CN109673334B - Heat-preservation, aging-resistant and fog-dissipation agricultural greenhouse film and preparation method thereof - Google Patents

Heat-preservation, aging-resistant and fog-dissipation agricultural greenhouse film and preparation method thereof Download PDF

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CN109673334B
CN109673334B CN201910132494.1A CN201910132494A CN109673334B CN 109673334 B CN109673334 B CN 109673334B CN 201910132494 A CN201910132494 A CN 201910132494A CN 109673334 B CN109673334 B CN 109673334B
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parts
layer
resistant
master batch
aging
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CN109673334A (en
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卞希惠
魏玉强
李承阳
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Jiangsu Zhixin Plastic Technology Co ltd
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Jiangsu Zhixin Plastic Technology Co ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/14—Greenhouses
    • A01G9/1438—Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/552—Fatigue strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2410/00—Agriculture-related articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/267—Magnesium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Soil Sciences (AREA)
  • Environmental Sciences (AREA)
  • Greenhouses (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to the field of agricultural greenhouse films, in particular to a heat-insulating, ageing-resistant and fog-dissipating agricultural greenhouse film and a preparation method thereof. The agricultural greenhouse film comprises a basic film layer and a coating layer, wherein the basic film layer consists of an inner layer, a middle layer, an outer layer and an outer layer, and the layers are sequentially stacked from the inner layer to the outer layer. The agricultural greenhouse film prepared by the invention has the functions of heat preservation, aging resistance and fog dissipation, and is particularly characterized in that the agricultural greenhouse film has better coating efficiency, can improve the fog drop reduction effect of the greenhouse film, improve the light transmittance, improve the aging resistance when pesticides containing chlorine, sulfur and the like are used, is beneficial to the photosynthesis of crops, reduces the crop diseases, and is suitable for overwintering cultivation of various leaf vegetables, flowers and fruits in a sunlight greenhouse in various large and medium arched sheds and sunlight greenhouses.

Description

Heat-preservation, aging-resistant and fog-dissipation agricultural greenhouse film and preparation method thereof
Technical Field
The invention belongs to the field of agricultural greenhouse films, and particularly relates to a heat-insulating, ageing-resistant and fog-dissipating agricultural greenhouse film and a preparation method thereof.
Background
The greenhouse is one of important facilities of modern agriculture, and changes the dependence of the traditional planting method on natural conditions. Effectively improves the yield and the quality of crops in unit area and relatively reduces the production cost. Therefore, the greenhouse planting technology is gradually replacing the traditional planting technology in agriculture and planting industry and is accepted by people, and the covered area of the greenhouse film in China exceeds 16000km according to statistics2The annual using amount of the greenhouse film is about 1500kt/a, the annual updating demand is about 700kt, and the annual updating demand is increased gradually. A huge industry has been formed. Production ofThe agricultural greenhouse film is mainly made of polyethylene resin, and when the common polyethylene greenhouse film is used, a layer of white reflective water drops are condensed on the inner surface of the greenhouse film, so that the light transmission is influenced; moreover, water drops drip, so that the humidity in the greenhouse is increased, and the crops are easy to suffer from diseases; the water drops drop on the crops and are easy to rot, thereby causing the reduction of yield. The problem of dripping water in the use of the polyethylene greenhouse film is solved by two methods: one is an internal addition method, which is to mix and blow-mold a substance with surface activity and polyethylene resin to prepare a dripping greenhouse film, wherein the hydrophilic end migrates to the surface of the film, so that water drops are changed into a water film to achieve the effect of preventing water drops; the other method is an external coating method, namely, the dripping agent is coated on the surface of the film to ensure that the film has hydrophilicity so as to achieve the effect of preventing dripping.
The flow drop fog dissipation duration of the flow drop fog dissipation greenhouse film prepared by the internal addition method is short, generally about 3-4 months, and the growth requirement of crops cannot be met. The coating type dripping fog reduction shed film has longer lasting period of dripping fog dissipation, generally more than 8 months. The preparation method is to directly coat a layer of dripping fog-reducing agent on the surface of the polyethylene greenhouse film, and the polyethylene and the coating type dripping fog-reducing agent have great polarity difference, so that the coating is difficult and the adhesion between the coating and the polyethylene surface is poor, so that the greenhouse film has short dripping fog-reducing lasting period and can not meet the requirements. Therefore, the invention aims to solve the problems of poor adhesion between the coating liquid and the base film layer, low coating efficiency and influence on fog and drop reducing effect, and simultaneously solves the problems of short acting period caused by gradual loss of the fog and drop reducing function due to continuous migration of auxiliary agent molecules such as the drop reducing agent, the fog and the like to the surface of the film and drop loss along with the water drop.
Disclosure of Invention
In order to solve the problems, the invention provides a heat-insulating, ageing-resistant and fog-dissipating agricultural greenhouse film in a first aspect, which comprises a base film layer and a coating layer, wherein the base film layer consists of an inner layer, a middle layer, an outer layer and an outer layer, and the layers are stacked from the inner layer to the outer layer in sequence.
As a preferred technical solution, the base film layer comprises, by weight: 10-15 parts of an inner layer, 8-12 parts of an inner two layer, 15-20 parts of a middle layer, 15-20 parts of an outer two layer and 20-30 parts of an outer layer.
As a preferred technical scheme, the inner layer comprises the following components in parts by weight: 40-70 parts of mLLDPE, 20-30 parts of LDPE and 5-10 parts of anti-ultraviolet aging resistant master batch.
As a preferred technical scheme, the inner two layers comprise the following components in parts by weight: 30-50 parts of mLLDPE-1, 20-40 parts of LDPE-1 and 3-8 parts of ultraviolet-resistant and aging-resistant master batch.
As a preferred technical scheme, the middle layer comprises the following components in parts by weight: 40-70 parts of EVA (ethylene-vinyl acetate), 30-45 parts of LDPE-2 and 5-10 parts of heat-insulating master batch.
As a preferred technical scheme, the outer two layers comprise the following components in parts by weight: 30-40 parts of mLLDPE-2, 20-30 parts of LDPE-2, 5-10 parts of ultraviolet-resistant and aging-resistant master batch and 1-3 parts of dustproof master batch.
As a preferred technical solution, the outer layer comprises, in parts by weight: 50-70 parts of mLLDPE-3, 10-20 parts of LDPE-3, 5-10 parts of ultraviolet-resistant and aging-resistant master batch and 3-7 parts of dustproof master batch.
As a preferable technical scheme, the coating layer is formed by coating a coating liquid, and the coating liquid comprises the following components in parts by weight: 3-5 parts of functional additive, 0.1-0.5 part of antifogging agent, 0.5-1 part of dripping agent, 0.5-1.5 parts of surfactant and 35-55 parts of water.
As a preferable technical scheme, the ultraviolet-resistant and aging-resistant master batch comprises the following components in parts by weight: 10-20 parts of LDPE, 0.1-2 parts of hindered amine light stabilizer, 1-3 parts of ultraviolet absorber, 3-5 parts of composite antioxidant, 0.1-0.5 part of functional assistant and 0.3-0.8 part of slipping agent.
As a preferred technical scheme, the heat-preservation master batch comprises the following components in parts by weight: 20-30 parts of LDPE, 15-20 parts of transparent heat-insulating agent, 3-5 parts of basic magnesium carbonate and 1-1.5 parts of PPA (poly (phenylene benzobisoxazole)) assistant.
Has the advantages that: the agricultural greenhouse film prepared by the invention has the functions of heat preservation, aging resistance and fog dissipation, and is particularly characterized in that the agricultural greenhouse film has better coating efficiency, can improve the fog drop reduction effect of the greenhouse film, improve the light transmittance, improve the aging resistance when pesticides containing chlorine, sulfur and the like are used, has good drop property, can form water drops which flow down along the film, has long drop duration, quick temperature rise, strong heat preservation, obvious yield increase effect and strong weather resistance and wind resistance, has better fog prevention function and light transmittance, can reduce or eliminate fog in the greenhouse, is beneficial to photosynthesis of crops, reduces crop diseases, and is suitable for overwintering cultivation of various leaf vegetables, flowers and plants in various large and medium-sized arched sheds and sunlight greenhouses for sunlight greenhouse cultivation.
Detailed Description
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.
The words "preferred", "more preferred", and the like, in the present invention refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to solve the problems, the invention provides a heat-insulating, ageing-resistant and fog-dissipating agricultural greenhouse film in a first aspect, which comprises a base film layer and a coating layer, wherein the base film layer consists of an inner layer, a middle layer, an outer layer and an outer layer, and the layers are stacked from the inner layer to the outer layer in sequence.
