Mildew-proof agent, preparation process and preparation method of mildew-proof bond paper

Abstract

The invention relates to a mildewproof agent, a preparation process and a preparation method of mildewproof bond paper, and belongs to the technical field of mildewproof agent preparation. According to the mildew preventive disclosed by the invention, composite zirconium phosphate is taken as a carrier, mould permeation is physically blocked through a layered structure, and zinc ions and epsilon-polylysine are slowly released, so that a multi-dimensional long-acting antibacterial effect is realized; the styrene-acrylic emulsion base material and the silane coupling agent construct a brick-mud interpenetrating network structure, so that the oxygen permeability of the coating is reduced, and mould permeation is further prevented. According to the preparation method of the mildew-proof bond paper, N2 / CF4 mixed plasma treatment is adopted, so that the surface energy of the paper is improved, meanwhile, a fluorocarbon group and a silane coupling agent form a covalent bond, the interface bonding strength is improved, and uniform permeation of a mildew-proof agent is promoted; according to the gradient drying process, through three-stage temperature control, the internal stress of the coating is reduced, and the silane crosslinking degree and the water resistance are improved. Through collaborative innovation of a mildew inhibitor formula and a preparation method, the mildew inhibition rate of the mildew inhibitor is enhanced, and meanwhile, the loading efficiency of the mildew inhibitor is improved compared with that of a traditional process.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of mildew-proof agent preparation, and relates to a mildew-proof agent, a preparation process and a preparation method of mildew-proof film paper. BACKGROUND

[0002] Mold pollution has become a key technical bottleneck restricting the application of high polymer materials in the fields of packaging, building materials and the like. The traditional mildew-proof system has many technical bottlenecks. First, although organic mildew-proof agents such as triazoles and organic tin compounds have the characteristics of rapid sterilization, long-term use can easily induce microorganisms to produce degradation enzymes, resulting in the emergence of drug-resistant strains; second, inorganic mildew-proof agents such as cuprous oxide and nano-silver are prone to migration and precipitation, and in a humid environment, the continuous loss of effective components is easy to occur, and the overall mildew-proof durability is insufficient; in addition, although natural mildew-proof agents such as chitosan and vanillin meet the environmental protection requirements, they have poor heat resistance and are prone to decomposition, and are difficult to adapt to higher temperature coating processes.

[0003] The existing mildew-proof film paper preparation technology also has certain defects. The physical blending method mixes the mildew-proof agent into the paper base through mechanical mixing, but when the particle size of the mildew-proof agent exceeds a certain particle size, the surface micro-roughness of the paper increases, the diffusion path of the mildew-proof factor is lengthened, and the mildew-proof efficiency is reduced; although the chemical grafting method can achieve nanoscale dispersion, it needs to use highly toxic catalysts such as thionyl chloride, and there are process safety hazards. In addition, the modification depth of traditional surface treatment technologies such as corona and chemical immersion on paper fibers is limited, and the loading capacity of the mildew-proof agent is difficult to improve. Therefore, it is of great significance to develop a new mildew-proof system with the characteristics of high efficiency, durability and environmental protection. SUMMARY

[0004] The purpose of the present application is to provide a mildew-proof agent, a preparation process and a preparation method of mildew-proof film paper, which has the characteristics of excellent mildew-proof effect.

[0005] The purpose of the present application can be achieved by the following technical solutions: A mildew-proof agent, the formula of the mildew-proof agent is as follows, calculated by weight parts, 5-10 parts of composite zirconium phosphate, 65-75 parts of benzene propylene emulsion, 3-5 parts of dipentaerythritol dimethyl ammonium chloride, 1-3 parts of defoaming agent, 2-3 parts of 3-glycidyl ether oxypropyl trimethoxysilane, The preparation method of the composite zirconium phosphate is as follows, S1-1: 4-8 parts by weight of zinc acetate and 2-5 parts by weight of polyvinylpyrrolidone are dissolved in 100 parts by weight of isopropyl alcohol, heated to reflux state, 10 parts by weight of deionized water is added dropwise under stirring at a speed of 350-450 rpm, reflux stirring is continued for 2-3 h, zirconium phosphate powder is added, stirring is continued for 30-60 min, and then rotary evaporation is carried out at 53-55 DEG C until the solvent is evaporated, to obtain powder A; S1-2: dispersing the powder A in 100 parts by weight of deionized water, adding 5-15 parts by weight of an e-polylysine solution, heating and stirring at 45-55 DEG C for 4-6 hours, then washing with deionized water, and drying in a vacuum drying oven at 60 DEG C for 12 hours to obtain the composite zirconium phosphate.

