CN115517125A - Coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dissipation greenhouse film and preparation method thereof - Google Patents
Coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dissipation greenhouse film and preparation method thereof Download PDFInfo
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- CN115517125A CN115517125A CN202211350102.7A CN202211350102A CN115517125A CN 115517125 A CN115517125 A CN 115517125A CN 202211350102 A CN202211350102 A CN 202211350102A CN 115517125 A CN115517125 A CN 115517125A
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Classifications
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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
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
- A01G13/0256—Ground coverings
- A01G13/0268—Mats or sheets, e.g. nets or fabrics
- A01G13/0275—Films
-
- 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
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
-
- 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of agricultural film preparation, and particularly relates to a coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dissipation greenhouse film and a preparation method thereof. Comprises an inner layer, a secondary inner layer, a middle layer, a secondary outer layer, an outer layer and a coating layer; the inner layer is a dustproof aging-resistant layer, the secondary inner layer is a heat-insulating aging-resistant layer, the middle layer is a high-insulating barrier layer, the secondary outer layer is a light conversion layer, the outer layer is an aging-resistant layer, and the coating layer is a long-acting dripping defogging layer. The coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dissipation shed film has the advantages that the light transmittance is more than 92%, and the fog degree is less than 11.5%; the infrared transmittance is less than 28%, and the heat insulation performance of the greenhouse at night is obviously improved; the intensity ratio of the light inside and outside the greenhouse is still larger than 88% at 600 days after film covering; the dustproof function ensures that the annual attenuation rate of the light transmittance is less than 1.1%; the duration of the dripping fog dissipation function is more than 7 years.
Description
Technical Field
The invention belongs to the technical field of agricultural film preparation, and particularly relates to a coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dissipation greenhouse film and a preparation method thereof.
Background
Currently, the yield and the consumption of polyolefin agricultural greenhouse films are in the forefront of the world in China, and the market development speed of the multifunctional high-end agricultural greenhouse films is increasing by two digits every year. There are two main types of compositions of functional greenhouse films of greenhouse covering materials currently on the market.
One is to add light conversion agent, dust-proof agent, heat-insulating agent and various surfactants into the film to prepare the light conversion dust-proof high heat-insulating flowing drop fog-eliminating greenhouse film, and the flowing drop fog-eliminating function is achieved by gradual deposition of the surfactants in the film, the flowing drop lasting period of the internal addition type greenhouse film is usually only 4-6 months, and the requirement of modern high-efficiency agricultural development cannot be met.
The other method is to mix inorganic sol with a small amount of organic glue solution to prepare coating solution, and soak the polyolefin substrate subjected to corona treatment in the coating solution to form an inorganic coating layer on the inner surface of the membrane. The method has the advantages that the inorganic coating does not run off along with water, and the lasting period of dripping and fog dissipation can be synchronous with the service life of the film. However, the prior art is still relatively lagged behind in the aspect of adding comprehensive functions of dust prevention, light modulation and conversion and high heat preservation in the long-acting and long-life greenhouse film. The dustproof function and the light conversion function of the shed film in the market can not coexist in a synergistic manner, and the dustproof function, the light conversion function, the high heat preservation function and the dripping and fog dissipation function are only one or two.
The patent 2018115586536 discloses a high-dustproof long-acting light conversion five-layer co-extrusion greenhouse film and a preparation method thereof, wherein the greenhouse film comprises an outer layer, a secondary outer layer, a middle layer, a secondary inner layer and an inner layer, the outer layer and the secondary outer layer are drip layers of the greenhouse film, the middle layer is a heat insulation layer of the greenhouse film, and the inner layer and the secondary inner layer are long-life layers of the greenhouse film; wherein, add the masterbatch that changes the light in inferior inlayer, add dustproof masterbatch in the inlayer. The production process described in the above patent is an internal addition type, and the light-conversion dustproof high-heat-insulation flowing-drop fog-dispersal greenhouse film is prepared by adding a light conversion agent, a dustproof agent, a heat-insulating agent and various surfactants into the film, and the flowing-drop fog-dispersal function is achieved by gradual precipitation of the surfactants in the film, so that the flowing-drop lasting period of the internal addition type greenhouse film is usually only 4-6 months, and the requirement of modern high-efficiency agricultural development cannot be met. For the greenhouse film, the dripping fog dissipation performance has long lasting period and synchronous service life with the film, and the functions of high light transmission, high heat preservation, dust prevention and accurate light adjustment and light conversion are main indexes for evaluating the quality and performance of a greenhouse film product.