In a preferred embodiment, the base film layer comprises, in parts by weight: 10-15 parts of an inner layer, 8-12 parts of an inner two layer, 15-20 parts of a middle layer, 15-20 parts of an outer two layer and 20-30 parts of an outer layer.
< inner layer >
In a preferred embodiment, the inner layer of the present invention comprises, in parts by weight: 40-70 parts of mLLDPE, 20-30 parts of LDPE and 5-10 parts of anti-ultraviolet aging resistant master batch.
(mLLDPE)
The mLLDPE is metallocene linear low-density polyethylene, has the characteristics of narrow relative molecular mass distribution and uniform comonomer distribution, and has the advantages of high toughness, good transparency, pollution resistance, puncture resistance, wide heat sealing temperature range and the like, so that the mLLDPE is widely applied.
The mLLDPE of the inner layer is not particularly limited in the present invention and may be various mLLDPE conventionally used in the art and may be commercially available, for example commercially available mLLDPE including but not limited to products available from exxonmobil under the trade mark 1327 CA.
(LDPE)
The LDPE, namely the low-density polyethylene, also called high-pressure polyethylene, is a plastic material, is suitable for various molding processes of thermoplastic molding and processing, and has good molding processability.
The LDPE of the inner layer is not particularly limited in the present invention and may be any of the various LDPE's conventionally used in the art and may be obtained commercially, for example, commercially available LDPE's include, but are not limited to, products available from Exxon Mobil under the trademark LD171 BA.
(anti-ultraviolet aging resistant master batch)
In a preferred technical scheme, the ultraviolet-resistant and aging-resistant master batch comprises the following components in parts by weight: 10-20 parts of LDPE, 0.1-2 parts of hindered amine light stabilizer, 1-3 parts of ultraviolet absorber, 3-5 parts of composite antioxidant, 0.1-0.5 part of functional assistant and 0.3-0.8 part of slipping agent.
LDPE
The LDPE, namely the low-density polyethylene, also called high-pressure polyethylene, is a plastic material, is suitable for various molding processes of thermoplastic molding and processing, and has good molding processability.
The LDPE in the ultraviolet-resistant and aging-resistant master batch is not particularly limited, and can be various LDPE which is conventionally used in the field and can be obtained commercially, for example, the commercially available LDPE includes but is not limited to the product which is obtained from Exxon Mobil and has the trademark of LD171 BA.
Hindered amine light stabilizers
The hindered amine light stabilizer is an organic amine compound with steric hindrance. The hindered amine has good inhibition effect on the photo-oxidative degradation reaction of high polymers and organic compounds, and is a light stabilizer with excellent performance.
Preferably, the hindered amine light stabilizer in the anti-ultraviolet aging-resistant master batch is selected from bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate, tris (1,2,2,6, 6-pentamethyl-4-piperidyl) phosphite, poly [ [6- [ (1,1,3, 3-tetramethylbutyl) amine ] -1,3, 5-triazine-2, 4-diyl ] [ (2,2,6, 6-tetramethyl-4-piperidyl) imine ] -1, 6-diadipyl [ (2,2,6, 6-tetramethyl-4-piperidine) imine ] ] ].
In a preferred embodiment, the hindered amine light stabilizer in the UV resistant masterbatch of the present invention is TH9944, available from Zheng Akme chemical Co., Ltd.
Ultraviolet absorber
The ultraviolet absorbent is a light stabilizer which is most widely applied at present, can absorb the ultraviolet part in sunlight and a fluorescent light source, and does not change. They can be classified into salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, triazines, etc. according to their structures.
Preferably, the ultraviolet absorber in the ultraviolet resistant and aging resistant master batch is selected from one or more of benzophenones and benzotriazoles.
As examples of benzophenones, include, but are not limited to: 2-hydroxy-4- (3-methacryloxy-2-hydroxypropoxy) benzophenone, 2- (4-benzoyl-3-hydroxyphenoxy) ethyl 2-acrylate, 2-hydroxy-4-acryloyloxyethoxy benzophenone.
As examples of benzotriazoles, include, but are not limited to: one or more of [2- (2-hydroxy-4-methacryloxyphenyl) benzotriazole ], RUVA-93, [2- (2-hydroxy-4-acryloxyphenyl) benzotriazole ], 2- [ 2-hydroxy-5- [2- (methacryloyloxy) ethyl ] phenyl ] -2H-benzotriazole, 2 (2-hydroxy-4-methacryloxyphenyl) 5-chloro-2H-benzotriazole, and 2 (2-hydroxy-4-allylphenyl) 5-chloro-2H-benzotriazole.
In a preferred embodiment, the ultraviolet absorbent in the ultraviolet resistant and aging resistant master batch is UV-416, which is purchased from Xiangyang Furun chemical Co.
Composite antioxidant
The antioxidants of the present invention are a class of chemicals which, when present in only small amounts in a polymer system, retard or inhibit the progress of the polymer oxidation process, thereby retarding polymer aging and extending its useful life.
Preferably, the composite antioxidant in the ultraviolet-resistant and aging-resistant master batch is selected from at least two of amine antioxidants, ester antioxidants and phenol antioxidants; wherein the amine antioxidant is selected from hindered amine antioxidants; the ester antioxidant is selected from phosphite ester antioxidants; the phenolic antioxidant is selected from hindered phenolic antioxidants.
Examples of amine antioxidants include, but are not limited to: antioxidant 445, hindered amine 5057, hindered amine 944.
Examples of phenolic antioxidants include, but are not limited to: BHT, antioxidant 1010, antioxidant 1076, antioxidant DLTDP, antioxidant 1135 and antioxidant 245.
Examples of phosphite antioxidants include, but are not limited to: antioxidant 168, antioxidant 3010, and antioxidant 626.
In a preferred embodiment, the antioxidant in the ultraviolet-resistant and aging-resistant master batch is antioxidant 1010 and antioxidant 168, and the weight ratio of the antioxidant 1010 to the antioxidant 168 is 1: 1 is obtained by compounding.
Functional auxiliary agent
In some embodiments, the functional additive in the aging-resistant dripping master batch is prepared from L-lysine triisocyanate, behenyl alcohol and a functional monomer.
In a more preferred embodiment, the functional monomers of the present invention are propylene diamine and imidazoline caproate.
In some embodiments, the functional additives of the present invention are prepared by steps comprising: adding L-lysine triisocyanate into a reaction kettle provided with a thermometer and a reflux device, diluting with acetone, dropwise adding behenyl alcohol and an acetone solution containing dibutyltin dilaurate serving as a catalyst, stirring at 55 ℃ for reacting for 1-2 hours, dropwise adding a functional monomer, and reacting for 2-3 hours under heat preservation to obtain the functional auxiliary agent.
In a preferred embodiment, the step of preparing the hexanoic acid imidazoline of the present invention comprises: adding caproic acid and diethylenetriamine into a three-neck flask at the temperature of 80 ℃, adding toluene, stirring and refluxing for 30min, then heating to 140 ℃ for reaction for 1 hour, then heating to 180 ℃ for reaction for 2 hours, cooling reactants to 110 ℃ when no water drop occurs in a condensation tube, distilling out the toluene and the excessive diethylenetriamine, and cooling to room temperature to obtain the hexanoic acid imidazoline monomer.
In a preferred embodiment, the molar ratio of L-lysine triisocyanate to behenyl alcohol in the process of preparing the functional additive according to the present invention is 1: (1.8-2.2); the molar ratio of the L-lysine triisocyanate to the functional monomer is 1: (0.5 to 1.2); the functional monomer is propane diamine and caproic acid imidazoline, and the weight ratio of the propane diamine to the caproic acid imidazoline is (1-3): 1; wherein the CAS of the L-lysine triisocyanate is 69878-18-8, and the CAS of the behenyl alcohol is 661-19-8.
Slipping agent
The slipping agent is used for enhancing the mechanical stirring resistance and shearing force resistance, so that the material is plumper, slippery, fine, comfortable and rich in silky feeling, and can prevent a series of problems of edge sticking, mildew, deterioration, odor and the like when stacked at a high temperature, thereby prolonging the service life of the product.
Preferably, the slip agent in the ultraviolet-resistant and aging-resistant master batch is selected from one or more of oleamide, erucamide and ethylene bis stearamide.
In a preferred embodiment, the slip agent in the ultraviolet-resistant and aging-resistant masterbatch is erucamide and diethenyloleamide in a weight ratio of 1: (0.5-1) compounding.
