacterial PVC floor, and a UV photocuring layer effectively prevents zinc, silver and copper ions in an inorganic antibacterial agent from peeling off; the organic antibacterial agent and the inorganic antibacterial agent have synergistic effect, and the antibacterial persistence of the antibacterial and mildewproof functions of the antibacterial PVC floor is further improved.
In order to realize the process effect, the technical scheme of the invention is as follows: an antibacterial PVC floor comprises an antibacterial base material layer, wherein the surface layer of the antibacterial base material layer is an antibacterial wear-resistant layer, and an antibacterial binding layer and an antibacterial UV layer which are sequentially stacked are arranged on the surface of the antibacterial wear-resistant layer from bottom to top; the main components of the antibacterial UV layer comprise an organic antibacterial agent and/or an inorganic antibacterial agent and urethane acrylate; the main components of the antibacterial binding layer comprise an inorganic antibacterial agent, an organic antibacterial agent and PVC resin; the main components of the antibacterial wear-resistant layer comprise an inorganic antibacterial agent and PVC paste resin; the inorganic antibacterial agent is a silver-zinc-copper ion compound antibacterial agent; the organic antibacterial agent is benzisothiazolinone organic antibacterial agent.
Furthermore, the benzisothiazolinone organic antibacterial agent is an n-butyl-1, 2-benzisothiazolin-3-one organic antibacterial agent, and the n-butyl-1, 2-benzisothiazolin-3-one organic antibacterial agent is called BBIT organic antibacterial agent for short, and has the antibacterial principle of destroying the cytoplasmic membrane of target bacteria and inhibiting the cell metabolism of pathogenic bacteria. The inorganic antibacterial agent is prepared into an inorganic antibacterial agent solvent, and further, the inorganic antibacterial agent solvent is zinc-silver-copper ion compound antibacterial liquid, and the antibacterial principle of the zinc-silver-copper ion compound antibacterial agent is that when metal ions are contacted with cell membranes of bacteria, the metal ions are attracted with the cell membranes with negative charges, penetrate through the cell membranes to enter the bacteria bodies and react with sulfydryl, amino and the like on protein, so that the active centers of the protein are destroyed, and the bacteria bodies die or lose the division and proliferation capacity; the zinc, silver and copper ions entering the bacteria body are dissociated after the bacteria die, and the process of adsorbing, penetrating and killing the bacteria can be carried out repeatedly. The antibacterial base material layer is combined with the antibacterial binding layer and the antibacterial UV layer to act synergistically, so that on one hand, the antibacterial effect of the antibacterial PVC floor is improved, and the antibacterial continuity and stability are improved; on the other hand, the UV light curing layer effectively prevents the stripping of zinc, silver and copper ions in the inorganic antibacterial agent. The compound antibacterial performance of the zinc-silver-copper ion compound antibacterial agent and the BBIT organic antibacterial agent is improved, and the antibacterial persistence is also improved. Further, the main components of the antibacterial UV layer comprise BBIT organic antibacterial agent and urethane acrylate; furthermore, the zinc-silver-copper ion compound antibacterial liquid is P210S; the antibacterial UV coating liquid of the antibacterial UV layer is V-100.
In order to ensure that the zinc-silver-copper ion compound antibacterial agent has the best antibacterial effect and the silver ion, zinc ion and copper ion compound function, improve the antibacterial performance, avoid the damage to human bodies caused by the overlarge use amount of the single-ion inorganic antibacterial agent and the delay of the antibacterial performance of the single-ion inorganic antibacterial agent, the preferable technical scheme is that the mass ratio of the silver ion, the zinc ion and the copper ion in the silver-zinc-copper ion compound antibacterial agent is 1: (0.8-1): (0.8 to 1). Further, the silver-zinc-copper ion compound antibacterial agent is prepared into a silver-zinc-copper ion compound antibacterial liquid, and the mass fraction of silver-zinc-copper ion compounds in the silver-zinc-copper ion compound antibacterial liquid is 27-36%.
In order to increase the compatibility of the organic antibacterial agent and the inorganic antibacterial agent and improve the bonding firmness of the antibacterial bonding layer and the antibacterial wear-resistant layer, the preferable technical scheme is that the components of the antibacterial bonding layer further comprise a titanate coupling agent.