[0006] As a preferred technical solution of the present application, the dropping speed of the deionized water in S1-1 is 3-5 mL / min.

[0007] As a preferred technical solution of the present application, the amount of the zirconium phosphate powder added in S1-1 is 1.3-1.5 times the mass of the zinc acetate.

[0008] As a preferred technical solution of the present application, the concentration of the e-polylysine solution in S1-2 is 2 M.

[0009] As a preferred technical solution of the present application, the defoaming agent is a mineral oil-based defoaming agent.

[0010] A preparation process of a mildew-proof agent, the specific steps of the preparation process of the mildew-proof agent are as follows, S6-1: mixing and high-speed dispersing the composite zirconium phosphate and 3-glycidyloxypropyltrimethoxysilane according to the formula proportion for 10-20 minutes to obtain a pre-dispersion liquid B; S6-2: adding a defoaming agent to the styrene-acrylic emulsion, stirring at a speed of 200-300 rpm for 30-60 minutes to obtain an emulsion C; S6-3: adding the pre-dispersion liquid B to the emulsion C, stirring at a speed of 200-300 rpm for 30-60 minutes, adding didecyl dimethyl ammonium chloride, increasing the speed to 350-450 rpm, and stirring at 45-50 DEG C for 30 minutes to obtain the mildew-proof agent.

[0011] As a preferred technical solution of the present application, the speed of high-speed dispersion in S6-1 is 3000-5000 rpm.

[0012] As a preferred technical solution of the present application, the adding speed of the pre-dispersion liquid B in S6-3 is 10-15 mL / min.

[0013] A preparation method of a mildew-proof film-coated paper, the specific steps of the preparation method of the mildew-proof film-coated paper are as follows, The surface of the base paper is activated by low-temperature plasma to obtain pretreated base paper, and the mildew-proof agent is coated on the surface of the pretreated base paper, and the coating amount is controlled at 8-12 g / m 2The dry temperature gradient is sequentially set as 80 DEG C, 100 DEG C and 120 DEG C, and drying is carried out for 5 min under each temperature gradient, to obtain the mildew-proof adhesive film paper.

[0014] As a preferred technical solution of the application, the parameters of the low-temperature plasma are set as N2 / CF4 mixed gas, wherein the volume ratio of N2 and CF4 is (4-6):1, the power is 80-100 W, the processing time is 40-60 s, the gas flow is 100-120 mL / min, the temperature is 30-36 DEG C, and the vacuum degree is 50-80 Pa.

[0015] Zirconium phosphate, as an inorganic layered compound, can inhibit the penetration and reproduction of microorganisms through physical barrier effect, and the exchangeable protons or metal ions between layers can destroy the integrity of microbial cell membranes, causing cell content leakage, thereby directly killing bacteria or mold. In addition, the rich hydroxyl groups on the surface of zirconium phosphate can adsorb water through hydrogen bonding, reducing the environmental humidity and forming a microenvironment that is not conducive to the survival of microorganisms.

[0016] The application synthesizes zinc oxide quantum dots by sol-gel method, and obtains zinc oxide quantum dots by controlling the ratio of zinc acetate and polyvinylpyrrolidone, the reflux temperature and time. The pyrrolidone groups in the polyvinylpyrrolidone molecules are adsorbed on the surface of zinc oxide crystal nucleus through non-covalent interaction, forming a stereoscopic barrier to prevent the excessive growth of crystal grains; and the long chain structure can also reduce the van der Waals force between quantum dots through steric hindrance effect to prevent agglomeration. The zinc oxide quantum dots can be excited to produce electron-hole pairs under light conditions, and then react with water or oxygen to generate active oxygen species such as hydroxyl radicals and superoxide anions. These active oxygen species can penetrate the microbial cell membrane, attack DNA, proteins and lipids, cause oxidative stress, and ultimately trigger cell apoptosis.