The inventor of the application finds that the corona and coating process of the greenhouse film can be well improved by regulating and controlling the components and the weight proportion of the slipping agent, the adhesive force of the coating liquid to the basic film layer is improved, and the fog and droplet reduction effect of the greenhouse film is improved. The possible reason is that because erucamide and diethenyloleamide have polar amide groups and non-polar flexible fatty chains at the same time, polar groups in erucamide and diethenyloleamide migrate to the surface of the membrane due to intermolecular force, compatibility and the like between the erucamide and diethenyloleamide and polyolefin materials, an elastic layer with stronger polarity is formed on the surface of the membrane, and the strong polarity characteristic is also beneficial to the adsorption of components such as functional additives with polar groups such as hydroxyl groups, amino groups and the like in the coating liquid to a basic membrane layer. The migration speed of the two components is accelerated under the synergistic effect of the symmetrical structure of the diethenyloleamide and the erucamide, and the loss along with the water in the greenhouse is avoided, so that the fog and droplet reduction effect of the double-component erucamide is improved.
< inner two layers >
In a preferred embodiment, the inner two layers of the present invention comprise, in parts by weight: 30-50 parts of mLLDPE-1, 20-40 parts of LDPE-1 and 3-8 parts of ultraviolet-resistant and aging-resistant master batch.
(mLLDPE-1)
The mLLDPE is metallocene linear low-density polyethylene, has the characteristics of narrow relative molecular mass distribution and uniform comonomer distribution, and has the advantages of high toughness, good transparency, pollution resistance, puncture resistance, wide heat sealing temperature range and the like, so that the mLLDPE is widely applied.
The preferred density of the mLLDPE-1 is 0.919-0.935 g/cm3The mLLDPE of (a) can be obtained commercially, for example, commercially available mLLDPE-1 includes, but is not limited to, products available from Exxon Mobil under the trade designations 1327CA, 1327ED, having a density of 0.927g/cm3。
(LDPE-1)
The LDPE, namely the low-density polyethylene, also called high-pressure polyethylene, is a plastic material, is suitable for various molding processes of thermoplastic molding and processing, and has good molding processability.
The preferred density of the LDPE-1 is 0.912-0.918 g/cm3For example, commercially available LDPE-1 includes, but is not limited to, the product available from Exxon Mobil under the designation 350D65, having a density of 0.917g/cm3。
(anti-ultraviolet aging resistant master batch)
The ultraviolet-resistant and aging-resistant master batches of the inner two layers are the same as the ultraviolet-resistant and aging-resistant master batches of the inner layer.
< middle layer >
In a preferred embodiment, the middle layer of the present invention comprises, in parts by weight: 40-70 parts of EVA (ethylene-vinyl acetate), 30-45 parts of LDPE-2 and 5-10 parts of heat-insulating master batch.
(EVA)
The EVA is prepared by copolymerizing ethylene and caproic acid, and has the Chinese cultural name: ethylene-vinyl caproate copolymer (ethylene-vinyl acetate copolymer), the content of general ethylene caproate (VA) is 5% -40%, compared with Polyethylene (PE), EVA because introduces vinyl caproate monomer in the molecular chain, thus has reduced the high degree of crystallinity, has improved toughness, impact resistance, filler intermiscibility and heat sealability, is used in fields such as foaming shoe material, functional shed membrane, packaging mould, hot melt adhesive, wire and cable and toy extensively.
The content of VA in the EVA is preferably 15-25 wt%, and the melt index at 190 ℃ and 2.16kg is 0.5-2 g/10 min; more preferably, the content of VA in the EVA is preferably 16-20 wt%, and the melt index at 190 ℃ under 2.16kg is 0.5-1 g/10 min; commercially available EVA, for example, includes but is not limited to 1807V product available from Seranis, USA, with a VA content of 18 wt% and a melt index of 0.7g/10 min.
The inventor finds that the VA with specific content in the EVA can cause the polarity and cohesive energy density of the component to be high, and improves the material molecular internal acting force, thereby improving the strength of the greenhouse film and avoiding premature wear and damage of the greenhouse film in the using process. However, the VA content cannot be too high, otherwise incompatible regions and interfaces exist between materials due to the polarity difference between the VA content and other components, and the strength of the greenhouse film is reduced. Secondly, the applicant finds that the content of VA is in the range of 8-18 wt%, which is beneficial to improving the heat preservation effect of the greenhouse film, and the probable reason is that the EVA with specific VA content increases the density of the middle layer of the greenhouse film and reduces heat loss in the greenhouse film on the premise of not influencing the compatibility among various materials, thereby improving the heat preservation effect. In addition, applicants have unexpectedly discovered that the use of EVA with the above specified VA content also helps to prolong the haze reduction, drip reduction effect of the greenhouse film. The possible reason is that the EVA has a relatively compact structure and relatively high density, so that functional additives, dripping agents and other ingredients in the inner two layers are prevented from migrating to the middle layer or the outer layer, and the functional additives are slowly migrated to the inner layer under the extrusion of the EVA component, namely, the functional additives are slowly released, the corresponding effect of the greenhouse film is prevented from disappearing along with the loss of time, and the corresponding effect of the greenhouse film can be fully exerted.
(LDPE-2)
The LDPE, namely the low-density polyethylene, also called high-pressure polyethylene, is a plastic material, is suitable for various molding processes of thermoplastic molding and processing, and has good molding processability.
The optimized density of the LDPE-2 is 0.912-0.935 g/cm3The LDPE of (A) can be obtained commercially, for example commercially available LDPE includes but is not limited to that purchased from Exxon Mobil under the trademark LD171BA and has a density of 0.929g/cm3。
(Heat-insulating Master batch)
In a preferred embodiment, the insulation masterbatch comprises the following components in parts by weight: 20-30 parts of LDPE, 15-20 parts of transparent heat-insulating agent, 3-5 parts of basic magnesium carbonate and 1-1.5 parts of PPA (poly (phenylene benzobisoxazole)) assistant.
LDPE
The LDPE, namely the low-density polyethylene, also called high-pressure polyethylene, is a plastic material, is suitable for various molding processes of thermoplastic molding and processing, and has good molding processability.
The LDPE in the insulation masterbatch is not particularly limited in the invention, can be various LDPE which is conventionally used in the field, and can be obtained commercially, for example, the commercially available LDPE includes but is not limited to the product which is obtained from Exxon Mobil and has the trademark LD171 BA.
Transparent heat-insulating agent
The novel infrared absorbent of the transparent heat-insulating agent can improve the barrier property, the antistatic property, the dustproof property, the weather resistance and the like when being used in an agricultural greenhouse film. Can block infrared rays in a wavelength range of 713 mu m in general, and can shield ultraviolet rays in the whole wavelength range, particularly 200385nm ultraviolet rays, so that the light transmittance of the film is increased.
The transparent heat-insulating agent in the heat-insulating master batch is not particularly limited, and can be various transparent heat-insulating agents which are conventionally used in the field and can be obtained commercially, for example, the commercially available transparent heat-insulating agent comprises but is not limited to a product which is purchased from Shanghai Hexin Fine chemical Co., Ltd and is of the brand number HX-898.
Basic magnesium carbonate
The basic magnesium carbonate is white monoclinic crystal or amorphous powder, is pentatoxic and tasteless, and is stable in air. It is used as excellent filler and reinforcing agent for rubber products, and can be used as heat-insulating, high-temp. resisting, fire-resisting and heat-insulating material.
The basic magnesium carbonate in the heat-preservation master batch is not particularly limited, can be various basic magnesium carbonates conventionally used in the field, and can be obtained commercially.
PPA auxiliary agent
The PPA additive is a polymer processing additive taking a fluorine-containing high-molecular polymer as a basic structure, improves the glossiness of a film in a composite co-extruded film to a certain extent, improves the processability of resin, improves the extrusion efficiency of co-extrusion, and reduces the processing temperature of the resin.
The PPA auxiliary agent in the heat-insulating master batch is not particularly limited, can be various PPA auxiliary agents conventionally used in the field and can be obtained commercially, and the PPA auxiliary agent is purchased from Beijia polymer materials Co., Ltd, Jining, and the brand is F-5.
< outer two layers >
In a preferred embodiment, the outer two layers of the present invention comprise, in parts by weight: 30-40 parts of mLLDPE-2, 20-30 parts of LDPE-2, 5-10 parts of ultraviolet-resistant and aging-resistant master batch and 1-3 parts of dustproof master batch.
(mLLDPE-2)
The mLLDPE is metallocene linear low-density polyethylene, has the characteristics of narrow relative molecular mass distribution and uniform comonomer distribution, and has the advantages of high toughness, good transparency, pollution resistance, puncture resistance, wide heat sealing temperature range and the like, so that the mLLDPE is widely applied.
