Long-acting dripping antifogging master batch as well as preparation method and application thereof

Abstract

The invention provides a long-acting dripping antifogging master batch as well as a preparation method and application thereof, and the long-acting dripping antifogging master batch comprises the following components in parts by weight: 40-90 parts of matrix resin, 10-40 parts of a dripping agent, 1-20 parts of metal salt and 1-20 parts of a high-molecular-weight slow release agent. According to the long-acting dripping antifogging master batch disclosed by the invention, the dripping agent, the metal salt and the high-molecular-weight slow-release agent are compounded, and the long-acting dripping antifogging master batch is used for preparing a thin film material, so that the dripping lasting period of the thin film material can be effectively prolonged, and meanwhile, the thin film has relatively high light transmittance.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a long-lasting anti-drip and anti-fogging masterbatch, its preparation method, and its application. Background Technology

[0002] Agricultural greenhouse films are typically made of polyolefin films. However, they have poor hydrophilicity, leading to condensation and fogging in areas with large temperature differences between day and night, and during autumn and winter. The high humidity and temperature variations between the inside and outside of the greenhouse film cause these phenomena. The presence of dew and fog weakens crop photosynthesis, and the condensed water droplets falling on the crops can cause wilting, seedling rot, and other problems, severely impacting crop yield.

[0003] To address the aforementioned problems, anti-drip agents are typically introduced into greenhouse films. These agents, with their numerous hydrophilic groups, regulate the wettability of the film surface, causing condensed water droplets to drip off, thus achieving an anti-fogging effect. Existing anti-drip greenhouse films are categorized into two types based on the method of agent introduction: external coating and internal addition. Internally added anti-drip films are widely used and developed due to their advantages such as simple processing, low processing cost, and good quality stability. However, internally added anti-drip films suffer from the problem of excessively rapid agent migration. A large amount of anti-drip agent is lost with water droplets in the initial stage of its effectiveness, resulting in a short-lived anti-fogging effect. The anti-drip effect of typical internally added anti-drip films is less than 6 months, while the lifespan of greenhouse films with added anti-aging additives is 2-3 years. The anti-drip effect is far shorter than the lifespan, requiring frequent replacement to maintain anti-fogging performance, leading to resource waste and environmental pollution, which is detrimental to sustainable development.

[0004] Currently, to address the issue of excessively rapid dripping agent migration, practical production mainly employs methods such as compounding dripping agents and adding sustained-release agents to extend the dripping persistence of dripping films. Compounding dripping agents involves using dripping agents with different migration rates together, ensuring dripping agent migration at different stages of the film's lifespan. However, the amount of dripping agent added is limited, and to maintain a balance between dripping performance and dripping persistence, this method's delaying effect is insufficient. Adding sustained-release agents can further extend the dripping persistence of dripping films. Existing sustained-release agents mainly control dripping agent release through physical adsorption and hydrogen bonding, but their effectiveness is limited and still cannot meet the requirements for long-term use.

[0005] Therefore, developing a masterbatch that can effectively extend the dripping persistence of thin film materials while also enabling the film to have high light transmittance is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a long-lasting anti-drip and anti-fogging masterbatch, its preparation method, and its application. The film material prepared from the long-lasting anti-drip and anti-fogging masterbatch exhibits a long anti-drip duration and high light transmittance.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a long-lasting anti-drip and anti-fogging masterbatch, wherein, by weight, the long-lasting anti-drip and anti-fogging masterbatch comprises 40-90 parts of matrix resin, 10-40 parts of anti-drip agent, 1-20 parts of metal salt and 1-20 parts of high molecular weight slow-release agent.

[0009] In this invention, the high molecular weight sustained-release agent can be a polymer or a compound with a large molecular weight; when selected from polymers, it refers to polymers with an index-average molecular weight > 1000; when selected from compounds with a large molecular weight, it refers to compounds with a molecular weight > 1000.

[0010] In this invention, the anti-dripping agent and the high molecular weight sustained-release agent can undergo coordination reactions with the metal salt to form complexes, which helps to reduce the migration rate of the anti-dripping agent and prolong the anti-dripping effect of the material. At the same time, the anti-dripping agent, the high molecular weight sustained-release agent, and the metal salt can form complexes of different molecular weights to achieve the stepwise release of the anti-dripping agent, thereby achieving the effect of sustained and controlled release and further prolonging the anti-dripping effect of the material. In addition, it can also ensure good light transmittance of the film material. Furthermore, it is low in cost, simple and convenient to operate, and can be mass-produced.

[0011] In this invention, 40 to 90 parts of the matrix resin can be, for example, 42 parts, 45 parts, 48 ​​parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts, 78 parts, 80 parts, 82 parts, 85 parts, 88 parts, etc.