[0017] Epsilon-polylysine is a natural cationic antibacterial peptide, and the positively charged amino groups can be combined with the negatively charged phospholipid molecules on the surface of microbial cell membranes through electrostatic interaction, which can destroy the permeability barrier of the cell membrane, cause the leakage of cytoplasm, interfere with the function of membrane proteins, inhibit the activity of respiratory chain enzymes, and ultimately cause cell death.

[0018] As a carrier, zirconium phosphate not only physically fixes zinc oxide quantum dots and epsilon-polylysine through layered structure to prevent agglomeration or loss and ensure the stability of the composite material, but also slowly releases zinc ions and epsilon-polylysine molecules through ion exchange to realize the continuous supply of antibacterial components. In addition, the interlayer space of zirconium phosphate can limit the particle size growth of zinc oxide quantum dots, promote quantum confinement effect, and enhance the photocatalytic activity of zinc oxide quantum dots.

[0019] The composite zirconium phosphate prepared in the present application has a synergistic antibacterial mechanism, and the zinc oxide quantum dots can produce reactive oxygen species to kill bacteria through photocatalysis, and the epsilon-polylysine can achieve broad-spectrum antibiosis by destroying the cell membrane, so that more bacteria can be covered and the risk of drug resistance can be reduced. In addition, the zirconium phosphate itself also has a certain antibacterial and mildew-proof effect, and the zirconium phosphate carrier also has a slow-release property, which can prolong the antibacterial time, reduce the addition amount, and meet the green chemistry trend.

[0020] The styrene-acrylic emulsion serves as a film-forming base material, provides skeleton support and coating performance of the mildew-proof agent system, can form a continuous and dense film layer, blocks the penetration of external moisture and mold spores, and at the same time imparts flexibility to the coating. The emulsion molecular chain is inserted between the zirconium phosphate layers to form a structure similar to bricks and mortar, which significantly improves the denseness of the coating and reduces the oxygen transmission rate; in addition, the flexible segment of the styrene-acrylic emulsion compensates for the rigidity of the zirconium phosphate, and imparts the coating with bending resistance.

[0021] The mineral oil-based defoaming agent can eliminate harmful foam in the production process, reduce the surface tension of the system, and prevent air entrainment caused by foam from causing coating defects; avoid the formation of shrinkage holes, pinholes and other coating defects caused by the rupture of foam. 3-glycidyloxypropyltrimethoxysilane as an interfacial coupling agent, strengthens the compatibility of inorganic-organic phase, and its hydrolysis can generate silanol groups, which condense with the surface hydroxyl groups of the composite zirconium phosphate to form covalent bonds; the epoxy group reacts with the carboxyl group in the styrene-acrylic emulsion to build a chemical bridge, thereby improving the interfacial bonding strength and preventing the coating from falling off.

[0022] The composite zirconium phosphate and the didecyldimethylammonium chloride have a synergistic effect, so that the mildew-proof agent has multiple antibacterial mechanisms. The didecyldimethylammonium chloride quickly targets the phospholipid bilayer on the surface of the mold cell membrane through the electrostatic adsorption of the quaternary ammonium salt cation, forms a transient pore, and causes the cytoplasm to leak. After the didecyldimethylammonium chloride destroys the cell membrane, the intracellular glutathione and other antioxidant substances leak, which causes the mold to be unable to effectively neutralize the ROS generated by ZnO photocatalysis, and accelerates the cell apoptosis process; the contact sterilization effect of didecyldimethylammonium chloride and the persistent photocatalytic sterilization of zinc oxide are complementary, avoiding the resistance of mold through metabolic adjustment under a single mechanism. The epsilon-polylysine modification imparts the composite zirconium phosphate with positive charge, which synergistically enhances the electrostatic adsorption of the quaternary ammonium salt on the negatively charged mold; the flexible long chain of epsilon-polylysine can also form a network conformation at the adsorption interface, preventing the mold from forming a biofilm by secreting extracellular polysaccharides, and further inhibiting the quorum sensing effect.

[0023] The step of variable speed stirring in the preparation process S6-3 of the mildew-proof agent of the present application realizes the uniform dispersion of the composite zirconium phosphate through pre-mixing at 200-300 rpm, and then the speed is increased to 350-450 rpm to promote the synergistic adsorption of the quaternary ammonium salt cation of didecyldimethylammonium chloride and epsilon-polylysine, so that the electrostatic binding energy of the mildew-proof agent on the negatively charged mold is improved.