The preferred density of the mLLDPE-2 is 0.919-0.935 g/cm3The mLLDPE of (a) can be obtained commercially, for example, commercially available mLLDPE-2 includes, but is not limited to, products available from Exxon Mobil under the trade designations 1327CA, 1327ED, having a density of 0.927g/cm3。
(LDPE-2)
The LDPE, namely the low-density polyethylene, also called high-pressure polyethylene, is a plastic material, is suitable for various molding processes of thermoplastic molding and processing, and has good molding processability.
The optimized density of the LDPE-2 is 0.912-0.935 g/cm3The LDPE of (A) can be obtained commercially, for example commercially available LDPE includes but is not limited to that purchased from Exxon Mobil under the trademark LD171BA and has a density of 0.929g/cm3。
(anti-ultraviolet aging resistant master batch)
The ultraviolet-resistant and aging-resistant master batches on the outer two layers are the same as those on the inner layer.
(dustproof masterbatch)
The dustproof master batch can prevent dust adsorption of most plastic products during storage and use, avoids influencing the appearance and performance of a final product, reduces the interference of static charges on a processing process when a film with a large area is processed by adding the dustproof master batch, prevents the normal winding of the film, and improves the processing performance.
The dustproof master batch in the outer two layers is not particularly limited, various dustproof master batches which are conventionally used in the field can be obtained by commercial purchase, and the dustproof master batch in the outer two layers is purchased from Huizzinew material company of Dongguan city.
< outer layer >
In a preferred embodiment, the outer layer of the present invention comprises, in parts by weight: 50-70 parts of mLLDPE-3, 10-20 parts of LDPE-3, 5-10 parts of ultraviolet-resistant and aging-resistant master batch and 3-7 parts of dustproof master batch.
(mLLDPE-3)
The mLLDPE is metallocene linear low-density polyethylene, has the characteristics of narrow relative molecular mass distribution and uniform comonomer distribution, and has the advantages of high toughness, good transparency, pollution resistance, puncture resistance, wide heat sealing temperature range and the like, so that the mLLDPE is widely applied.
The preferred density of the mLLDPE-3 is 0.912-0.918 g/cm3The mLLDPE of (a) can be obtained commercially, for example, commercially available mLLDPE-3 includes, but is not limited to, the product available from Exxon Mobil under the trademark E1012HA, and has a density of 0.912g/cm3。
(LDPE-3)
The LDPE, namely the low-density polyethylene, also called high-pressure polyethylene, is a plastic material, is suitable for various molding processes of thermoplastic molding and processing, and has good molding processability.
The preferred density of the LDPE-3 is 0.912-0.935 g/cm3For example, commercially available LDPE-3 includes, but is not limited to, the product available from Exxon Mobil under the trademark LD171BA, having a density of 0.929g/cm3。
(anti-ultraviolet aging resistant master batch)
The ultraviolet-resistant and aging-resistant master batch of the outer layer is the same as that of the inner layer.
(dustproof masterbatch)
The dustproof master batch of the outer layer is the same as the dustproof master batch of the outer two layers.
< coating layer >
In a preferred embodiment, the coating layer of the present invention is formed by coating a coating liquid, wherein the coating liquid comprises the following components in parts by weight: 3-5 parts of functional additive, 0.1-0.5 part of antifogging agent, 0.5-1 part of dripping agent, 0.5-1.5 parts of surfactant and 35-55 parts of water.
In a more preferred embodiment, the coating liquid is applied in an amount of 12 to 15g/m per square content2。
Functional auxiliary agent
The functional additive in the coating liquid is the same as the functional additive in the ultraviolet-resistant and aging-resistant master batch.
The inventor of the application finds that the drip effect of the greenhouse film can be improved by controlling the selection and the dosage proportion of the monomer components prepared from the functional additives, so that the acting period of the greenhouse film is prolonged, and the fog reducing effect of the greenhouse film can be improved at the same time. The possible reason is that the functional assistant is helpful to improve the activity of the surface of the inner layer of the greenhouse film under the synergistic action of the dripping agent, other components of the master batch and the like, so that water molecules are quickly adsorbed and condensed on the inner surface of the greenhouse film, and simultaneously, the surface tension of the water molecules is reduced, so that the water molecules flow into the ground along the film wall. In addition, the applicant unexpectedly finds that the interaction between the functional assistant and the dripping agent can improve the service life of the greenhouse film, the greenhouse film does not burst even under the condition of a large amount of pesticides containing chlorine, sulfur and the like, and the dripping and fog reducing effects do not disappear in a short time. When pesticides containing chlorine, sulfur and other elements are used in the conventional greenhouse film, the elements can accelerate the precipitation of assistants such as dripping agents and the like and shorten the acting period of fog reduction and dripping effects of the greenhouse film, and the problems are solved under the synergistic action of the functional assistants, the dripping agents and the like in the invention. The probable reason is that amino groups and other groups in the molecules of the functional auxiliary agent are basic to a certain extent, and can be combined with elements such as chlorine, sulfur and the like of pesticide, so that the elements are prevented from damaging light stabilizers, anti-aging agents and the like in the greenhouse film, and the acceleration of the migration speed of related components caused by the degradation of the greenhouse film is avoided.
Fog eliminating agent
The antifogging agent is a surfactant with extremely strong surface activity, and the surface tension of water can be further reduced to 15mN/m by coating the antifogging agent in a greenhouse film, so that the water film is spread into a thinner water layer and flows to the ground more quickly, and the efficiency of absorbing fog drops by the water layer is improved.
The antifogging agent is selected from one or more of polyalcohol fatty acid ester, fluorine antifogging agent and silicon antifogging agent.
Examples of polyol fatty acid esters include, but are not limited to: KF650, la-2, la-6, la8, la18, ly6, ly9, Ts705, Ts600, TST 238.
Examples of fluorine-based antifogging agents include, but are not limited to: AF-38, TF-31, TS 403.
Examples of silicon-based antifogging agents include, but are not limited to: AF-10, AF-31, AF-7000.
In a preferred embodiment, the antifogging agent of the present invention is AF-31, purchased from Pasteur, Germany.
Drip agent
The dripping agent is a surfactant which is an aid for destroying the interfacial tension between water drops and a film and preventing the water drops from forming on the surface. Generally, the surfactant is added in the polymer processing process, so that condensed water drops can be distributed into a continuous transparent thin layer, and the function of the thin layer is to reduce the contact angle between water and the surface of the polymer and prevent the surface from forming water drops.
In a preferred embodiment, the drip-forming agent in the aging-resistant drip-forming concentrate of the present invention is selected from polyol fatty acid esters.
In a more preferred embodiment, the drip-off agent of the present invention is FWD650, available from shanghai' an yi chemical company, ltd.
Surface active agent
The surfactant is a substance which is added in a small amount and can cause the interface state of a solution system of the surfactant to change obviously. Has fixed hydrophilic and lipophilic groups and can be directionally arranged on the surface of the solution. Can be divided into ionic surfactants (including cationic surfactants and anionic surfactants), nonionic surfactants, amphoteric surfactants, complex surfactants, other surfactants and the like.
The surfactant is selected from one or more of anionic surfactant, cationic surfactant, nonionic surfactant and zwitterionic surfactant.
As examples of anionic surfactants, include, but are not limited to: stearic acid and sodium dodecyl benzene sulfonate.
As examples of cationic surfactants, include, but are not limited to: a quaternary ammonium compound.
As examples of amphoteric surfactants, include, but are not limited to: lecithin, amino acid type, betaine type
As examples of nonionic surfactants, include, but are not limited to: alkyl glucoside (APG), fatty acid glyceride, fatty acid sorbitan (span), polysorbate (tween).
In a preferred embodiment, the surfactant provided by the invention is sodium carboxyethyl cellulose and fatty alcohol-polyoxyethylene ether in a weight ratio of (1-2.5): 1 is obtained by compounding.
In the process of research, the inventor of the application finds that the activity of components such as an antifogging agent, a dripping agent and the like in the coating liquid needs to be improved, and the water in the greenhouse cannot be condensed into mist well, and the mist flows into the ground along the interior of the film. The anionic surfactant and the nonionic surfactant can well improve the stability of the coating liquid and improve the adhesion of the coating liquid on the base film layer. In addition, the applicant finds that the adoption of the compound surfactant can help to prolong the dripping and fog-reducing effect of the greenhouse film, and the adoption of the cationic surfactant can influence the coating effect of the coating liquid and easily cause the poor adhesion between the coating layer and the base film layer. The reason for this is probably that the cationic surfactant has a positive charge and repels the cationic groups such as amino groups on the functional additives, etc., and the coating liquid itself has poor stability, and the adhesion to the base film layer is affected by the repulsion between the functional additives, etc., present in a small amount in the base film layer during the coating process. In addition, the cationic surfactant may have strong adsorbability on pesticides with elements such as chlorine and sulfur, and can promote volatilization of the elements such as chlorine and sulfur, so that the capability of the pesticides for providing nutrition to crops and exerting effects is influenced, and the further degradation and aging of the greenhouse film are accelerated. The problems can be solved skillfully by adopting the compound surfactant.