In order to solve the problems in the prior art, the development of a greenhouse film with comprehensive functions and reliable quality is urgently needed. Under the promotion of quality agriculture and green agriculture, the high-end functional greenhouse film market has great potential. The high-end comprehensive functional greenhouse film disclosed by the invention realizes ultra-long service life, accurate dimming and light conversion, converts a solar spectrum with low utilization rate into a spectrum band required by crops, has high-efficiency light conversion become one of important indexes of the functional agricultural film, and simultaneously realizes the functions of high heat preservation, self-cleaning, dust prevention, long-acting dripping and fog dissipation, thus being the subject of research of the invention.
Disclosure of Invention
The purpose of the invention is: provides a coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dissipation greenhouse film. The greenhouse film has the comprehensive functions of dust prevention, light modulation and light conversion, high heat preservation, long-acting dripping fog dissipation period and synchronous service life of the film; the invention also provides a preparation method thereof.
The coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dissipation greenhouse film comprises an inner layer, a secondary inner layer, a middle layer, a secondary outer layer, an outer layer and a coating layer; wherein the inner layer is a dustproof aging-resistant layer and consists of the following raw materials in percentage by mass: 15-25% of low-density polyethylene (LDPE), 60-70% of metallocene linear low-density polyethylene (mLLDPE), 6-12% of anti-aging master batch and 3-8% of dustproof master batch; the secondary inner layer is a heat-insulating and anti-aging layer and comprises the following raw materials in percentage by mass: 78-87% of ethylene-vinyl acetate copolymer resin (EVA), 5-10% of anti-aging master batch and 6-12% of barrier heat-insulation master batch; the middle layer is a high-heat-insulation barrier layer and consists of the following raw materials in percentage by mass: 75-85% of ethylene-vinyl acetate copolymer resin (EVA), 5-10% of anti-aging master batch and 8-15% of barrier heat-insulation master batch; the secondary outer layer is a light conversion layer and consists of the following raw materials in percentage by mass: 25-31% of Low Density Polyethylene (LDPE), 20-25% of Linear Low Density Polyethylene (LLDPE), 30-40% of metallocene linear low density polyethylene (mLLDPE), 6-12% of light conversion master batch and 3-5% of ageing-resistant master batch; the outer layer is an aging-resistant layer and comprises the following raw materials in percentage by mass: 20% -28% of Low Density Polyethylene (LDPE), 65% -75% of metallocene linear low density polyethylene (mLLDPE) and 5% -8% of ageing-resistant master batch; the coating layer is a long-acting dripping fog-eliminating layer.
Wherein:
the ethylene-vinyl acetate copolymer resin (EVA) in the starting material for the inner sublayer had a VA content of 12% and a Melt Index (MI) of 0.5g/10min.
The VA content of the ethylene-vinyl acetate copolymer resin (EVA) in the middle layer raw material is 14-18%, and the Melt Index (MI) is 0.25-0.37g/10min.
Preferably, the ethylene-vinyl acetate copolymer resin (EVA) is any one or two of FL00012, FL00014 and FL00018 manufactured by Exxon Mobil corporation, 2050 manufactured by Korea, and 14/0.7 manufactured by Beijing organic chemical industry.
The coating layer is a coating liquid dry matter prepared from inorganic aluminum sol, silica sol and organic mixed glue solution.
The coating layer comprises the following raw materials in percentage by mass: 6-8% of coating liquid stock solution and 92-90% of deionized water; the coating liquid stock solution is any one of TG-150 or TF-820G; wherein the TG-150 was manufactured by Nippon bamboo fat Co., ltd, and the TF-820G was manufactured by Loran Green Source Ltd.