[0024] The mold-proof film paper preparation method of the present application first uses low-temperature plasma surface activation. N2 plasma removes the weak interface layer on the surface of the paper by physical bombardment. CF4 dissociation produces F radicals which react with cellulose molecules to produce fluorination, significantly increasing the surface energy and significantly improving the wettability of the mold-proof agent, ensuring uniform penetration of the mold-proof agent during coating. The fluorine-containing groups introduced by CF4 react with 3-glycidyloxypropyltrimethoxysilane in the mold-proof agent to form a covalent bond, significantly improving the interfacial bonding strength and preventing the mold-proof agent from falling off and failing during use. At a power of 80-100 W, the energy of the active particles in the plasma is sufficient to break the cellulose molecular chain, but excessive etching is avoided to prevent a decrease in paper strength. At the same time, within a treatment time of 40-60 seconds, the fluorocarbon group coverage reaches 1.2-1.5 monolayers, balancing surface modification and substrate protection. However, insufficient activation occurs if the time is too short, and fiber oxidation and chain breaking are easily induced if the time is too long. The subsequent gradient drying process rapidly evaporates the surface solvent in the first stage to prevent mold-proof agent particles from settling during the leveling process. The second stage promotes the formation of a three-dimensional network structure by the water-based styrene-acrylic emulsion. The third stage realizes the cross-linking reaction of the silane coupling agent, further solidifying the coating and promoting the stability of the mold-proof agent in a humid environment. Gradient heating can effectively reduce thermal shock, significantly reduce the internal stress of the coating, and avoid cracking defects.

[0025] The present application has the following advantages: (1) The composite zirconium phosphate carrier of the present application physically blocks the penetration of mold through the layered structure, and simultaneously releases zinc ions and ε-polylysine, imparting long-acting antibacterial properties and reducing the migration rate compared to traditional inorganic mold-proof agents. The quantum dots of zinc oxide achieve quantum size effect through the confinement effect of zirconium phosphate, improving photocatalytic activity and generating active oxygen species that form a contact sterilization-oxidative stress cascade response with didecyldimethylammonium chloride, effectively preventing drug resistance. The brick-mud structure formed by the styrene-acrylic emulsion substrate and the silane coupling agent significantly reduces the oxygen permeability of the coating. (2) The mold-proof film paper preparation method of the present application first uses N2 / CF4 plasma treatment to increase the surface energy of the paper and significantly improve the wettability of the mold-proof agent. The fluorocarbon groups form chemical bonds with the silane coupling agent, increasing the interfacial bonding strength. Precise control of the specific power range achieves controlled breaking of the cellulose molecular chain, balancing the activation effect and substrate protection. The gradient drying process reduces the internal stress of the coating and eliminates cracking defects through three-stage temperature control. The silane cross-linking degree is increased, and the water resistance of the coating is improved. The dual action of plasma fluorination and gradient curing significantly improves the mold-proof agent loading efficiency compared to traditional processes. DETAILED DESCRIPTION

[0026] In order to further illustrate the technical means and effects adopted by the present application to achieve the predetermined object of the present application, the specific embodiments, structures, features and effects according to the present application are described in detail as follows in combination with the embodiments.

[0027] In the examples and comparative examples of the present application: Zinc acetate: purchased from Lianyungang Kexin Chemical Co., Ltd., purity 99%; Polyvinylpyrrolidone: purchased from Qingdao Chenxi New Energy Co., Ltd., purity pharmaceutical grade; Isopropyl alcohol: purchased from Jiangsu Lunfeng Synthetic Technology Co., Ltd., purity 99%; Zirconium phosphate powder: purchased from Hubei Widelis Chemical Technology Co., Ltd., purity 99%; Epsilon-polylysine: purchased from Beijing Thompson Biotech Co., Ltd., purity 99%; 3-glycidyloxypropyltrimethoxysilane: purchased from Jiangxi Hongbai New Material Co., Ltd., purity 97%; Didecyldimethylammonium chloride: purchased from Hubei Deshao Chemical Co., Ltd., purity 99%; Styrene-acrylic emulsion: purchased from Wuhan Jiyexing Chemical Co., Ltd., solid content 40%, viscosity 800 mPa·s; Mineral oil-based defoaming agent: purchased from Foshan Nanhai Datian Chemical Co., Ltd., model PA-311.