In order to improve the adhesion between the antibacterial UV layer and the antibacterial bonding layer and further improve the antibacterial durability and stability of the antibacterial agent, it is preferable that the antibacterial UV layer further comprises a vinyl chloride-vinyl acetate copolymer. The polymerization degree of the chloroethylene-vinyl acetate copolymer is 600-700. The mass fraction of the chloroethylene-vinyl acetate copolymer in the antibacterial UV layer is 1.5-2.2%. The components of the antibacterial UV layer comprise urethane acrylate, a BBIT organic antibacterial agent, an active monomer, a photoinitiator, a chloroethylene-vinyl acetate copolymer and an auxiliary agent. The surface of the antibacterial UV layer forms a hydrophilic structure, the polyurethane acrylate has a urethane bond, and the molecular chains interact with water molecules to form a hydrogen bond to obtain a hydration layer, so that the hydration layer further effectively prevents bacteria from adhering to the hydration layer, and effectively prevents inactivated bacteria from gathering on the surface of the antibacterial UV layer to influence the antibacterial efficiency and durability of the PVC floor. The mass fraction of the BBIT organic antibacterial agent in the antibacterial UV layer is 0.15-0.22%, and the skin is irritated due to excessive amount of the BBIT organic antibacterial agent, so that the cost is increased, and skin allergy is caused; too little antibacterial effect is poor. The mass fraction of the polyurethane acrylate in the antibacterial UV layer is 45-56%, and the viscosity of the antibacterial UV material liquid is too high, so that the organic antibacterial agent is easy to agglomerate and is not beneficial to uniform dispersion, and the coating processing is difficult on the other side; too little negatively affects the abrasion resistance on the one hand, and reduces the antibacterial effect and antibacterial persistence on the other hand. The auxiliary agent comprises a delustering agent, an inhibition oil-water emulsion, a stabilizer, a dispersing agent and the like.
In order to optimize the composition of the antibacterial binding layer and the antibacterial wear-resistant layer, and the optimal antibacterial performance is achieved by compounding the inorganic antibacterial agent and the organic antibacterial agent, the preferable technical scheme is that the components of the antibacterial binding layer comprise, by mass, 100 parts of PVC resin, 1.5-2.5 parts of inorganic antibacterial agent solvent, 0.15-0.2 part of organic antibacterial agent, 0.5-1 part of titanate coupling agent, 25-35 parts of plasticizer, 2.5-3.5 parts of stabilizer and 0.8-1.4 parts of odor adsorbent; the components of the antibacterial wear-resistant layer comprise 100 parts of PVC paste resin, 1.5-2.5 parts of inorganic antibacterial agent solvent, 35-45 parts of plasticizer, 2.5-3.5 parts of stabilizer and 0.8-1.4 parts of odor adsorbent. In order to improve the thermal degradation phenomenon of the polyvinyl chloride paste resin in the processing process, avoid influencing the compatibility of the zinc-silver-copper ion compound antibacterial agent, improve the processing stability and improve the mechanical property of the product, further, the stabilizing agent is a calcium-zinc stabilizing agent. The calcium zinc stabilizer has small relative smell and is more beneficial to environmental protection. In order to improve the physical and chemical properties and the stability of the physical and chemical properties of the PVC paste resin, the plasticizer is dioctyl terephthalate. The dioctyl terephthalate has low toxicity and is more beneficial to environmental protection. The plasticizer is excessive in amount, so that the number of plasticizer molecules inserted among polyvinyl chloride molecular chains is increased, the intermolecular attraction is damaged and weakened while the intermolecular distance is increased, the polymer chains are loosened and moved, the hardness of the antibacterial wear-resistant layer is reduced, the wear resistance of the PVC floor is negatively influenced, and the stability of the zinc-silver-copper ion compound antibacterial agent in the antibacterial wear-resistant layer is also negatively influenced. The odor adsorbent has physical adsorption and chemical adsorption effects, and can reduce VOC (volatile organic compounds) and odor, wherein VOC refers to organic compounds of atmospheric photochemical reaction and indirectly prevents the release of a bacterial carbon source nutrition source.
In order to prolong the action of the sustained-release antibacterial agent and improve the stability of the antibacterial agent in the material, and improve the wear resistance and aging resistance of the PVC floor. The preferable technical scheme is that the polymerization degree of PVC paste resin in the antibacterial wear-resistant layer is 1600-1800, and the polymerization degree of PVC resin in the antibacterial binding layer is 1250-1350. With the increase of the polymerization degree of the PVC resin, the entanglement degree of molecular chains is increased, and the molecular chains can also form a cross-linked network structure even in a plasticizing system, so that the macromolecular movement is inhibited to a certain degree, irreversible slippage is not easy to generate, and the impact resilience of a product is improved along with the increase of the polymerization degree; meanwhile, PVC has certain crystallization capacity, the PVC molecular chain arrangement tends to be regular along with the increase of the polymerization degree, the crystallization degree is improved, the antibacterial agent is coated between PVC polymers, the tensile strength of the PVC paste resin with too low polymerization degree in the components of the antibacterial wear-resistant layer is reduced, the wear resistance is also negatively influenced, the ageing resistance is reduced, the phenomenon of separation of the antibacterial agent is easily caused, and the stability of the antibacterial performance is negatively influenced. The PVC resin with low polymerization degree in the components of the antibacterial binding layer has negative influence on the tensile strength, the wear resistance and the ageing resistance of the material, the antibacterial agent is easily separated out, and the stability of the antibacterial property has negative influence.