[0012] In this invention, 10 to 40 parts of the dripping agent can be, for example, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, etc.

[0013] In this invention, if the content of the anti-dripping agent is too low, it cannot form a complete hydrophilic spreading layer on the membrane surface, resulting in early failure of the anti-dripping performance; if the content is too high, it will cause excessive migration and precipitation of the anti-dripping agent, which will not only accelerate the decay of the anti-dripping performance due to the loss of effective ingredients, but also cause "blooming" due to saturation precipitation, forming visible "white frost" on the membrane surface and damaging the light transmittance of the film.

[0014] In this invention, 1 to 20 parts of metal salt can be, for example, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, etc.

[0015] In this invention, if the content of the metal salt is too low, the coordination reaction with the dropper is not easy to occur, making it difficult to effectively delay its precipitation; if the content is too high, it will be over-crosslinked to form a dense network, which will restrict the functional migration of the dropper and may cause aggregation, resulting in uneven dropper performance.

[0016] In this invention, 1 to 20 parts of high molecular weight sustained-release agent can be, for example, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, etc.

[0017] In this invention, if the content of the high molecular weight sustained-release agent is too low, it cannot form an effective synergistic coordination network with the dripping agent, and its effect on delaying the precipitation of the dripping agent is insufficient; if the content is too high, it will excessively compete with the dripping agent for metal ions, causing the metal ions to tend to react with the coordination groups of the high molecular weight sustained-release agent, resulting in self-crosslinking of the high molecular weight sustained-release agent, affecting the melt processing performance of the masterbatch, and at the same time causing the dripping agent itself to precipitate prematurely due to insufficient coordination.

[0018] Preferably, the matrix resin includes at least one of polyethylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, polypropylene, polyolefin elastomer, polycarbonate, polyethylene terephthalate, and polylactic acid.

[0019] Preferably, the dripping agent includes at least one of polyol fatty acid ester dripping agents, amine dripping agents, polyoxyethylene ether dripping agents, ionic dripping agents, and organoboron dripping agents.

[0020] Preferably, the polyol fatty acid ester dripping agent includes at least one of the following: glyceryl monostearate, sorbitan monostearate, sorbitan monooleate, glyceryl monooleate, polyglyceryl stearate, polyglyceryl oleate, pentaerythritol monostearate, pentaerythritol oleate, mannitol monooleate, sucrose monolaurate, sucrose dilaurate, dehydrated sorbitan monooleate, pentaerythritol difatty acid ester, sorbitan monopalmitate, xylitol monostearate, polyglycerol laurate, and dioctyl adipate.

[0021] Preferably, the amine dripping agent includes at least one of N,N-dihydroxyethyloctadecylamine, octadecyl diethanolamine, coconut oil diethanolamide, stearic acid diethanolamide, oleic acid diethanolamide, lauric acid diethanolamide, coconut oil monoethanolamide, stearic acid monoethanolamide, oleic acid monoethanolamide, lauric acid monoethanolamide, coconut oil-based triethanolamine, and palmitic acid diethanolamide.

[0022] Preferably, the polyoxyethylene ether-based anti-dripping agent includes at least one of alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, fatty alcohol polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether, castor oil polyoxyethylene ether, polyoxyethylene alkyl ether, alkylphenol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, alkylphenol polyoxyethylene ether sulfate, alkylphenol polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether carboxylate, fatty amine polyoxyethylene ether, fatty alcohol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether sulfate, arylphenol polyoxyethylene ether, and alkylphenol polyoxyethylene ether carboxylate.

[0023] Preferably, the ionic dripping agent includes at least one of lignin sulfonate, alkylbenzene sulfonate, α-olefin sulfonate, fatty alcohol polyoxyethylene ether sulfonate, stearoyl lactate, oleic acid fatty acid salt, and lauric acid fatty acid salt.

[0024] Preferably, the organoboron-based dripping agent includes at least one of glyceryl monostearate borate, triethanolamine borate, sorbitan borate, pentaerythritol borate, polyglyceryl borate, diethanolamide borate, ethoxylated alkylamine borate, polyol ethoxylated borate, glyceryl distearate, and dioleopropylene borate.

[0025] Preferably, the metal salt includes organometallic salts and / or inorganic metal salts.

[0026] Preferably, the organometallic salt includes at least one of carboxylates, organic carbonates, organic sulfonates, organic borates, organic phosphates, alkoxides, acetylene salts, cyanides, porphyrin salts, and metal salts containing carbocations.