[0028] Example 1: a kind of antifungal agent, the formula 1 of the antifungal agent is as follows, calculated by weight parts, composite zirconium phosphate 7 parts, styrene-acrylic emulsion 70 parts, didecyldimethylammonium chloride 4 parts, mineral oil-based defoaming agent 2 parts, 3-glycidyloxypropyltrimethoxysilane 2.5 parts, The preparation method of the composite zirconium phosphate is as follows, S1-1: 6 parts by weight of zinc acetate and 3 parts by weight of polyvinylpyrrolidone were dissolved in 100 parts by weight of isopropyl alcohol, heated to reflux state, 10 parts by weight of deionized water was added at a speed of 4 mL / min with stirring at a speed of 400 rpm, reflux stirring was continued for 2.5 h, 1.4 times the mass of zinc acetate of zirconium phosphate powder was added, stirring was continued for 45 min, then rotary evaporation was carried out at 54 ℃ until the solvent was evaporated, to obtain powder A; S1-2: powder A was dispersed in 100 parts by weight of deionized water, 10 parts by weight of 2 M epsilon-polylysine solution was added, heated and stirred at 50 ℃ for 5 h, then washed with deionized water, and dried in a 60 ℃ vacuum drying oven for 12 h to obtain the composite zirconium phosphate.

[0029] A preparation process of an antifungal agent, the specific steps of the preparation process of the antifungal agent are as follows, S6-1: The composite zirconium phosphate and 3-glycidyloxypropyltrimethoxysilane were mixed in a ratio according to the formula 1 and dispersed at a high speed of 4000 rpm for 15 min to obtain a pre-dispersion liquid B; S6-2: A mineral oil-based defoaming agent was added to the styrene-acrylic emulsion, stirred at a speed of 250 rpm for 45 min to obtain an emulsion C; S6-3: The pre-dispersion liquid B was added to the emulsion C at an adding speed of 12 mL / min, stirred at a speed of 250 rpm for 45 min, and then a didecyl dimethyl ammonium chloride was added, the stirring speed was increased to 400 rpm, and the stirring was performed at 47 ℃ for 30 min to obtain the antifungal agent.

[0030] A preparation method of the antifungal film paper, the specific steps of the preparation method of the antifungal film paper are as follows, The surface of the base paper was activated by low-temperature plasma, the parameters of the low-temperature plasma were set as follows: N2 / CF4 mixed gas, the volume ratio of N2 and CF4 was 5:1, the power was 90 W, the treatment time was 50 s, the gas flow was 110 mL / min, the temperature was 33 ℃, and the vacuum degree was 60 Pa, to obtain the pretreated base paper, the antifungal agent was coated on the surface of the pretreated base paper, and the coating amount was controlled at 10 g / m 2 The drying temperature gradient was set as 80 ℃, 100 ℃ and 120 ℃ in sequence, and the drying was performed at each temperature gradient for 5 min to obtain the antifungal film paper.

[0031] Example 2: An antifungal agent, the formula 2 of the antifungal agent is as follows, calculated by weight parts: composite zirconium phosphate 5 parts, styrene-acrylic emulsion 65 parts, didecyl dimethyl ammonium chloride 3 parts, mineral oil-based defoaming agent 1 part, 3-glycidyloxypropyltrimethoxysilane 2 parts, The preparation method of the composite zirconium phosphate is as follows, S1-1: 4 parts by weight of zinc acetate and 2 parts by weight of polyvinylpyrrolidone were dissolved in 100 parts by weight of isopropyl alcohol, heated to reflux state, 10 parts by weight of deionized water was added at a speed of 3 mL / min, and stirred at a speed of 350 rpm, and the reflux stirring was continued for 2 h, then 1.3 times the mass of the zinc acetate of zirconium phosphate powder was added, and the stirring was continued for 30 min, and then rotary evaporation was performed at 53 ℃ until the solvent was evaporated to dryness to obtain powder A; S1-2: The powder A was dispersed in 100 parts by weight of deionized water, 5 parts by weight of ε-polylysine solution with a concentration of 2 M was added, heated and stirred at 45 ℃ for 4 h, then washed with deionized water, and dried in a 60 ℃ vacuum drying oven for 12 h to obtain the composite zirconium phosphate.