The invention also aims to overcome the defects in the prior art and provide a preparation method of the antibacterial PVC floor, which comprises the following steps:
s1: respectively mixing the raw materials of each layer of the antibacterial base material layer and the raw material of the antibacterial binding layer;
s2: sequentially coating an antibacterial wear-resistant layer, performing first high-temperature curing, coating a reinforcing layer, performing second high-temperature curing, coating an elastic bottom layer on a carrier, and removing the carrier after the third high-temperature curing to obtain an antibacterial base material layer;
s3: plasticizing the raw material of the antibacterial bonding layer, and calendering to prepare the antibacterial bonding layer;
s4: hot-pressing and compounding the antibacterial bonding layer and the antibacterial wear-resistant layer;
s5: an antibacterial UV layer is sprayed on the surface of the antibacterial bonding layer;
the temperature of the first high-temperature curing and the second high-temperature curing is lower than that of the third high-temperature curing;
the temperature of the first high-temperature curing and the second high-temperature curing is not less than 170 ℃.
In step S1, the antibacterial wear-resistant layer: firstly mixing and dispersing zinc, silver and copper ion compound antibacterial liquid, a plasticizer, a stabilizer and a smell adsorbent for 3-5 min; adding PVC paste resin, and mixing and stirring for 15-20 min;
reinforcing layer: firstly mixing and dispersing zinc, silver and copper ion compound antibacterial liquid, a plasticizer, a stabilizer and a smell adsorbent for 3-5 min; then adding PVC paste resin and a filler, and mixing and stirring for 15-20 min;
an elastic bottom layer: firstly mixing and dispersing zinc, silver and copper ion compound antibacterial liquid, a plasticizer, a stabilizer and a smell adsorbent for 3-5 min; and adding PVC paste resin, finally adding a foaming agent, and mixing and stirring for 15-20 min.
The polymerization degree of PVC paste resin in the components of the reinforcing layer is 1000-1200, and the polymerization degree of PVC paste resin in the components of the elastic bottom layer is 900-1100. The layer thickness of the reinforcing layer is thicker than that of other layers, the PVC paste resin in the components has overlarge polymerization degree and is difficult to plasticize, the precipitation of the zinc-silver-copper ion compound antibacterial liquid is influenced, and the tensile strength of the material is reduced; the tensile strength and the tearing strength of the PVC paste resin are reduced when the polymerization degree is too low. The PVC paste resin in the components of the elastic bottom layer has too high polymerization degree and is not easy to foam, so that the overall elasticity of the antibacterial PVC floor is poor; the tensile strength and the tearing strength of the PVC paste resin with too low polymerization degree are reduced, so that the bottom layer is easily damaged, and the antibacterial performance is reduced.
Furthermore, the thickness of the antibacterial UV layer is 5-20 mu m. In order to fully cure the antibacterial UV layer and ensure the wear resistance of the floor surface layer and the stability of the organic antibacterial agent, the energy of photocuring is 950-1050 mJ/cm2. The light curing is ultraviolet light curing, the energy of the light curing is too low, the curing is incomplete, the wear resistance of the floor is poor, and the organic antibacterial agent is easy to precipitate out and the antibacterial continuity is reduced. When the energy of photocuring is too high, the antibacterial UV layer is cured excessively, the stress of the film layer is increased, the hardness of the film layer is increased and becomes brittle, the adhesion between the film layer and the antibacterial wear-resistant layer is deteriorated, the antibacterial performance is reduced, and the wear resistance is greatly reduced. In order to fully plasticize the antibacterial bonding layer and prevent the organic antibacterial agent and the inorganic antibacterial agent from being separated out, the plasticizing temperature of the antibacterial bonding layer in S3 is 170-180 ℃. The bonding firmness of the bonding surface of the antibacterial bonding layer and the antibacterial wear-resistant layer is improved, and further, the hot pressing temperature of S4 is 140-150 ℃.
In order to fully cure the antibacterial base material layer, ensure the mechanical properties of each layer and improve the compatibility and stability of the inorganic antibacterial agent in the antibacterial base material layer, the preferable technical scheme is that the temperature of the first high-temperature curing in S2 is
The temperature of the second high-temperature curing is
The temperature of the third high-temperature curing is
Furthermore, the first high-temperature curing time is 1.5-2.7 min, the second high-temperature curing time is 1.7-3 min, and the third high-temperature curing time is 5.5-6.7 min.