[0027] Preferably, the carboxylate comprises a fatty acid salt with ≥2 carbon atoms and / or an aromatic acid salt, for example, a fatty acid salt or aromatic acid salt with 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, or 30 carbon atoms; the carboxylate comprises at least one of acetate, butyrate, hexanoate, decanoate, laurate, stearate, oleate, epoxylinolenic acid salt, myristate, rosinate, palmitate, castor oil, and benzoate; more preferably, it comprises at least one of stearate, acetate, oleate, and benzoate.

[0028] Preferably, the inorganic metal salt includes at least one of chloride, nitrate, carbonate, phosphate, nitrite, sulfate, sulfite, borate, sulfide, cyanide, bromide, fluoride, and bicarbonate.

[0029] Preferably, the metal ions in the metal salt include La. 3+ Ce 3+ Eu 3+ Eu 2+ Yb 3+ Gd 3+ 、Tb 3+ 、Sm 3+ Dy 3+ 、Nd 3+ Ho 3+ Er 3+ Tm 3+ Pr 3+ Zn 2+ Cr 3+ Mn 2+ Co 3+ Ni 3+ Au 3+ Fe 2+ Fe 3+ Cu 2+ Mg 2+ Ba 2+ Ca 2 + Al 3+ At least one of them.

[0030] Preferably, the high molecular weight sustained-release agent contains a coordinating group, which includes at least one of hydroxyl, carboxyl, acid anhydride, sulfonic acid, β-diketone, amino, amide, imidazole, pyridinyl, catechol, and thiol groups.

[0031] Preferably, the high molecular weight sustained-release agent comprises at least one of maleic anhydride-grafted polyethylene, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, oxidized polyethylene wax, carboxyl-terminated polyethylene wax, glycidyl methacrylate-grafted polyethylene, glycidyl methacrylate-grafted polypropylene, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl alcohol copolymer, polystyrene sulfonic acid, polyvinylpyrrolidone, chitosan, tannic acid, polyacrylamide, polyethyleneimine, polyethylene glycol, polyvinylpyridine, vinylimidazole-grafted polyethylene, polydopamine, and thiol-modified polyolefins.

[0032] Preferably, the long-lasting anti-drip and anti-fog masterbatch further includes 1 to 10 parts of other additives, such as 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, etc.

[0033] Preferably, the other additives include at least one of functional fillers, lubricants, coupling agents, antioxidants, antistatic agents, plasticizers, light stabilizers, flame retardants, and compatibilizers.

[0034] In this invention, the functional filler includes, but is not limited to, at least one of silica, kaolin, diatomaceous earth, zeolite, porous alumina, and hydrotalcite-like materials.

[0035] In this invention, the lubricant includes, but is not limited to, at least one of polyethylene wax, polypropylene wax, paraffin wax, organosiloxane, silicone, polytetrafluoroethylene, erucamide, oleamide, stearic acid, glyceryl stearate, and N,N'-ethylene bis-stearamide.

[0036] In this invention, the coupling agent includes silane coupling agents, which include, but are not limited to, at least one of the following: aminosilane coupling agents (such as γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane), epoxysilane coupling agents (such as γ-glycidoxypropyltrimethoxysilane), vinylsilane coupling agents (such as vinyltriethoxysilane, vinyltrimethoxysilane), methacryloxysilane coupling agents (γ-methacryloxypropyltrimethoxysilane), and mercaptosilane coupling agents (such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane).

[0037] In this invention, the antioxidants include primary antioxidants and / or secondary antioxidants; the primary antioxidants include, but are not limited to, any one or a combination of at least two of 2,6-di-tert-butyl-p-cresol (BHT), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis(4-methyl-6-nonylphenol), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, and pentaerythritol tetra(3,5-di-tert-butyl-4-hydroxyhydrocinnamate); the secondary antioxidants include, but are not limited to, tri(nonylphenyl) phosphite and / or dilauryl thiodipropionate.

[0038] In this invention, the antistatic agent includes, but is not limited to, at least one of hexadecyltrimethylammonium chloride, dioctadecyldimethylammonium chloride, sodium dodecylbenzenesulfonate, dodecylaminopropionic acid, alkyldimethyl betaine, polyether ester amide, and polyaniline.

[0039] In this invention, the plasticizer includes, but is not limited to, at least one of di(2-ethylhexyl) phthalate, dibutyl phthalate, diethyl phthalate, dioctyl adipate, dioctyl sebacate, and epoxidized soybean oil.

[0040] In this invention, the light stabilizer includes, but is not limited to, at least one of benzotriazole UV absorbers (such as UV-P, UV-327, UV-326), benzophenone UV absorbers (such as UV-531, UV-9), triazine UV absorbers (such as UV-1164, UV-400), and hindered amine light stabilizers (such as Chimassorb 944, Tinuvin 770, Tinuvin 622).