[0032] A preparation process of a mildew-proof agent, the specific steps of the preparation process of the mildew-proof agent are as follows, S6-1: The composite zirconium phosphate and 3-glycidyloxypropyltrimethoxysilane are mixed in a ratio according to formula 2 and are high-speed dispersed at a speed of 3000 rpm for 10 min to obtain a pre-dispersed liquid B; S6-2: Mineral oil-based defoaming agent is added to the styrene-acrylic emulsion, stirring at a speed of 200 rpm for 30 min to obtain an emulsion C; S6-3: The pre-dispersed liquid B is added to the emulsion C at an adding speed of 10 mL / min, stirring at a speed of 200 rpm for 30 min, adding didecyl dimethyl ammonium chloride, increasing the speed to 350 rpm, and stirring at 45 ℃ for 30 min to obtain the mildew-proof agent.

[0033] A preparation method of a mildew-proof film-coated paper, the specific steps of the preparation method of the mildew-proof film-coated paper are as follows, The raw paper is surface-activated by low-temperature plasma, the parameters of the low-temperature plasma are set as follows: N2 / CF4 mixed gas, the volume ratio of N2 and CF4 is 4:1, the power is 80 W, the processing time is 40 s, the gas flow is 100 mL / min, the temperature is 30 ℃, and the vacuum degree is 50 Pa, to obtain the pretreated raw paper, the mildew-proof agent is coated on the surface of the pretreated raw paper, and the coating amount is controlled at 8 g / m 2 The drying temperature gradient is set as 80 ℃, 100 ℃ and 120 ℃ in sequence, and each temperature gradient is dried for 5 min to obtain the mildew-proof film-coated paper.

[0034] Example 3: A mildew-proof agent, the formula 3 of the mildew-proof agent is as follows, calculated by weight parts, composite zirconium phosphate 10 parts, styrene-acrylic emulsion 75 parts, didecyl dimethyl ammonium chloride 5 parts, mineral oil-based defoaming agent 3 parts, 3-glycidyloxypropyltrimethoxysilane 3 parts, The preparation method of the composite zirconium phosphate is as follows, S1-1: 8 parts by weight of zinc acetate and 5 parts by weight of polyvinylpyrrolidone are dissolved in 100 parts by weight of isopropyl alcohol, heated to reflux state, 10 parts by weight of deionized water is added at a speed of 5 mL / min with stirring at a speed of 450 rpm, and the reflux stirring is continued for 3 h, 1.5 times the mass of the zinc acetate of zirconium phosphate powder is added, and the stirring is continued for 60 min, followed by rotary evaporation at 55 ℃ until the solvent is evaporated to dryness, to obtain powder A; S1-2: Powder A is dispersed in 100 parts by weight of deionized water, 15 parts by weight of an ε-polylysine solution with a concentration of 2 M is added, heated and stirred at 55 ℃ for 6 h, then washed with deionized water, and dried in a 60 ℃ vacuum drying oven for 12 h to obtain the composite zirconium phosphate.

[0035] A preparation process of a mildew-proof agent, the specific steps of the preparation process of the mildew-proof agent are as follows, S6-1: The composite zirconium phosphate and 3-glycidyloxypropyltrimethoxysilane are mixed in a ratio according to the formula 3 and are high-speed dispersed at a speed of 5000 rpm for 20 min to obtain a pre-dispersed liquid B; S6-2: Mineral oil-based defoaming agent is added to the styrene-acrylic emulsion, and stirring is performed at a speed of 300 rpm for 60 min to obtain an emulsion C; S6-3: The pre-dispersed liquid B is added to the emulsion C at an adding speed of 15 mL / min, stirring is performed at a speed of 300 rpm for 60 min, didecyldimethylammonium chloride is added, the speed is increased to 450 rpm, and stirring is performed at 50 ℃ for 30 min to obtain the mildew-proof agent.

[0036] A preparation method of a mildew-proof film-coated paper, the specific steps of the preparation method of the mildew-proof film-coated paper are as follows, The raw paper is surface-activated by low-temperature plasma, the parameters of the low-temperature plasma are set as follows: N2 / CF4 mixed gas, the volume ratio of N2 and CF4 is 6:1, the power is 100 W, the processing time is 60 s, the gas flow is 120 mL / min, the temperature is 36 ℃, and the vacuum degree is 80 Pa, to obtain the pretreated raw paper, the mildew-proof agent is coated on the surface of the pretreated raw paper, and the coating amount is controlled to be 12 g / m 2 , and the drying temperature gradient is set to be 80 ℃, 100 ℃ and 120 ℃ in sequence, and the drying is performed at each temperature gradient for 5 min to obtain the mildew-proof film-coated paper.