In order to improve the compatibility of the organic antibacterial agent and the inorganic antibacterial agent solvent in the material and prevent the organic antibacterial agent and the inorganic antibacterial agent from being precipitated, the preferable technical scheme is that the benzisothiazolinone organic antibacterial agent, the inorganic antibacterial agent solvent and the titanate coupling agent which are used for forming the antibacterial bonding layer in the S3 are mixed to form a first mixed solution; and mixing the plasticizer, the stabilizer and the odor adsorbent to form a second mixed solution, adding the second mixed solution into the PVC resin, fully mixing, and then adding the first mixed solution. In the step of S3, the first mixed solution is uniformly mixed for 1-2 min, and the second mixed solution is uniformly mixed for 3-5 min.
In order to optimize the antibacterial performance and the antibacterial continuity of the antibacterial base material layer, the preferable technical scheme is that the components of the reinforcing layer and the elastic bottom layer respectively comprise a silver-zinc-copper ion compound antibacterial agent, and the mass ratio of the silver-zinc-copper ion compound antibacterial agent in the components of the antibacterial wear-resistant layer, the reinforcing layer and the elastic bottom layer is (3-4.5): 1: (3-4). Furthermore, the mass ratio of the zinc-silver-copper ion compound antibacterial agent in the components of the antibacterial wear-resistant layer, the reinforcing layer and the elastic bottom layer is (3.5-4.5): 1: (3.5-4). In order to further enhance the stability of the antibacterial PVC floor, the reinforcing layer is connected with glass fiber gridding cloth in an immersed manner. In order to optimize the composition of the reinforcing layer and the elastic bottom layer, the reinforcing layer comprises 100 parts by weight of PVC paste resin, 0.8-1.5 parts by weight of zinc-silver-copper ion compound antibacterial liquid, 50-60 parts by weight of plasticizer, 2.5-3.5 parts by weight of stabilizer, 140-160 parts by weight of filler and 0.8-1.4 parts by weight of odor adsorbent; the elastic bottom layer comprises 100 parts of PVC paste resin, 1.5-2.5 parts of zinc-silver-copper ion compound antibacterial liquid, 45-55 parts of plasticizer, 2.5-3.5 parts of stabilizer, 4-5 parts of foaming agent and 0.8-1.4 parts of odor adsorbent. Further, the filler is calcium carbonate. Furthermore, the particle size of the calcium carbonate is 300-500 meshes.
The invention has the advantages and beneficial effects that:
the antibacterial base material layer of the antibacterial PVC floor is combined with the antibacterial binding layer and the antibacterial UV layer to act synergistically, so that the antibacterial performance of the PVC floor is improved; meanwhile, the antibacterial continuous property and the antibacterial stability of the antibacterial PVC floor are improved by the antibacterial bonding layer, and the stripping of zinc, silver and copper ions in the inorganic antibacterial agent is effectively prevented by the UV photocuring layer; the antibacterial performance is further improved by the compounding and synergistic effect of the zinc-silver-copper ion compound antibacterial agent and the benzisothiazolinone organic antibacterial agent.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The PVC paste resin in the components of the antibacterial wear-resistant layer is produced by Taibo industry (Ningbo) Co., Ltd, and has the model of PR-1069;
the PVC paste resin in the components of the reinforcing layer is produced by Taibo industry Co., Ltd, and the model is PR-440;
the PVC paste resin in the components of the elastic bottom layer is produced by Taibo industry (Ningbo) Co., Ltd, and the model is PR-450;
the PVC resin in the components of the antibacterial bonding layer is produced by Taibo industries, Ltd, and the model is S75;
the BBIT organic antibacterial agent is produced by Okaqi of America, and has a model number of VANQUISH 100;
the titanate coupling agent is produced by Guangzhou Zhengzheng chemical engineering and technology Limited and has the model number of OL 800;
the model of the zinc-silver-copper ion compound antibacterial liquid is P210S;
the plasticizer is produced by Shandong Qilu plasticizer Co., Ltd;
the stabilizer is produced by Shanghai Pudong Runlu chemical plant;
the foaming agent is an AC foaming agent;
the filler is produced by forced plasticized filler Limited, Changxing county, Zhejiang province.
Example 1
Antibiotic PVC floor includes antibiotic UV layer, antibiotic anchor coat, antibiotic wearing layer, enhancement layer, glass fibre net layer and elasticity bottom in proper order by table to lining, and antibiotic wearing layer, enhancement layer, glass fibre net layer and elasticity bottom constitute antibiotic substrate layer.