[0041] In this invention, the flame retardant includes, but is not limited to, at least one of aluminum hydroxide, magnesium hydroxide, melamine cyanurate, ammonium polyphosphate, tricresyl phosphate, triphenyl phosphate, resorcinol bis(diphenyl phosphate), and aluminum diethylphosphite.

[0042] In this invention, the compatibilizer includes, but is not limited to, at least one of vinyltrimethoxysilane, titanate, styrene-maleic anhydride random copolymer, epoxy silicone oil grafted maleic anhydride, fluorinated methacrylate-epoxy copolymer, and ethylene-(meth)acrylic acid ionomer (such as Surlyn 8940, Surlyn 9720, Surlyn 9650).

[0043] In a second aspect, the present invention provides a method for preparing a long-lasting anti-drip and anti-fogging masterbatch according to the first aspect, the method comprising the following steps: mixing a matrix resin, an anti-drip agent, a metal salt, a high molecular weight slow-release agent, and optional other additives, followed by intensive mixing, melt extrusion, and granulation to obtain the long-lasting anti-drip and anti-fogging masterbatch.

[0044] Preferably, the mixing speed is 100~5000 r / min, for example, it can be 200 r / min, 400 r / min, 600 r / min, 800 r / min, 1000 r / min, 1200 r / min, 1500 r / min, 1800 r / min, 2000 r / min, 2500 r / min, 3000 r / min, 3500 r / min, 4000 r / min, 4500 r / min, 4800 r / min, etc.; the mixing time is 1~100 min, for example, it can be 2 min, 4 min, 6 min, 8 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, 65 min, 70 min, 75 min, 80 min, 85 min, 90 min, 95 min, etc.

[0045] In this invention, the mixing is carried out in a high-speed mixer.

[0046] Preferably, the mixing temperature is 50~300℃, for example, it can be 80℃, 100℃, 120℃, 150℃, 180℃, 200℃, 220℃, 250℃, 280℃, etc.; the mixing time is 1~50 min, for example, it can be 2 min, 4 min, 6 min, 8 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, etc.; the mixing speed is 10~200 r / min, for example, it can be 20 r / min, 40 r / min, 60 r / min, 80 r / min, 100 r / min, 120 r / min, 140 r / min, 160 r / min, 180 r / min, etc.

[0047] In this invention, the mixing is carried out in a mixing machine.

[0048] Preferably, the temperature of the melt extrusion is 50~400℃, for example, it can be 80℃, 100℃, 120℃, 150℃, 180℃, 200℃, 220℃, 250℃, 280℃, 300℃, 320℃, 350℃, 380℃, etc.; the rotation speed of the melt extrusion is 10~200 r / min, for example, it can be 20 r / min, 40 r / min, 60 r / min, 80 r / min, 100 r / min, 120 r / min, 140 r / min, 160 r / min, 180 r / min, etc.

[0049] In this invention, the melt extrusion is carried out in a twin-screw extruder.

[0050] Thirdly, the present invention provides a polymer film comprising the long-lasting anti-drip and anti-fogging masterbatch described in the first aspect.

[0051] In this invention, the polymer film further includes a film-forming resin.

[0052] In this invention, the film-forming resin includes at least one of polyethylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, polypropylene, polyolefin elastomer, polycarbonate, polyethylene terephthalate, and polylactic acid.

[0053] In this invention, the mass ratio of the long-lasting anti-drip and anti-fogging masterbatch to the film-forming resin is (1~30):(70~99), wherein the specific values ​​of (1~30) can be, for example, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, etc.; and the specific values ​​of (70~99) can be, for example, 72, 75, 78, 80, 82, 85, 88, 90, 92, 95, 98, etc.

[0054] In this invention, the method for preparing the polymer film includes: mixing a film-forming resin with a long-lasting anti-drip and anti-fogging masterbatch, then melting and extruding the mixture to form the polymer film.

[0055] In this invention, the molding method includes, but is not limited to, extrusion blow molding.

[0056] In this invention, the molding temperature is 100~400℃, for example, it can be 120℃, 150℃, 180℃, 200℃, 220℃, 250℃, 280℃, 300℃, 320℃, 350℃, 380℃, etc.

[0057] In this invention, the polymer film can serve as a drip-proof functional layer, forming a multilayer composite film with at least one other film layer; wherein the drip-proof functional layer is disposed in the innermost layer of the multilayer composite film.

[0058] In this invention, the multilayer composite film can be prepared by co-extruding the material of the dripping functional layer with the materials of other film layers through multiple layers.

[0059] Fourthly, the present invention provides an application of the polymer film according to the third aspect in the field of agriculture or microalgae cultivation.

[0060] Preferably, the polymer film is used for agricultural greenhouse films, open ponds for microalgae cultivation, or closed reactor films.