The second aspect of the invention provides a preparation method of the ultraviolet-resistant and aging-resistant master batch, which comprises the following steps: and putting the LDPE, the hindered amine light stabilizer, the ultraviolet absorbent, the composite antioxidant, the functional assistant and the slipping agent into a high-speed mixer, mixing for 10-15 min, transferring to a double-screw extruder for melt extrusion at the extrusion temperature of 150-200 ℃, and performing air cooling to obtain the ultraviolet-resistant and aging-resistant master batch.
The third aspect of the invention provides a preparation method of the heat preservation master batch, which comprises the following steps: and (3) putting the LDPE, the transparent heat-insulating agent, the basic magnesium carbonate and the PPA auxiliary agent into a high-speed mixer, mixing for 10-15 min, transferring to a double-screw extruder, melting and extruding at the extrusion temperature of 150-200 ℃, and air-cooling to obtain the heat-insulating master batch.
The fourth aspect of the invention provides a preparation method of the agricultural greenhouse film, which comprises the following steps: preparing materials according to a production formula, mixing the materials of the inner layer, the inner two layers, the middle layer, the outer two layers and the outer layer uniformly, extruding, compounding the materials to a machine head, blowing, drawing a guide roller to the upper part through a foam stabilizing frame, carrying out corona treatment, carrying out secondary drawing, entering a coating liquid groove to coat a film product, controlling the drawing speed of a coating layer, drying, carrying out tertiary drawing, carrying out fourth drawing after passing through the guide roller, folding and rolling to obtain the heat-preservation, aging-resistant and fog-dissipation agricultural greenhouse film.
The present invention will now be described in detail by way of examples, and the starting materials used are commercially available unless otherwise specified.
Examples
Example 1
Embodiment 1 provides a heat-insulating, aging-resistant and fog-dissipating agricultural greenhouse film, which comprises a basic film layer and a coating layer, wherein the basic film layer consists of an inner layer, a middle layer, an outer layer and an outer layer, and the layers are sequentially stacked from the inner layer to the outer layer; wherein the base film layer comprises the following components in parts by weight: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
The inner layer comprises the following components in parts by weight: 40 parts of mLLDPE, 20 parts of LDPE and 5 parts of ultraviolet-resistant and aging-resistant master batch.
The sources of the components of the inner layer are as follows:
the mLLDPE of the inner layer is a product purchased from Exxon Mobil and the grade is 1327 CA;
the LDPE of the inner layer is a product purchased from Exxon Mobil and having the trademark LD171 BA;
wherein, by weight, the anti-ultraviolet aging-resistant master batch comprises: 10 parts of LDPE, 0.1 part of hindered amine light stabilizer, 1 part of ultraviolet absorber, 3 parts of composite antioxidant, 0.1 part of functional assistant and 0.3 part of slipping agent;
wherein the LDPE in the ultraviolet-resistant aging-resistant master batch is a product purchased from Exxon Mobil and having the trademark LD171 BA;
the hindered amine light stabilizer in the ultraviolet-resistant and aging-resistant master batch is TH9944 purchased from Zhengzhou Akhm chemical Co., Ltd;
the ultraviolet absorbent in the ultraviolet-resistant and aging-resistant master batch is UV-416, and is purchased from Xiangyang Furun chemical Co., Ltd;
the antioxidant in the uvioresistant aging-resistant master batch is antioxidant 1010 and antioxidant 168 according to the weight ratio of 1: 1, compounding to obtain;
the functional auxiliary agent in the ultraviolet-resistant and aging-resistant master batch is prepared from L-lysine triisocyanate, behenyl alcohol and a functional monomer; wherein the functional monomer is propane diamine and imidazoline caproate;
wherein the preparation steps of the functional auxiliary agent comprise: adding L-lysine triisocyanate into a reaction kettle provided with a thermometer and a reflux device, diluting with acetone, then dropwise adding behenyl alcohol and an acetone solution containing a catalyst dibutyltin dilaurate, stirring at 55 ℃ for reacting for 2 hours, then dropwise adding a functional monomer, and carrying out heat preservation reaction for 2 hours to obtain the functional auxiliary agent;
the preparation method of the hexanoic acid imidazoline comprises the following steps: adding caproic acid and diethylenetriamine into a three-neck flask at the temperature of 80 ℃, adding toluene, stirring and refluxing for 30min, then heating to 140 ℃ for reaction for 1 hour, then heating to 180 ℃ for reaction for 2 hours, cooling reactants to 110 ℃ when no water drop occurs in a condensation tube, distilling out the toluene and excessive diethylenetriamine, and cooling to room temperature to obtain the hexanoic acid imidazoline monomer;
in the preparation process of the functional auxiliary agent, the molar ratio of the L-lysine triisocyanate to the behenyl alcohol is 1: 1.8; the molar ratio of the L-lysine triisocyanate to the functional monomer is 1: 0.5; the functional monomer is propane diamine and imidazoline caproate, and the weight ratio of the propane diamine to the imidazoline caproate is 1: 1; wherein the CAS of the L-lysine triisocyanate is 69878-18-8, and the CAS of the behenyl alcohol is 661-19-8;
the slipping agent in the ultraviolet-resistant aging-resistant master batch is erucamide and diethenyloleamide according to the weight ratio of 1: 0.5 is compounded to obtain.
The preparation method of the ultraviolet-resistant and aging-resistant master batch comprises the following steps: and putting the LDPE, the hindered amine light stabilizer, the ultraviolet absorbent, the composite antioxidant, the functional assistant and the slipping agent into a high-speed mixer, mixing for 15min, transferring to a double-screw extruder, melting and extruding at the extrusion temperature of 180 ℃, and cooling by air to obtain the ultraviolet-resistant and aging-resistant master batch.
The inner two layers comprise the following components in parts by weight: 30 parts of mLLDPE-1, 20 parts of LDPE-1 and 3 parts of ultraviolet-resistant and aging-resistant master batch.
The components of the inner two layers are derived from sources such asShown below:
the mLLDPE-1 is a product purchased from Exxon Mobil and having a grade of 1327CA and the density is 0.927g/cm3；
The LDPE-1 is a product purchased from Exxon Mobil and having a grade of 350D65 and has a density of 0.917g/cm3；
The ultraviolet-resistant and aging-resistant master batches of the inner two layers are the same as the ultraviolet-resistant and aging-resistant master batches of the inner layer.
According to the weight portion, the middle layer comprises: 40 parts of EVA, 30 parts of LDPE-2 and 5 parts of heat-insulating master batch.
The sources of the components of the middle layer are as follows:
the EVA is a product purchased from American Seranian and having the grade of 1807V, the content of the VA is 18 wt%, and the melt index is 0.7g/10 min;
the LDPE-2 is a product purchased from Exxon Mobil and having the trademark LD171BA and the density of the LDPE-2 is 0.929g/cm3；
Wherein, by weight, the heat preservation master batch comprises: 20 parts of LDPE, 15 parts of transparent heat-insulating agent, 3 parts of basic magnesium carbonate and 1 part of PPA (polyphthalamide) assistant;
wherein the LDPE in the heat-insulating master batch is a product purchased from Exxon Mobil and having the grade of LD171 BA;
the transparent heat-insulating agent in the heat-insulating master batch is a product which is purchased from Shanghai Hexin Fine chemical Co., Ltd and has the brand number of HX-898;
the basic magnesium carbonate in the heat-preservation master batch is purchased from Shanghai Yangtze titanium white chemical products, Co.Ltd;
the PPA auxiliary agent in the heat-insulating master batch is purchased from Beijia polymer materials Limited company of Jining, and the brand is F-5.
The preparation method of the heat preservation master batch comprises the following steps: and (3) putting the LDPE, the transparent heat preservation agent, the basic magnesium carbonate and the PPA auxiliary agent into a high-speed mixer, mixing for 15min, transferring to a double-screw extruder, melting and extruding at the extrusion temperature of 180 ℃, and air cooling to obtain the heat preservation master batch.
The outer two layers of the invention comprise, by weight: 30 parts of mLLDPE-2, 20 parts of LDPE-2, 5 parts of ultraviolet-resistant and aging-resistant master batch and 1 part of dustproof master batch.
The sources of the components of the outer two layers are as follows:
the mLLDPE-2 is a product purchased from Exxon Mobil and having the brands of 1327CA and 1327ED, and the density is 0.927g/cm3；
The LDPE-2 is a product purchased from Exxon Mobil and having the trademark LD171BA and the density of the LDPE-2 is 0.929g/cm3；
The ultraviolet-resistant and aging-resistant master batches on the outer two layers are the same as those on the inner layer;
the dustproof master batch in the outer two layers is purchased from Huizzinew materials Co., Ltd, Dongguan city.