The components of the antibacterial UV layer comprise an organic antibacterial agent, polyurethane acrylate and vinyl chloride-vinyl acetate copolymer;
the components of the antibacterial binding layer comprise, by mass, 100 parts of PVC resin, 2.3 parts of an inorganic antibacterial agent solvent, 0.18 part of an organic antibacterial agent, 0.9 part of a titanate coupling agent, 31 parts of a plasticizer, 3 parts of a stabilizer and 1 part of an odor adsorbent;
the components of the antibacterial wear-resistant layer comprise, by mass, 100 parts of PVC paste resin, 2 parts of zinc-silver-copper ion compound antibacterial liquid, 40 parts of plasticizer, 3 parts of stabilizer and 1 part of odor adsorbent.
The inorganic antibacterial agent solvent is silver, zinc and copper ion compound antibacterial liquid; the mass fraction of the silver-zinc-copper ion compound in the silver-zinc-copper ion compound antibacterial liquid is 32%; the mass ratio of silver ions to zinc ions to copper ions in the zinc-silver-copper ion compound antibacterial agent is 1: 1: 1.
the organic antibacterial agent is n-butyl-1, 2-benzisothiazolin-3-one organic antibacterial agent, and the n-butyl-1, 2-benzisothiazolin-3-one organic antibacterial agent is BBIT organic antibacterial agent for short.
The components of the reinforcing layer comprise 100 parts of PVC paste resin, 1 part of zinc-silver-copper ion compound antibacterial liquid, 55 parts of plasticizer, 3 parts of stabilizer, 150 parts of filler and 1 part of odor adsorbent by mass;
the elastic bottom layer comprises 100 parts by mass of PVC paste resin, 2 parts by mass of zinc-silver-copper ion compound antibacterial liquid, 50 parts by mass of plasticizer, 3 parts by mass of stabilizer, 4.5 parts by mass of foaming agent and 1 part by mass of odor adsorbent.
The polymerization degree of the PVC resin in the antibacterial binding layer is 1300, the polymerization degree of the PVC paste resin in the components of the antibacterial wear-resistant layer is 1700, the polymerization degree of the PVC paste resin in the components of the reinforcing layer is 1200, and the polymerization degree of the PVC paste resin in the components of the elastic bottom layer is 1000.
The preparation method of the antibacterial PVC floor comprises the following steps:
in step S1, the antibacterial wear-resistant layer: mixing and dispersing zinc, silver and copper ion compound antibacterial liquid, a plasticizer, a stabilizer and a smell adsorbent for 5 min; adding PVC paste resin, and mixing and stirring for 18 min;
reinforcing layer: mixing and dispersing zinc, silver and copper ion compound antibacterial liquid, a plasticizer, a stabilizer and a smell adsorbent for 5 min; adding PVC paste resin and filler, and mixing and stirring for 18 min;
an elastic bottom layer: mixing and dispersing zinc, silver and copper ion compound antibacterial liquid, a plasticizer, a stabilizer and a smell adsorbent for 5 min; then adding PVC paste resin and foaming agent, and mixing and stirring for 18 min.
S2: sequentially carrying out coating of an antibacterial wear-resistant layer, first high-temperature curing, coating of a reinforcing layer, second high-temperature curing, coating of an elastic bottom layer and third high-temperature curing on a carrier; the temperature of the first high-temperature curing is 180 ℃ and the time is 2 min; the temperature of the second high-temperature curing is 180 ℃ and the time is 2 min; the temperature of the third high-temperature curing is 210 ℃ and the time is 6 min.
S3: the BBIT organic antibacterial agent, the zinc-silver-copper ion compound antibacterial liquid and the coupling agent which are formed by the antibacterial binding layer are mixed and dispersed for 2min to form a first mixed liquid; and mixing and dispersing the plasticizer, the stabilizer and the odor adsorbent for 5min to form a second mixed solution, adding the second mixed solution into the PVC resin, fully mixing, and then adding the first mixed solution. And uniformly mixing the raw materials of the antibacterial bonding layer, plasticizing and calendering to obtain the film. The plasticizing temperature was 175 ℃.
S4: and (3) hot-pressing and compounding the antibacterial bonding layer and the antibacterial wear-resistant layer at the temperature of 145 ℃ and under the pressure of 3.5 mPa.
S5: the surface of the antibacterial bonding layer is sprayed with an antibacterial UV layer, and the photocuring energy of the antibacterial UV layer is 1000mJ/cm2。
18 mu m of antibacterial UV layer, 0.4mm of antibacterial binding layer, 0.4mm of antibacterial wear-resistant layer, 0.8mm of reinforcing layer, 0.3mm of glass fiber grid layer and 3.8mm of elastic bottom layer.