[0061] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0062] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0063] The long-lasting anti-drip and anti-fogging masterbatch provided by this invention is formulated by compounding anti-drip agents, metal salts, and high molecular weight slow-release agents in specific proportions. During the mixing process, a coordination reaction occurs to form a high molecular weight anti-drip agent, resulting in film materials containing the long-lasting anti-drip and anti-fogging masterbatch exhibiting good anti-drip and anti-fogging effects and a long anti-drip duration. The anti-drip duration obtained from accelerated anti-drip testing can reach up to 30 days, and the actual anti-drip duration can reach 18 months or more; it also has good light transmittance. Moreover, the preparation method of the long-lasting anti-drip and anti-fogging masterbatch provided by this invention fully utilizes existing anti-drip and anti-fogging masterbatch preparation processes and equipment, requiring no additional investment or process modifications, which is more conducive to large-scale application. Attached Figure Description

[0064] Figure 1 The infrared spectra of the long-lasting anti-drip and anti-fogging masterbatch provided in Embodiment 1 and the long-lasting anti-drip and anti-fogging masterbatch provided in Comparative Example 1 are shown. Detailed Implementation

[0065] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0066] All materials used in this invention can be purchased commercially or prepared using conventional methods. Unless otherwise specified, the materials used in this invention are as follows.

[0067] Matrix resin

[0068] Linear low-density polyethylene resin (LLDPE): Jilin Petrochemical DFDA-7042 powder.

[0069] High molecular weight sustained-release agent

[0070] Maleic anhydride-grafted polyethylene: Aladdin P304899.

[0071] Example 1

[0072] This embodiment provides a long-lasting anti-drip and anti-fogging masterbatch, which, by weight, comprises 20 parts of anti-drip agent glyceryl monostearate (GMS), 2 parts of lanthanum stearate, 2 parts of maleic anhydride-grafted polyethylene, and 76 parts of linear low-density polyethylene resin.

[0073] This embodiment provides a method for preparing a long-lasting anti-drip and anti-fogging masterbatch, specifically including the following steps:

[0074] According to the formulation, glyceryl monostearate, lanthanum stearate, maleic anhydride-grafted polyethylene, and linear low-density polyethylene resin were uniformly mixed using a high-speed mixer at a speed of 600 r / min for 15 min. The uniformly mixed raw materials were then added to an internal mixer and kneaded for 10 min at a temperature of 170℃ and a rotor speed of 50 r / min. Finally, the masterbatch obtained from the internal mixing was poured into a twin-screw extruder at a speed of 40 r / min, with the three temperature zones set to 130℃, 150℃, and 170℃ respectively. After extrusion, cooling, and pelletizing, the long-lasting anti-drip and anti-fogging masterbatch was obtained.

[0075] This embodiment also provides a polymer film, which comprises the long-lasting anti-drip and anti-fogging masterbatch and linear low-density polyethylene resin in a mass ratio of 10:90.

[0076] The preparation method of the polymer film includes: melt blending long-lasting anti-drip and anti-fogging masterbatch and linear low-density polyethylene resin, and then extruding and blow molding to obtain the polymer film, i.e., obtaining a long-lasting anti-fogging and anti-drip film. During the extrusion blow molding process, the temperatures of zones one, two, three, and four of the barrel are 165℃, 175℃, 180℃, and 185℃, respectively; the die temperature is 195℃; the screw speed is 50 r / min; and the traction speed is 5 m / min.

[0077] Example 2

[0078] This embodiment provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Example 1 only in that GMS is replaced with an equal mass of octadecyl diethanolamine. All other components, dosages, and preparation methods are the same as in Example 1.

[0079] Example 3

[0080] This embodiment provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Example 1 only in that maleic anhydride-grafted polyethylene is replaced with an equal mass of polyacrylic acid (Sent Chemical 9003-01-4). The remaining components, dosages, and preparation methods are the same as in Example 1.

[0081] Example 4

[0082] This embodiment provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Example 1 only in that lanthanum stearate is replaced with an equal mass of zinc stearate, while the remaining components, dosages, and preparation methods are the same as in Example 1.

[0083] Example 5

[0084] This embodiment provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Example 1 only in that the contents of GMS, lanthanum stearate and maleic anhydride grafted polyethylene are increased to 30 parts, 18 parts and 17 parts respectively, and the content of the matrix resin LLDPE is adjusted to make the total amount 100 parts. The remaining components, dosages and preparation methods are the same as in Example 1.

[0085] Example 6

[0086] This embodiment provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Example 1 only in that the contents of GMS, lanthanum stearate and maleic anhydride grafted polyethylene are increased to 12 parts, 10 parts and 10 parts respectively, and the content of the matrix resin LLDPE is adjusted to make the total amount 100 parts. The remaining components, dosages and preparation methods are the same as in Example 1.