The outer layer comprises the following components in parts by weight: 50 parts of mLLDPE-3, 10 parts of LDPE-3, 5 parts of ultraviolet-resistant and aging-resistant master batch and 3 parts of dustproof master batch.
The sources of the components of the outer layer are as follows:
the mLLDPE-3 is a product purchased from Exxon Mobil and having the grade of E1012HA, and the density is 0.912g/cm3；
The LDPE-3 is a product purchased from Exxon Mobil and having the trademark LD171BA and the density of the LDPE-3 is 0.929g/cm3；
The outer layer of the ultraviolet-resistant and aging-resistant master batch is the same as the inner layer of the ultraviolet-resistant and aging-resistant master batch;
the dustproof master batch of the outer layer is the same as the dustproof master batches of the outer two layers.
The coating layer is formed by coating liquid, and the coating liquid comprises the following components in parts by weight: 3 parts of functional assistant, 0.1 part of antifogging agent, 0.5 part of dripping agent, 0.5 part of surfactant and 35 parts of water.
The coating amount of the coating liquid is 13g/m per square content2。
The sources of the components of the coating liquid are as follows:
the functional auxiliary agent in the coating liquid is the same as the functional auxiliary agent in the ultraviolet-resistant and aging-resistant master batch;
the antifogging agent is AF-31 and is purchased from Pasteur Germany;
the dripping agent is FWD650 purchased from Shanghai' an Yiyi chemical Co., Ltd;
the surfactant is sodium carboxyethyl cellulose and fatty alcohol-polyoxyethylene ether in a weight ratio of 1: 1, compounding to obtain;
the preparation method of the agricultural greenhouse film comprises the following steps: preparing materials according to a production formula, mixing the materials of the inner layer, the inner two layers, the middle layer, the outer two layers and the outer layer uniformly, extruding, compounding the materials to a machine head, blowing, drawing a guide roller to the upper part through a foam stabilizing frame, carrying out corona treatment, carrying out secondary drawing, entering a coating liquid groove to coat a film product, controlling the drawing speed of a coating layer, drying, carrying out tertiary drawing, carrying out fourth drawing after passing through the guide roller, folding and rolling to obtain the heat-preservation, aging-resistant and fog-dissipation agricultural greenhouse film.
Example 2
Embodiment 2 provides an agricultural greenhouse film with heat preservation, aging resistance and fog dissipation, which comprises a basic film layer and a coating layer, wherein the basic film layer consists of an inner layer, a middle layer, an outer layer and an outer layer, and the layers are sequentially stacked from the inner layer to the outer layer; wherein the base film layer comprises the following components in parts by weight: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
The inner layer comprises the following components in parts by weight: 70 parts of mLLDPE, 30 parts of LDPE and 10 parts of ultraviolet-resistant and aging-resistant master batch.
The sources of the components of the inner layer are as follows:
the mLLDPE of the inner layer is a product purchased from Exxon Mobil and the grade is 1327 CA;
the LDPE of the inner layer is a product purchased from Exxon Mobil and having the trademark LD171 BA;
wherein, by weight, the anti-ultraviolet aging-resistant master batch comprises: 20 parts of LDPE, 2 parts of hindered amine light stabilizer, 3 parts of ultraviolet absorbent, 5 parts of composite antioxidant, 0.5 part of functional assistant and 0.8 part of slipping agent;
wherein the LDPE in the ultraviolet-resistant aging-resistant master batch is a product purchased from Exxon Mobil and having the trademark LD171 BA;
the hindered amine light stabilizer in the ultraviolet-resistant and aging-resistant master batch is TH9944 purchased from Zhengzhou Akhm chemical Co., Ltd;
the ultraviolet absorbent in the ultraviolet-resistant and aging-resistant master batch is UV-416, and is purchased from Xiangyang Furun chemical Co., Ltd;
the antioxidant in the uvioresistant aging-resistant master batch is antioxidant 1010 and antioxidant 168 according to the weight ratio of 1: 1, compounding to obtain;
the functional auxiliary agent in the ultraviolet-resistant and aging-resistant master batch is the same as that in the embodiment 1;
the slipping agent in the ultraviolet-resistant aging-resistant master batch is erucamide and diethenyloleamide according to the weight ratio of 1: 1 is obtained by compounding.
The preparation method of the ultraviolet-resistant and aging-resistant master batch is the same as that of the example 1.
The inner two layers comprise the following components in parts by weight: 50 parts of mLLDPE-1, 40 parts of LDPE-1 and 8 parts of ultraviolet-resistant and aging-resistant master batch.
The sources of the components of the inner two layers are as follows:
the mLLDPE-1 is a product purchased from Exxon Mobil and having a grade of 1327CA and the density is 0.927g/cm3；
The LDPE-1 is a product purchased from Exxon Mobil and having a grade of 350D65 and has a density of 0.917g/cm3；
The ultraviolet-resistant and aging-resistant master batches of the inner two layers are the same as the ultraviolet-resistant and aging-resistant master batches of the inner layer.
According to the weight portion, the middle layer comprises: 70 parts of EVA, 45 parts of LDPE-2 and 10 parts of heat-insulating master batch.
The sources of the components of the middle layer are as follows:
the EVA is a product purchased from American Seranian and having the grade of 1807V, the content of the VA is 18 wt%, and the melt index is 0.7g/10 min;
the LDPE-2 is a product purchased from Exxon Mobil and having the trademark LD171BA and the density of the LDPE-2 is 0.929g/cm3；
Wherein, by weight, the heat preservation master batch comprises: 30 parts of LDPE, 20 parts of transparent heat-preserving agent, 5 parts of basic magnesium carbonate and 1.5 parts of PPA (polyphthalamide) assistant;
wherein the LDPE in the heat-insulating master batch is a product purchased from Exxon Mobil and having the grade of LD171 BA;
the transparent heat-insulating agent in the heat-insulating master batch is a product which is purchased from Shanghai Hexin Fine chemical Co., Ltd and has the brand number of HX-898;
the basic magnesium carbonate in the heat-preservation master batch is purchased from Shanghai Yangtze titanium white chemical products, Co.Ltd;
the PPA auxiliary agent in the heat-insulating master batch is purchased from Beijia polymer materials Limited company of Jining, and the brand is F-5.
The preparation method of the heat preservation master batch is the same as that of the example 1.
The outer two layers of the invention comprise, by weight: 40 parts of mLLDPE-2, 30 parts of LDPE-2, 10 parts of ultraviolet-resistant and aging-resistant master batch and 3 parts of dustproof master batch.
The sources of the components of the outer two layers are as follows:
the mLLDPE-2 is a product purchased from Exxon Mobil and having the brands of 1327CA and 1327ED, and the density is 0.927g/cm3；
The LDPE-2 is a product purchased from Exxon Mobil and having the trademark LD171BA and the density of the LDPE-2 is 0.929g/cm3；
The ultraviolet-resistant and aging-resistant master batches on the outer two layers are the same as those on the inner layer;
the dustproof master batch in the outer two layers is purchased from Huizzinew materials Co., Ltd, Dongguan city.
The outer layer comprises the following components in parts by weight: 70 parts of mLLDPE-3, 20 parts of LDPE-3, 10 parts of ultraviolet-resistant and aging-resistant master batch and 7 parts of dustproof master batch.
The sources of the components of the outer layer are as follows:
the mLLDPE-3 is a product purchased from Exxon Mobil and having the grade of E1012HA, and the density is 0.912g/cm3；
The LDPE-3 is a product purchased from Exxon Mobil and having the trademark LD171BA and the density of the LDPE-3 is 0.929g/cm3；
The outer layer of the ultraviolet-resistant and aging-resistant master batch is the same as the inner layer of the ultraviolet-resistant and aging-resistant master batch;
the dustproof master batch of the outer layer is the same as the dustproof master batches of the outer two layers.
The coating layer is formed by coating liquid, and the coating liquid comprises the following components in parts by weight: 5 parts of functional assistant, 0.5 part of antifogging agent, 1 part of dripping agent, 1.5 parts of surfactant and 55 parts of water.
The coating amount of the coating liquid is 13g/m per square content2。
The sources of the components of the coating liquid are as follows:
the functional auxiliary agent in the coating liquid is the same as the functional auxiliary agent in the ultraviolet-resistant and aging-resistant master batch;
the antifogging agent is AF-31 and is purchased from Pasteur Germany;
the dripping agent is FWD650 purchased from Shanghai' an Yiyi chemical Co., Ltd;
the surfactant is sodium carboxyethyl cellulose and fatty alcohol-polyoxyethylene ether in a weight ratio of 2.5: 1, compounding to obtain;
the preparation method of the agricultural greenhouse film is the same as that of the embodiment 1.