Example 2
Example 2 is based on example 1, except that the mass ratio of the zinc-silver-copper ion compound antibacterial agent in the components of the antibacterial wear-resistant layer, the reinforcing layer and the elastic bottom layer is 2.8: 1: 2.8 of;
example 3
Example 3 is based on example 1 with the difference that the coupling agent in the composition of the antimicrobial bonding layer is a silane coupling agent.
Example 4
Example 4 is based on example 1 with the difference that no coupling agent is added to the components of the antimicrobial bonding layer.
Example 5
Example 5 is based on example 1 with the difference that the composition of the antimicrobial UV layer does not include a vinyl chloride-vinyl acetate copolymer.
Example 6
Example 6 is based on example 1 with the difference that the degree of polymerisation of the PVC resin in the antimicrobial tie layer is 1000.
Example 7
Example 7 is based on example 1 with the difference that the PVC paste resin of the composition of the antibacterial wear layer has a degree of polymerization of 1500, and the PVC paste resin of the other layers has no change in degree of polymerization.
Example 8
Example 8 is based on example 1 except that the temperatures of the first high temperature curing, the second high temperature curing and the third high temperature curing in S2 are all 200 ℃.
Example 9
Example 9 is based on example 1 with the difference that the temperature of the first high temperature cure in S2 is
The temperature of the second high-temperature curing is
The temperature for the third high temperature curing was 210 ℃.
Example 10
Example 10 is based on example 1, except that the BBIT organic antibacterial agent, the zinc-silver-copper ion complex antibacterial liquid, and the titanate coupling agent, which are components of the antibacterial bonding layer in S3, are mixed and dispersed to form a first mixed solution; and mixing and dispersing the plasticizer, the stabilizer and the odor adsorbent to form a second mixed solution, and adding the first mixed solution and the second mixed solution into the PVC resin for fully mixing.
Example 11
Example 11 is based on example 1, except that the reinforcing layer and the elastic base layer in the antibacterial base material layer do not contain a zinc-silver-copper ion compound antibacterial agent, and the other compositions are unchanged.
Comparative example 1
Comparative example 1 is based on example 1 with the difference that in the blank experiment no antimicrobial agent was added to each layer of the PVC flooring.
Comparative example 2
Comparative example 2 is based on example 1 except that the components of the antimicrobial UV layer do not include a BBIT organic antimicrobial agent, but only urethane acrylate, a reactive monomer, a photoinitiator, vinyl chloride-vinyl acetate copolymer, and an adjuvant.
Comparative example 3
Comparative example 3 is based on example 1, except that the components of the antibacterial wear-resistant layer in the antibacterial base material layer do not include the zinc-silver-copper ion compound antibacterial agent, the other components are unchanged, and the components of the other layers are unchanged.
Comparative example 4
Comparative example 4 is based on example 1 with the difference that the components of the antimicrobial wear layer in the antimicrobial substrate layer also include a BBIT organic antimicrobial agent.
Comparative example 5
Comparative example 5 is based on example 1 with the difference that the inorganic antimicrobial agent in the components of the antimicrobial bonding layer, the antimicrobial wear layer, the reinforcement layer and the resilient bottom layer is a silver ion antimicrobial agent.
Comparative example 6
Comparative example 6 is based on example 1 with the difference that the inorganic antibacterial agent in the components of the antibacterial binding layer, the antibacterial wear layer, the reinforcing layer and the resilient backing layer is a copper ion antibacterial agent.
Comparative example 7
Comparative example 7 is based on example 1 with the difference that the inorganic antimicrobial agent of the components of the antimicrobial bonding layer, the antimicrobial wear layer, the reinforcement layer and the resilient bottom layer is a zinc ion antimicrobial agent.
Comparative example 8
Comparative example 8 is based on example 1 with the difference that the surface of the antimicrobial wear layer is not provided with an antimicrobial bonding layer.
1. Method for testing antibacterial property of test sample
(1) Antibacterial activity: according to the ISO22196:2011 standard; detecting strains: e.coli ATCC 8739; staphylococcus aureus ATCC 6538P;
(2) the specific determination method of the viable count comprises the following steps: the number of viable bacteria obtained after elution within 24h of contact time;
(3) log of viable count: the number of viable bacteria is measured by Log10Solving a function;
(4) antibacterial activity: the difference between the log-average value after the inoculation of the sample without antibacterial treatment (comparative example 1) and the log-average value after the inoculation of the sample with antibacterial treatment is examined for antibacterial performance, and the larger the antibacterial performance is, the better the antibacterial performance is.