[0087] Example 7

[0088] This embodiment provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Example 1 only in that GMS, lanthanum stearate, and maleic anhydride-grafted polyethylene are replaced with the same mass of sorbitan tristearate, cerium chloride, and ethylene-vinyl alcohol copolymer (Kuraray G110), respectively. The preparation method is the same as in Example 1.

[0089] Example 8

[0090] This embodiment provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Example 1 only in that GMS, lanthanum stearate, and maleic anhydride-grafted polyethylene are replaced with the same mass of lauric diethanolamide, lanthanum acetate, and ethylene-acrylic acid copolymer (Dow Chemical 5980), respectively. The preparation method is the same as in Example 1.

[0091] Example 9

[0092] This embodiment provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Embodiment 1 only in that the long-lasting anti-drip and anti-fogging masterbatch also includes 4 parts of silicon dioxide (SiO2), and the content of the matrix resin LLDPE is adjusted to make the total amount 100 parts. The remaining components, dosages and preparation methods are the same as in Embodiment 1.

[0093] Example 10

[0094] This embodiment provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Example 1 only in that lanthanum stearate is replaced with an equal mass of zirconium ethoxide, while the remaining components, dosages, and preparation methods are the same as in Example 1.

[0095] Comparative Example 1

[0096] This comparative example provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Example 1 only in that the long-lasting anti-drip and anti-fogging masterbatch does not contain lanthanum stearate and maleic anhydride-grafted polyethylene. The remaining components, dosages, and preparation methods are the same as in Example 1.

[0097] Comparative Example 2

[0098] This comparative example provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Example 1 only in that lanthanum stearate is not added to the long-lasting anti-drip and anti-fogging masterbatch, while the other components, dosages, and preparation methods are the same as in Example 1.

[0099] Comparative Example 3

[0100] This comparative example provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Example 1 only in that maleic anhydride-grafted polyethylene is not added to the long-lasting anti-drip and anti-fogging masterbatch. The remaining components, dosages, and preparation methods are the same as in Example 1.

[0101] Comparative Example 4

[0102] This comparative example provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Example 1 only in that 2 parts of maleic anhydride-grafted polyethylene are replaced with 4 parts of silicon dioxide (SiO2), and the content of the matrix resin LLDPE is adjusted so that the total amount is 100 parts. The remaining components, dosages, and preparation methods are the same as in Example 1.

[0103] Comparative Example 5

[0104] This comparative example provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Example 1 only in that 2 parts of maleic anhydride-grafted polyethylene are replaced with 7 parts of kaolin, and the content of the matrix resin LLDPE is adjusted so that the total amount is 100 parts. The remaining components, dosages, and preparation methods are the same as in Example 1.

[0105] Comparative Example 6

[0106] This comparative example provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Example 1 only in that the mass of the lanthanum stearate is 25 parts, and the content of the matrix resin LLDPE is adjusted to make the total amount 100 parts. The remaining components, dosages, and preparation methods are the same as in Example 1.

[0107] Comparative Example 7

[0108] This comparative example provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Example 1 only in that the mass of the lanthanum stearate is 0.5 parts, and the content of the matrix resin LLDPE is adjusted to make the total amount 100 parts. The remaining components, dosages, and preparation methods are the same as in Example 1.

[0109] Comparative Example 8

[0110] This comparative example provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Example 1 only in that the mass of the maleic anhydride-grafted polyethylene is 25 parts, and the content of the matrix resin LLDPE is adjusted to make the total amount 100 parts. The remaining components, dosages, and preparation methods are the same as in Example 1.

[0111] Comparative Example 9

[0112] This comparative example provides a long-lasting anti-drip and anti-fogging masterbatch, which differs from Example 1 only in that the mass of the maleic anhydride-grafted polyethylene is 0.5 parts, and the content of the matrix resin LLDPE is adjusted to make the total amount 100 parts. The remaining components, dosages, and preparation methods are the same as in Example 1.

[0113] Unless otherwise specified, the polymer films provided in other embodiments and comparative examples differ from the polymer films provided in Example 1 only in that the long-lasting anti-drip and anti-fogging masterbatch is replaced with an equal mass of the long-lasting anti-drip and anti-fogging masterbatch provided in the corresponding embodiments and comparative examples. Other components, dosages, and preparation methods are the same as in Example 1.