[0037] Comparative Example 1 The preparation of the composite zirconium phosphate does not add ε-polylysine solution, and the remaining steps are consistent with Example 1.

[0038] Comparative Example 2 The preparation of the composite zirconium phosphate does not add zinc acetate, and the remaining steps are consistent with Example 1.

[0039] Comparative Example 3 The preparation of the composite zirconium phosphate does not add zinc acetate, and the remaining steps are consistent with Example 1.

[0040] Comparative Example 4 The preparation of the mildew-proof agent does not add didecyldimethylammonium chloride, and the remaining steps are consistent with Example 1.

[0041] Comparative Example 5 The preparation of the mildew-proof agent does not add 3-glycidyloxypropyltrimethoxysilane, and the remaining steps are consistent with Example 1.

[0042] Comparative Example 6 The mold-proof adhesive film paper was prepared without low-temperature plasma activation treatment, and the other steps were consistent with those of Example 1.

[0043] Comparative Example 7 The mold-proof adhesive film paper was prepared by using single temperature 120 ℃ drying for 15 min instead of gradient drying, and the other steps were consistent with those of Example 1.

[0044] Mold-proof performance test The mold-proof performance of the mold-proof adhesive film paper prepared in the examples and comparative examples was tested according to the standard of ASTM G21 “Determination of the mold-proof performance of synthetic polymer materials”. The spore suspension of Aspergillus niger with a concentration of 1×10 6 cfc / mL was coated on the surface of the mold-proof adhesive film paper samples prepared in the examples and comparative examples, and the control group was the blank base paper without adding mold-proof agent. The test period was 28 days, the temperature was 28 ℃, and the humidity was ≥90%. The mold growth on the surface of each sample was observed and recorded. The mold inhibition rate (%) was calculated, and the calculation method was mold inhibition rate (%) = (mold coverage area of the control group - mold coverage area of the experimental group) / mold coverage area of the control group × 100%. The experimental results are recorded in the following table.

[0045]

[0046] Compared with Example 1, the mold inhibition rate in Comparative Example 1 is reduced from 98.6% to 68.2% without adding the epsilon-polylysine solution, indicating that the epsilon-polylysine is the core component of the mold-proof system, and its absence leads to a significant decrease in the inhibition rate, indicating that the epsilon-polylysine plays a major role in the antibacterial effect by destroying the cell membrane of mold or inhibiting key metabolic enzymes. In Comparative Example 2, the zinc acetate is not added in the preparation of the composite zirconium phosphate, and the inhibition rate is reduced to 76.3%, which is weaker than the effect of the epsilon-polylysine alone and plays a synergistic antibacterial effect with other components in the mold-proof agent. In Comparative Example 3, the untreated zirconium phosphate is used to replace the composite zirconium phosphate, and the inhibition rate is reduced to 53.7%. The untreated zirconium phosphate lacks the ability to load epsilon-polylysine and zinc acetate, and only relies on the antibacterial effect of zirconium phosphate and didecyldimethylammonium chloride, resulting in a significant decrease in the mold-proof effect. In Comparative Example 4, the didecyldimethylammonium chloride is not added, and the inhibition rate is reduced to 70.6%. As a quaternary ammonium salt bactericide, didecyldimethylammonium chloride can enhance the mold-proof effect by destroying the lipid layer of the cell membrane, but its effect depends on the synergy of other components, and the inhibition rate decreases less than the epsilon-polylysine when it is absent alone. In Comparative Example 5, the 3-glycidoxypropyltrimethoxysilane is not added, and the inhibition rate is reduced to 93.1%. The 3-glycidoxypropyltrimethoxysilane can improve the adhesion of the mold-proof agent to the film paper through chemical bonding, and its absence may lead to the shedding of part of the antibacterial components. In Comparative Example 6, the low-temperature plasma activation treatment is not performed, and the inhibition rate is reduced to 84.7%. The plasma treatment can increase the active groups on the surface of the film paper and promote the chemical bonding of the mold-proof agent, and its absence leads to a decrease in the stability of the antibacterial layer. In Comparative Example 7, the single temperature drying is used to replace the gradient drying process, and the inhibition rate is slightly reduced. The gradient drying can optimize the film uniformity of the mold-proof agent by controlling the solvent evaporation rate, thereby affecting the mold-proof effect. According to the experimental data of the above examples and comparative examples, the mold-proof film paper prepared by the present application has excellent mold-proof effect.