(5) Antibacterial persistence of the test sample: aging, taking a sample 300mm by 300mm, and exposing under the following conditions: relative humidity 40%, temperature 60 ℃, time: for 72 hours.
The size of the antibacterial performance test sample is as follows: 50 x 50 mm.
TABLE 1, examples and comparative examples the antibacterial results of E.coli ATCC8739 were determined
TABLE 2, examples and comparative examples the antibacterial results of Staphylococcus aureus ATCC6538P were determined
The antibacterial activity of Escherichia coli ATCC8739 measured by a conventional sample is more than or equal to 2.50, and the antibacterial performance is better when the antibacterial activity is more than or equal to 2.60;
the antibacterial activity of Escherichia coli ATCC8739 measured after the sample is aged is more than or equal to 2.20, and the antibacterial persistence and stability are better when the antibacterial activity is more than or equal to 2.40.
The antibacterial activity of staphylococcus aureus ATCC6538P measured by a conventional sample meets the requirement that the antibacterial activity is more than or equal to 3.30, and the antibacterial performance is better when the antibacterial activity is more than or equal to 3.50;
the antibacterial activity of the staphylococcus aureus ATCC6538P measured after the sample is aged is more than or equal to 3.20, and the antibacterial continuity and stability are better when the antibacterial activity is more than or equal to 3.50.
Example 8, the first and second high temperature cures were too high and equal to the third high temperature cure, and the antimicrobial substrate layer of the resulting sample was layered; in example 9, the temperatures of the first high-temperature curing and the second high-temperature curing were too low, and the antibacterial substrate layer of the obtained sample was not molded and had poor mechanical properties.
In comparative example 4, because the BBIT organic antibacterial agent contains solvent or water, the antibacterial base material layer adopts a coating process, and the BBIT organic antibacterial agent is added into the paste resin slurry, so that quality problems such as pinholes, bubbles and the like are easily caused in the plasticizing process.
From tables 1 and 2, it can be seen that:
compared with the example 1, the antibacterial activity and the antibacterial rate of the antibacterial agent are reduced in the examples 3 and 4, and the titanate coupling agent is more favorable for the compatibility of silver-zinc-copper ion compound antibacterial liquid and BBIT organic antibacterial agent with PVC resin, so that the antibacterial performance is improved.
In examples 6 and 7, compared with example 1, the polymerization degree of the PVC paste resin of the antibacterial wear-resistant layer and the PVC resin of the antibacterial bonding layer was small, and both the antibacterial performance was negatively affected.
Example 10 compared to example 1, the PVC resin in the antimicrobial bonding layer was well mixed with the second mixture solution to facilitate the dispersion and compatibility of the first mixture solution.
Example 11 compared with example 1, the addition of the inorganic antibacterial agent to the reinforcing layer and the elastic base layer in the antibacterial base layer had a positive effect on both the antibacterial performance and the antibacterial durability of the PVC floor.
Comparative example 2 and comparative example 3 compared to example 1, the antibacterial agent between the adjacent layers of the UV antibacterial layer, the antibacterial bonding layer and the antibacterial wear-resistant layer has a synergistic effect.
Compared with the example 1, the silver-zinc-copper ion compound antibacterial liquid and the BBIT organic antibacterial agent have better antibacterial performance and antibacterial lasting performance when used together in the comparative examples 5, 6 and 7.
In comparative example 8, compared to example 1, the antibacterial wear-resistant layer is not provided with the antibacterial bonding layer, the stability of the antibacterial performance of the PVC flooring is not good, and the antibacterial durability is also reduced.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An antibacterial PVC floor comprises an antibacterial base material layer and is characterized in that the surface layer of the antibacterial base material layer is an antibacterial wear-resistant layer, and an antibacterial binding layer and an antibacterial UV layer which are sequentially laminated are arranged on the surface of the antibacterial wear-resistant layer from bottom to top;
the main components of the antibacterial UV layer comprise an organic antibacterial agent and/or an inorganic antibacterial agent and urethane acrylate;
the main components of the antibacterial binding layer comprise an inorganic antibacterial agent, an organic antibacterial agent and PVC resin;
the main components of the antibacterial wear-resistant layer comprise an inorganic antibacterial agent and PVC paste resin;
the inorganic antibacterial agent is a silver-zinc-copper ion compound antibacterial agent;
the organic antibacterial agent is benzisothiazolinone organic antibacterial agent.
2. The antibacterial PVC floor according to claim 1, wherein the mass ratio of silver ions, zinc ions and copper ions in the silver-zinc-copper ion compound antibacterial agent is 1: (0.8-1): (0.8 to 1).