[0114] Performance testing

[0115] (1) Accelerated dripping test: Referring to the accelerated dripping test in standard GB / T 4455-2019, a film with a length of 45 cm, a width of 45 cm, and a thickness of about 0.12 mm was placed in a standard environment of (23±2)℃ for no less than 4 hours. Then, the film was placed in a dripping tester filled with two-thirds water (preheated at 60℃ for 30 minutes), and a pressure plate was placed on top. The tip of the pressure hammer was aligned with the center of the film, and the hose clamp was tightened. At this time, the angle between the film surface and the horizontal plane was 15°, forming a sealed environment. The time from the start of the test to the first drop of water collected at the lowest point of the film falling is the initial dripping time. Three groups of samples were recorded, and the average value was taken. When the area of ​​the droplets on the film surface exceeds 1 / 3 of the test film surface, the dripping performance is considered to have failed. The total time from the initial dripping to the end is regarded as the dripping duration of the film, that is, the accelerated dripping duration.

[0116] The actual dripping duration is calculated based on factory experience; one day of accelerated dripping duration corresponds to approximately 15 days of actual dripping duration.

[0117] (2) Light transmittance test: According to standard GB / T 2410-2008, the prepared film sample was placed on the measuring port of the haze meter for measurement to obtain the light transmittance of the sample. Each sample was measured 3 times and the average value of the result was taken.

[0118] In addition, Fourier transform infrared spectroscopy was used to test the long-lasting anti-drip and anti-fogging masterbatch provided in Example 1 and the long-lasting anti-drip and anti-fogging masterbatch provided in Comparative Example 1. The results are as follows: Figure 1As shown in the comparison, it was found that lanthanum stearate undergoes a coordination reaction with the dripping agent GMS to form a complex.

[0119] The specific test results are shown in Table 1.

[0120] Table 1

[0121]

[0122] As shown in Table 1, the anti-drip and anti-fogging film prepared by the long-lasting anti-drip masterbatch provided by the present invention has good anti-drip and anti-fogging effect and a long anti-drip duration; the anti-drip duration obtained by accelerated anti-drip test is ≥12 days, the actual anti-drip duration is ≥180 days, and it can even achieve the effect of anti-drip duration obtained by accelerated anti-drip test is ≥26 days and the actual anti-drip duration is ≥390 days.

[0123] As can be seen from Comparative Examples 1 to 3, the long-lasting anti-drip and anti-fogging masterbatch lacks metal salts and / or high molecular weight slow-release agents, resulting in a significantly shortened anti-drip duration of the polymer film.

[0124] As can be seen from Comparative Examples 4 and 5, compared with the addition of inorganic slow-release agents such as silica and kaolin to achieve a slow-release effect through physical adsorption, the long-lasting anti-fogging masterbatch provided by the present invention has a better slow-release effect and a longer drip retention period.

[0125] As can be seen from Example 1 and Comparative Examples 6-9, when the content of the metal salt or high molecular weight sustained-release agent is not within a specific range, the dripping duration of the obtained polymer film is significantly shortened.

[0126] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A long-lasting anti-drip and anti-fogging masterbatch, characterized in that, By weight, the long-lasting anti-drip and anti-fogging masterbatch comprises 40-90 parts of matrix resin, 10-40 parts of anti-drip agent, 1-20 parts of metal salt and 1-20 parts of high molecular weight slow-release agent.

2. The long-lasting anti-drip and anti-fogging masterbatch according to claim 1, characterized in that, The matrix resin includes at least one of polyethylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, polypropylene, polyolefin elastomer, polycarbonate, polyethylene terephthalate, and polylactic acid.

3. The long-lasting anti-drip and anti-fogging masterbatch according to claim 1 or 2, characterized in that, The dripping agent includes at least one of polyol fatty acid ester dripping agents, amine dripping agents, polyoxyethylene ether dripping agents, ionic dripping agents, and organoboron dripping agents; Preferably, the polyol fatty acid ester dripping agent includes at least one of the following: glyceryl monostearate, sorbitan monostearate, sorbitan monooleate, glyceryl monooleate, polyglyceryl stearate, polyglyceryl oleate, pentaerythritol monostearate, pentaerythritol oleate, mannitol monooleate, sucrose monolaurate, sucrose dilaurate, dehydrated sorbitan monooleate, pentaerythritol difatty acid ester, sorbitan monopalmitate, xylitol monostearate, polyglycerol laurate, and dioctyl adipate. Preferably, the amine dripping agent comprises at least one of N,N-dihydroxyethyloctadecylamine, octadecyl diethanolamine, coconut oil diethanolamide, stearic acid diethanolamide, oleic acid diethanolamide, lauric acid diethanolamide, coconut oil monoethanolamide, stearic acid monoethanolamide, oleic acid monoethanolamide, lauric acid monoethanolamide, coconut oil-based triethanolamine, and palmitic acid diethanolamide; Preferably, the polyoxyethylene ether-based anti-dripping agent comprises at least one of alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, fatty alcohol polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether, castor oil polyoxyethylene ether, polyoxyethylene alkyl ether, alkylphenol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, alkylphenol polyoxyethylene ether sulfate, alkylphenol polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether carboxylate, fatty amine polyoxyethylene ether, fatty alcohol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether sulfate, arylphenol polyoxyethylene ethers, and alkylphenol polyoxyethylene ether carboxylate. Preferably, the ionic dripping agent comprises at least one of lignin sulfonate, alkylbenzene sulfonate, α-olefin sulfonate, fatty alcohol polyoxyethylene ether sulfonate, stearoyl lactate, oleic acid fatty acid salt, and lauric acid fatty acid salt; Preferably, the organoboron-based dripping agent comprises at least one of glyceryl monostearate borate, triethanolamine borate, sorbitan borate, pentaerythritol borate, polyglyceryl borate, diethanolamide borate, ethoxylated alkylamine borate, polyol ethoxylated borate, glyceryl distearate, and dioleopropylene borate.