[0047] The above description is only a preferred embodiment of the present application, and does not limit the present application in any form. Although the present application has been disclosed as above with a preferred embodiment, it is not intended to limit the present application. Any person skilled in the art can make some changes or modifications to the above disclosed technical content without departing from the scope of the technical solution of the present application, and any simple modification, equivalent change and modification of the above examples according to the technical essence of the present application are still within the scope of the technical solution of the present application.

Claims

1. An antifungal agent, characterized by, The antifungal agent is prepared by the following steps, The preparation method of the composite zirconium phosphate is as follows, S1-1: 4-8 parts by weight of zinc acetate and 2-5 parts by weight of polyvinylpyrrolidone are dissolved in 100 parts by weight of isopropyl alcohol, heated to reflux state, and 10 parts by weight of deionized water is added dropwise at a stirring speed of 350-450 rpm, and the reflux stirring is continued for 2-3 h, then zirconium phosphate powder is added, and the stirring is continued for 30-60 min, and then rotary evaporation is carried out at 53-55 ℃ until the solvent is evaporated, to obtain powder A; S1-2: Powder A is dispersed in 100 parts by weight of deionized water, 5-15 parts by weight of ε-polylysine solution is added, heated and stirred at 45-55 ℃ for 4-6 h, then washed with deionized water, and dried in a 60 ℃ vacuum drying oven for 12 h to obtain the composite zirconium phosphate.

2. The antifungal agent according to claim 1, characterized in that, The dropping speed of deionized water in S1-1 is 3-5 mL / min.

3. The antifungal agent according to claim 1, characterized in that, The addition amount of zirconium phosphate powder in S1-1 is 1.3-1.5 times the mass of zinc acetate.

4. The antifungal agent of claim 1, wherein The concentration of ε-polylysine solution in S1-2 is 2 M.

5. The antifungal agent of claim 1, wherein The defoaming agent is a mineral oil-based defoaming agent.

6. A process for the preparation of the antifungal agent according to any one of claims 1 to 5, characterized in that, The specific steps of the preparation process of the antifungal agent are as follows, S6-1: The composite zirconium phosphate and 3-glycidyl ether oxypropyl trimethoxysilane are mixed and high-speed dispersed for 10-20 min to obtain a pre-dispersion B; S6-2: The defoaming agent is added to the styrene-acrylic emulsion, and stirred at a speed of 200-300 rpm for 30-60 min to obtain an emulsion C; S6-3: The pre-dispersion B is added to the emulsion C, stirred at a speed of 200-300 rpm for 30-60 min, the didecyl dimethyl ammonium chloride is added, the speed is increased to 350-450 rpm, and stirred at 45-50 ℃ for 30 min to obtain the antifungal agent.

7. The process for the preparation of an antifungal agent according to claim 6, characterized in that, The speed of high-speed dispersion in S6-1 is 3000-5000 rpm.

8. The process for the preparation of an antifungal agent according to claim 6, characterized in that, The addition speed of pre-dispersion B in S6-3 is 10-15 mL / min.

9. A method of producing the mold-proof film-coated paper according to any one of claims 1 to 5, characterized by, The specific steps of the preparation method of the antifungal adhesive film paper are as follows, The low-temperature plasma is used to activate the surface of the raw paper to obtain pretreated raw paper, and the antifungal agent is coated on the surface of the pretreated raw paper, and the coating amount is controlled at 8-12 g / m 2 The drying temperature gradient is set as 80℃, 100℃ and 120℃ in sequence, and the drying is performed for 5 min under each temperature gradient to obtain the antifungal film paper.

10. The method for preparing an anti-mildew adhesive film paper according to claim 9, characterized in that, The parameters of the low-temperature plasma are set as follows: N2 / CF4 mixed gas, volume ratio of N2 to CF4 (4-6):1, power 80-100 W, processing time 40-60 s, gas flow rate 100-120 mL / min, temperature 30-36 ℃, and vacuum degree 50-80 Pa.

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