3. The method of manufacturing an antimicrobial PVC flooring according to claim 1 or 2, wherein the components of the antimicrobial bonding layer further comprise a titanate coupling agent.
4. The method of preparing an antibacterial PVC floor according to claim 1, wherein the components of the antibacterial UV layer further include a vinyl chloride-vinyl acetate copolymer.
5. The method for preparing antibacterial PVC floor according to claim 3, characterized in that, according to the parts by mass,
the antibacterial binding layer comprises 100 parts of PVC resin, 1.5-2.5 parts of inorganic antibacterial agent solvent, 0.15-0.2 part of organic antibacterial agent, 0.5-1 part of titanate coupling agent, 25-35 parts of plasticizer, 2.5-3.5 parts of stabilizer and 0.8-1.4 parts of odor adsorbent;
the components of the antibacterial wear-resistant layer comprise 100 parts of PVC paste resin, 1.5-2.5 parts of inorganic antibacterial agent solvent, 35-45 parts of plasticizer, 2.5-3.5 parts of stabilizer and 0.8-1.4 parts of odor adsorbent.
6. The method for manufacturing the antibacterial PVC floor as claimed in claim 1, wherein the polymerization degree of PVC paste resin in the antibacterial wear-resistant layer is 1600-1800, and the polymerization degree of PVC resin in the antibacterial bonding layer is 1250-1350.
7. The preparation method of the antibacterial PVC floor is characterized by comprising the following steps: s1: respectively mixing the raw materials of each layer of the antibacterial base material layer and the raw material of the antibacterial binding layer;
s2: sequentially coating an antibacterial wear-resistant layer, performing first high-temperature curing, coating a reinforcing layer, performing second high-temperature curing, coating an elastic bottom layer on a carrier, and removing the carrier after the third high-temperature curing to obtain an antibacterial base material layer;
s3: plasticizing the raw material of the antibacterial bonding layer, and calendering to prepare the antibacterial bonding layer;
s4: hot-pressing and compounding the antibacterial bonding layer and the antibacterial wear-resistant layer;
s5: an antibacterial UV layer is sprayed on the surface of the antibacterial bonding layer;
the temperature of the first high-temperature curing and the second high-temperature curing is lower than that of the third high-temperature curing;
the temperature of the first high-temperature curing and the second high-temperature curing is not less than 170 ℃.
8. The method for preparing an antibacterial PVC floor according to claim 7, wherein the temperature of the first high-temperature curing in S2 is 175-185 ℃, the temperature of the second high-temperature curing is 175-185 ℃, and the temperature of the third high-temperature curing is 205-215 ℃.
9. The method for preparing an antibacterial PVC floor according to claim 7, wherein the benzisothiazolinone-based organic antibacterial agent, the inorganic antibacterial agent solvent and the titanate coupling agent which are components of the antibacterial bonding layer in S3 are mixed to form a first mixed solution; and mixing the plasticizer, the stabilizer and the odor adsorbent to form a second mixed solution, adding the second mixed solution into the PVC resin, fully mixing, and then adding the first mixed solution.
10. The preparation method of the antibacterial PVC floor according to claim 7, wherein the components of the reinforcing layer and the elastic bottom layer respectively comprise a silver-zinc-copper ion compound antibacterial agent, and the mass ratio of the silver-zinc-copper ion compound antibacterial agent in the components of the antibacterial wear-resistant layer, the reinforcing layer and the elastic bottom layer is (3-4.5): 1: (3-4).
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| CN202210175238.2A CN114347594A (en) | 2022-02-24 | 2022-02-24 | Antibacterial PVC floor and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1110766A (en) * | 1997-06-24 | 1999-01-19 | Toyobo Co Ltd | Anti-bacterial metal plate |
| CN104631778A (en) * | 2013-11-12 | 2015-05-20 | 江阴华诚汽车内饰件有限公司 | Odor removal and bacteria resistance type coiled material floor |
| CA3142127A1 (en) * | 2019-06-03 | 2020-12-10 | Mcmaster University | Omniphobic surfaces with hierarchical structures, and methods of making and uses thereof |
-
2022
- 2022-02-24 CN CN202210175238.2A patent/CN114347594A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1110766A (en) * | 1997-06-24 | 1999-01-19 | Toyobo Co Ltd | Anti-bacterial metal plate |
| CN104631778A (en) * | 2013-11-12 | 2015-05-20 | 江阴华诚汽车内饰件有限公司 | Odor removal and bacteria resistance type coiled material floor |
| CA3142127A1 (en) * | 2019-06-03 | 2020-12-10 | Mcmaster University | Omniphobic surfaces with hierarchical structures, and methods of making and uses thereof |
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