4. The long-lasting anti-drip and anti-fogging masterbatch according to any one of claims 1 to 3, characterized in that, The metal salts include organometallic salts and / or inorganic metal salts; Preferably, the organometallic salt includes at least one of carboxylates, organic carbonates, organic sulfonates, organic borates, organic phosphates, alkoxides, acetylene salts, cyanides, porphyrin salts, and metal salts containing carbocations. Preferably, the carboxylate includes fatty acid salts and / or aromatic acid salts with ≥2 carbon atoms, more preferably including at least one of stearate, acetate, oleate, and benzoate; Preferably, the inorganic metal salt includes at least one selected from chloride, nitrate, carbonate, phosphate, nitrite, sulfate, sulfite, borate, sulfide, cyanide, bromide, fluoride, and bicarbonate. Preferably, the metal ions in the metal salt include La. 3+ Ce 3+ Eu 3+ Eu 2+ Yb 3+ Gd 3+ 、Tb 3+ 、Sm 3+ Dy 3+ 、Nd 3+ Ho 3+ Er 3+ Tm 3+ Pr 3+ Zn 2+ Cr 3+ Mn 2+ Co 3+ Ni 3+ Au 3+ Fe 2+ Fe 3+ Cu 2+ Mg 2+ Ba 2+ Ca 2+ Al 3+ At least one of them.

5. The long-lasting anti-drip and anti-fogging masterbatch according to any one of claims 1 to 4, characterized in that, The high molecular weight sustained-release agent contains a coordinating group, which includes at least one of the following: hydroxyl, carboxyl, acid anhydride, sulfonic acid, β-diketone, amino, amide, imidazole, pyridyl, catechol, and thiol. Preferably, the high molecular weight sustained-release agent comprises at least one of maleic anhydride-grafted polyethylene, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, oxidized polyethylene wax, carboxyl-terminated polyethylene wax, glycidyl methacrylate-grafted polyethylene, glycidyl methacrylate-grafted polypropylene, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl alcohol copolymer, polystyrene sulfonic acid, polyvinylpyrrolidone, chitosan, tannic acid, polyacrylamide, polyethyleneimine, polyethylene glycol, polyvinylpyridine, vinylimidazole-grafted polyethylene, polydopamine, and thiol-modified polyolefins.

6. The long-lasting anti-drip and anti-fogging masterbatch according to any one of claims 1 to 5, characterized in that, The long-lasting anti-drip and anti-fogging masterbatch also includes 1 to 10 parts of other additives; Preferably, the other additives include at least one of functional fillers, lubricants, coupling agents, antioxidants, antistatic agents, plasticizers, light stabilizers, flame retardants, and compatibilizers.

7. A method for preparing a long-lasting anti-drip and anti-fogging masterbatch according to any one of claims 1 to 6, characterized in that, The preparation method includes the following steps: The base resin, anti-dripping agent, metal salt, high molecular weight slow-release agent, and other optional additives are mixed, and then subjected to intensive mixing, melt extrusion, and granulation to obtain the long-lasting anti-dripping and anti-fogging masterbatch.

8. The preparation method according to claim 7, characterized in that, The mixing speed is 100~5000 r / min, and the mixing time is 1~100 min; Preferably, the mixing temperature is 50~300℃, the mixing time is 1~50 min, and the mixing speed is 10~200 r / min; Preferably, the temperature of the melt extrusion is 50~400℃, and the rotation speed of the melt extrusion is 10~200 r / min.

9. A polymer film, characterized in that, The polymer film includes the long-lasting anti-drip and anti-fogging masterbatch as described in any one of claims 1 to 6; Preferably, the polymer film further includes a film-forming resin.

10. The application of the polymer film according to claim 9 in the field of agriculture or microalgae cultivation; Preferably, the polymer film is used for agricultural greenhouse films, open ponds for microalgae cultivation, or closed reactor films.

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