Example 3
Embodiment 3 provides a heat-insulating, aging-resistant and fog-dissipating agricultural greenhouse film, which comprises a basic film layer and a coating layer, wherein the basic film layer consists of an inner layer, a middle layer, an outer layer and an outer layer, and the layers are sequentially stacked from the inner layer to the outer layer; wherein the base film layer comprises the following components in parts by weight: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
The inner layer comprises the following components in parts by weight: 60 parts of mLLDPE, 25 parts of LDPE and 7 parts of ultraviolet-resistant and aging-resistant master batch.
The sources of the components of the inner layer are as follows:
the mLLDPE of the inner layer is a product purchased from Exxon Mobil and the grade is 1327 CA;
the LDPE of the inner layer is a product purchased from Exxon Mobil and having the trademark LD171 BA;
wherein, by weight, the anti-ultraviolet aging-resistant master batch comprises: 17 parts of LDPE, 0.8 part of hindered amine light stabilizer, 1.5 parts of ultraviolet absorber, 4 parts of composite antioxidant, 0.3 part of functional assistant and 0.5 part of slipping agent;
wherein the LDPE in the ultraviolet-resistant aging-resistant master batch is a product purchased from Exxon Mobil and having the trademark LD171 BA;
the hindered amine light stabilizer in the ultraviolet-resistant and aging-resistant master batch is TH9944 purchased from Zhengzhou Akhm chemical Co., Ltd;
the ultraviolet absorbent in the ultraviolet-resistant and aging-resistant master batch is UV-416, and is purchased from Xiangyang Furun chemical Co., Ltd;
the antioxidant in the uvioresistant aging-resistant master batch is antioxidant 1010 and antioxidant 168 according to the weight ratio of 1: 1, compounding to obtain;
the functional auxiliary agent in the ultraviolet-resistant and aging-resistant master batch is the same as that in the embodiment 1;
the slipping agent in the ultraviolet-resistant aging-resistant master batch is erucamide and diethenyloleamide according to the weight ratio of 1: 0.7 to obtain the compound.
The preparation method of the ultraviolet-resistant and aging-resistant master batch is the same as that of the example 1.
The inner two layers comprise the following components in parts by weight: 40 parts of mLLDPE-1, 30 parts of LDPE-1 and 5 parts of anti-ultraviolet aging-resistant master batch.
The sources of the components of the inner two layers are as follows:
the mLLDPE-1 is a product purchased from Exxon Mobil and having a grade of 1327CA and the density is 0.927g/cm3；
The LDPE-1 is a product purchased from Exxon Mobil and having a grade of 350D65 and has a density of 0.917g/cm3；
The ultraviolet-resistant and aging-resistant master batches of the inner two layers are the same as the ultraviolet-resistant and aging-resistant master batches of the inner layer.
According to the weight portion, the middle layer comprises: 55 parts of EVA, 40 parts of LDPE-2 and 8 parts of heat-insulating master batch.
The sources of the components of the middle layer are as follows:
the EVA is a product purchased from American Seranian and having the grade of 1807V, the content of the VA is 18 wt%, and the melt index is 0.7g/10 min;
the LDPE-2 is a product purchased from Exxon Mobil and having the trademark LD171BA and the density of the LDPE-2 is 0.929g/cm3；
Wherein, by weight, the heat preservation master batch comprises: 25 parts of LDPE, 18 parts of transparent heat-insulating agent, 4 parts of basic magnesium carbonate and 1.2 parts of PPA (polyphthalamide) assistant;
wherein the LDPE in the heat-insulating master batch is a product purchased from Exxon Mobil and having the grade of LD171 BA;
the transparent heat-insulating agent in the heat-insulating master batch is a product which is purchased from Shanghai Hexin Fine chemical Co., Ltd and has the brand number of HX-898;
the basic magnesium carbonate in the heat-preservation master batch is purchased from Shanghai Yangtze titanium white chemical products, Co.Ltd;
the PPA auxiliary agent in the heat-insulating master batch is purchased from Beijia polymer materials Limited company of Jining, and the brand is F-5.
The preparation method of the heat preservation master batch is the same as that of the example 1.
The outer two layers of the invention comprise, by weight: 35 parts of mLLDPE-2, 25 parts of LDPE-2, 7 parts of ultraviolet-resistant and aging-resistant master batch and 2 parts of dustproof master batch.
The sources of the components of the outer two layers are as follows:
the mLLDPE-2 is a product purchased from Exxon Mobil and having the brands of 1327CA and 1327ED, and the density is 0.927g/cm3；
The LDPE-2 is a product purchased from Exxon Mobil and having the trademark LD171BA and the density of the LDPE-2 is 0.929g/cm3；
The ultraviolet-resistant and aging-resistant master batches on the outer two layers are the same as those on the inner layer;
the dustproof master batch in the outer two layers is purchased from Huizzinew materials Co., Ltd, Dongguan city.
The outer layer comprises the following components in parts by weight: 60 parts of mLLDPE-3, 15 parts of LDPE-3, 7 parts of ultraviolet-resistant and aging-resistant master batch and 5 parts of dustproof master batch.
The sources of the components of the outer layer are as follows:
the mLLDPE-3 is a product purchased from Exxon Mobil and having the grade of E1012HA, and the density is 0.912g/cm3；
The LDPE-3 is a product purchased from Exxon Mobil and having the trademark LD171BA and the density of the LDPE-3 is 0.929g/cm3；
The outer layer of the ultraviolet-resistant and aging-resistant master batch is the same as the inner layer of the ultraviolet-resistant and aging-resistant master batch;
the dustproof master batch of the outer layer is the same as the dustproof master batches of the outer two layers.
The coating layer is formed by coating liquid, and the coating liquid comprises the following components in parts by weight: 4 parts of functional assistant, 0.3 part of antifogging agent, 0.7 part of dripping agent, 1 part of surfactant and 40 parts of water.
The coating amount of the coating liquid is 13g/m per square content2。
The sources of the components of the coating liquid are as follows:
the functional auxiliary agent in the coating liquid is the same as the functional auxiliary agent in the ultraviolet-resistant and aging-resistant master batch;
the antifogging agent is AF-31 and is purchased from Pasteur Germany;
the dripping agent is FWD650 purchased from Shanghai' an Yiyi chemical Co., Ltd;
the surfactant is sodium carboxyethyl cellulose and fatty alcohol-polyoxyethylene ether in a weight ratio of 2.2: 1, compounding to obtain;
the preparation method of the agricultural greenhouse film is the same as that of the embodiment 1.
Example 4
Embodiment 4 provides a heat-insulating, aging-resistant and fog-dissipating agricultural greenhouse film, which comprises a basic film layer and a coating layer, wherein the basic film layer consists of an inner layer, a middle layer, an outer layer and an outer layer, and the layers are sequentially stacked from the inner layer to the outer layer; wherein the base film layer comprises the following components in parts by weight: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 4 is the same as example 3, except that the ratio of the individual raw materials in the functional aid preparation process is different: in the preparation process of the functional auxiliary agent, the molar ratio of the L-lysine triisocyanate to the behenyl alcohol is 1: 2.2; the molar ratio of the L-lysine triisocyanate to the functional monomer is 1: 1.2; the functional monomer is propane diamine and imidazoline caproate, and the weight ratio of the propane diamine to the imidazoline caproate is 3: 1; wherein the CAS of the L-lysine triisocyanate is 69878-18-8, and the CAS of the behenyl alcohol is 661-19-8.
Example 5
Embodiment 5 provides a heat-insulating, aging-resistant and fog-dissipating agricultural greenhouse film, which comprises a base film layer and a coating layer, wherein the base film layer consists of an inner layer, a middle layer, an outer layer and an outer layer, and the layers are sequentially stacked from the inner layer to the outer layer; wherein the base film layer comprises the following components in parts by weight: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 5 is the same as example 3, except that the ratio of the individual raw materials in the functional aid preparation process is different: in the preparation process of the functional auxiliary agent, the molar ratio of the L-lysine triisocyanate to the behenyl alcohol is 1: 2; the molar ratio of the L-lysine triisocyanate to the functional monomer is 1: 1; the functional monomer is propane diamine and imidazoline caproate, and the weight ratio of the propane diamine to the imidazoline caproate is 2: 1; wherein the CAS of the L-lysine triisocyanate is 69878-18-8, and the CAS of the behenyl alcohol is 661-19-8.
Example 6
Embodiment 6 provides a heat-insulating, aging-resistant and fog-dissipating agricultural greenhouse film, which comprises a basic film layer and a coating layer, wherein the basic film layer consists of an inner layer, a middle layer, an outer layer and an outer layer, and the layers are sequentially stacked from the inner layer to the outer layer; wherein the base film layer comprises the following components in parts by weight: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 6 is the same as example 5, except that the coating solution is different: the coating liquid comprises the following components in parts by weight: 0.1 part of functional assistant, 0.3 part of antifogging agent, 0.7 part of dripping agent, 1 part of surfactant and 40 parts of water.
Example 7
Embodiment 7 provides a heat-insulating, aging-resistant and fog-dissipating agricultural greenhouse film, which comprises a base film layer and a coating layer, wherein the base film layer consists of an inner layer, a middle layer, an outer layer and an outer layer, and the layers are sequentially stacked from the inner layer to the outer layer; wherein the base film layer comprises the following components in parts by weight: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 7 is the same as example 5, except that the coating solution is different: the coating liquid comprises the following components in parts by weight: 40 parts of functional assistant, 0.3 part of antifogging agent, 0.7 part of dripping agent, 1 part of surfactant and 40 parts of water.
Example 8
Embodiment 8 provides a heat-insulating, aging-resistant and fog-dissipating agricultural greenhouse film, which comprises a base film layer and a coating layer, wherein the base film layer consists of an inner layer, a middle layer, an outer layer and an outer layer, and the layers are sequentially stacked from the inner layer to the outer layer; wherein the base film layer comprises the following components in parts by weight: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 8 is the same as example 5, except that the surfactant in the coating solution is different: the surfactant is sodium carboxyethyl cellulose and fatty alcohol-polyoxyethylene ether in a weight ratio of 0.5: 1 is obtained by compounding.
Example 9
Embodiment 9 provides a heat-insulating, aging-resistant and fog-dissipating agricultural greenhouse film, which comprises a base film layer and a coating layer, wherein the base film layer consists of an inner layer, a middle layer, an outer layer and an outer layer, and the layers are sequentially stacked from the inner layer to the outer layer; wherein the base film layer comprises the following components in parts by weight: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 9 is the same as example 5, except that the surfactant in the coating solution is different: the surfactant is sodium carboxyethyl cellulose and fatty alcohol-polyoxyethylene ether in a weight ratio of 20: 1 is obtained by compounding.
Example 10
Embodiment 10 provides a heat-insulating, aging-resistant, fog-dissipating agricultural greenhouse film, which includes a base film layer and a coating layer, wherein the base film layer is composed of an inner layer, a middle layer, an outer layer, and the layers are stacked in sequence from the inner layer to the outer layer; wherein the base film layer comprises the following components in parts by weight: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 10 is the same as example 5 except that the EVA was a product purchased from Taiconing under the trade designation 7870S, has a VA content of 28 wt% and a melt index of 15g/10 min.
Example 11
Embodiment 11 provides a heat-insulating, aging-resistant, fog-dissipating agricultural greenhouse film, which includes a base film layer and a coating layer, wherein the base film layer is composed of an inner layer, a middle layer, an outer layer, and the layers are stacked in sequence from the inner layer to the outer layer; wherein the base film layer comprises the following components in parts by weight: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 11 is the same as example 5 except that the EVA was a product purchased from Korea modern under the trade name EF221, the VA content was 3 wt%, and the melt index was 0.6g/10 min.
Example 12
Embodiment 12 provides a heat-insulating, aging-resistant, fog-dissipating agricultural greenhouse film, which includes a base film layer and a coating layer, wherein the base film layer is composed of an inner layer, a middle layer, an outer layer, and the layers are stacked in sequence from the inner layer to the outer layer; wherein the base film layer comprises the following components in parts by weight: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 12 is the same as example 5 except that the uv resistant and aging resistant master batch is different: the slipping agent in the ultraviolet-resistant aging-resistant master batch is erucamide and diethenyloleamide according to the weight ratio of 1: 0.05 to obtain the product.
Example 13
Embodiment 13 provides a heat-insulating, aging-resistant, fog-dissipating agricultural greenhouse film, which includes a base film layer and a coating layer, wherein the base film layer is composed of an inner layer, a middle layer, an outer layer, and the layers are stacked in sequence from the inner layer to the outer layer; wherein the base film layer comprises the following components in parts by weight: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 13 is the same as example 5 except that the uv resistant and aging resistant master batch is different: the slipping agent in the ultraviolet-resistant aging-resistant master batch is erucamide and diethenyloleamide according to the weight ratio of 1: 30 are compounded to obtain.
Evaluation of Performance
1. And (3) artificial accelerated aging test: the test was carried out according to the GB/T16422.3-2014 standard.
2. Testing the flow drop fog dissipation period, the transmittance and the haze: the test was carried out according to the GB/T20202-2006 standard.
3. And (3) mobility testing: the sample was left in a dry environment for six months, and the mobility was determined by measuring the rate of change in weight.
TABLE 1
Figure BDA0001975877710000261

Claims (3)

1. The agricultural greenhouse film is characterized by comprising a basic film layer and a coating layer, wherein the basic film layer consists of an inner layer, a middle layer, an outer layer and an outer layer, and the layers are stacked from the inner layer to the outer layer in sequence;
the inner layer comprises: 40-70 parts of mLLDPE, 20-30 parts of LDPE and 5-10 parts of anti-ultraviolet aging-resistant master batch;
the inner two layers include: 30-50 parts of mLLDPE-1, 20-40 parts of LDPE-1 and 3-8 parts of ultraviolet-resistant and aging-resistant master batch;
the middle layer includes: 40-70 parts of EVA (ethylene-vinyl acetate), 30-45 parts of LDPE-2 and 5-10 parts of heat-insulating master batch;
the outer two layers include: 30-40 parts of mLLDPE-2, 20-30 parts of LDPE-2, 5-10 parts of ultraviolet-resistant and aging-resistant master batch and 1-3 parts of dustproof master batch;
the outer layer comprises: 50-70 parts of mLLDPE-3, 10-20 parts of LDPE-3, 5-10 parts of ultraviolet-resistant and aging-resistant master batch and 3-7 parts of dustproof master batch;
the ultraviolet-resistant and aging-resistant master batch comprises the following components in parts by weight: 10-20 parts of LDPE, 0.1-2 parts of hindered amine light stabilizer, 1-3 parts of ultraviolet absorber, 3-5 parts of composite antioxidant, 0.1-0.5 part of functional assistant and 0.3-0.8 part of slipping agent; wherein the preparation steps of the functional auxiliary agent comprise: adding L-lysine triisocyanate into a reaction kettle provided with a thermometer and a reflux device, diluting with acetone, dropwise adding behenyl alcohol and an acetone solution containing a catalyst dibutyltin dilaurate, stirring at 55 ℃ for reacting for 1-2 hours, dropwise adding a functional monomer, and reacting for 2-3 hours under heat preservation to obtain the functional auxiliary agent; wherein the molar ratio of the L-lysine triisocyanate to the behenyl alcohol in the preparation process of the functional auxiliary agent is 1: (1.8-2.2); the molar ratio of the L-lysine triisocyanate to the functional monomer is 1: (0.5 to 1.2); the functional monomer is propane diamine and caproic acid imidazoline, and the weight ratio of the propane diamine to the caproic acid imidazoline is (1-3): 1; the slipping agent is erucamide and diethenyloleamide according to the weight ratio of 1: (0.5-1) compounding;
the coating layer is formed by coating liquid, and the coating liquid comprises the following components in parts by weight: 3-5 parts of functional assistant, 0.1-0.5 part of antifogging agent, 0.5-1 part of dripping agent, 0.5-1.5 parts of surfactant and 35-55 parts of water; the functional additive is the same as the functional additive in the ultraviolet-resistant and aging-resistant master batch; the surfactant is sodium carboxyethyl cellulose and fatty alcohol-polyoxyethylene ether in a weight ratio of (1-2.5): 1 is obtained by compounding.
2. The heat-insulating, aging-resistant and fog-dispersal agricultural greenhouse film as claimed in claim 1, wherein the base film layer comprises, in parts by weight: 10-15 parts of an inner layer, 8-12 parts of an inner two layer, 15-20 parts of a middle layer, 15-20 parts of an outer two layer and 20-30 parts of an outer layer.
3. The heat-insulating, aging-resistant and fog-dissipating agricultural greenhouse film as claimed in claim 1, wherein the heat-insulating master batch comprises, in parts by weight: 20-30 parts of LDPE, 15-20 parts of transparent heat-insulating agent, 3-5 parts of basic magnesium carbonate and 1-1.5 parts of PPA (poly (phenylene benzobisoxazole)) assistant.
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