The specific parameters of the raw materials adopted by the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer are as follows:
the Low Density Polyethylene (LDPE) has a density of 0.920-0.923g/cm 3 Melt Index (MI) of 0.2-1.0g/10min; preferably, the Low Density Polyethylene (LDPE) is any one or both of 2420D, 2426F from Mediterranean brand or LD165 from Exxon brand.
The Linear Low Density Polyethylene (LLDPE) has a density of from 0.918 to 0.926g/cm 3 Melt Index (MI) of 0.8-1.0g/10min; preferably, the Linear Low Density Polyethylene (LLDPE) is any one of 1001AV manufactured by Exxon Mobil, 9085 manufactured by Tianjin Union carbon, or 0209AA manufactured by Shanghai Saiko.
The metallocene linear low density polyethylene (m-LLDPE) has a density of from 0.916 to 0.922g/cm 3 Melt Index (MI) of 0.2-1.0g/10min; preferably, the metallocene linear low density polyethylene is one or more of 2010MA, 2005MC, XP6056ML, XP6026ML available from Exxon Mobil corporation, and D139 brand available from Philips snow-broken corporation.
Preferably, the dustproof master batch is a commercial product EFT997 produced by Tianjin research corporation; or maleic anhydride grafted dustproof master batch, the manufacturer is Jilin Baien plastic science and technology company, and the brand is BE-10F.
The anti-aging master batch comprises the following raw materials in percentage by mass: 42-45% of Low Density Polyethylene (LDPE), 37-40% of Linear Low Density Polyolefin (LLDPE), 12-15% of light stabilizer and 2-3% of antioxidant.
Wherein: the Melt Index (MI) of the Low Density Polyethylene (LDPE) in the aging-resistant masterbatch is 2.0g/10min, preferably any one of 2102TN00 of Qilu petrochemical production or 2426H mark of Daqing petrochemical production; the Linear Low Density Polyethylene (LLDPE) has a Melt Index (MI) of 2.0g/10min and is powder in appearance, and preferably, the Linear Low Density Polyethylene (LLDPE) is any one of the grade 7042 of the Qilu petrochemical production or 1820 of the Tianlian production; the light stabilizer is a hindered amine light stabilizer, preferably, the hindered amine light stabilizer is at least one of HALS944, HS-625, T-69 or XT-100, the manufacturers of the HALS944 (944 for short) and the XT-100 are Basofu company, and the manufacturers of the HS-625 and the T-69 are Beijing Tiangang company; the antioxidant is a compound of hindered phenols and phosphites, preferably, the antioxidant is any one of B215 or B225; the manufacturers of B215 or B225 are all Tianjin Lianlong.
The preparation method of the anti-aging master batch comprises the following steps: adding low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), a light stabilizer and an antioxidant into an internal mixer according to a certain proportion, kneading and plasticizing, feeding into a single-screw extrusion granulator through an open mill, carrying out hot granulation, and carrying out air cooling and drying to obtain the anti-aging master batch.
Wherein: the temperature of the internal mixer is 125-140 ℃, the plasticizing time is 15-20 minutes, and the temperature of the single-screw extrusion granulator is 140-170 ℃.
The blocking heat-insulation master batch comprises the following raw materials in percentage by mass: 18 to 25 percent of Low Density Polyethylene (LDPE), 15 to 20 percent of Linear Low Density Polyethylene (LLDPE), 50 to 60 percent of hydrotalcite heat preservation agent, 1.0 to 3.0 percent of coupling agent, 0.5 to 1.5 percent of lubricant and 0.5 to 1.5 percent of dispersant.
Wherein: the Melt Index (MI) of low-density polyethylene (LDPE) in the barrier heat-insulation master batch is 2.0g/10min, and preferably any one of 2102TN00 of Qilu petrochemical industry or 2426H mark of Daqing petrochemical industry; the Linear Low Density Polyethylene (LLDPE) has a Melt Index (MI) of 2.0g/10min and is powdery in appearance, and preferably, the Linear Low Density Polyethylene (LLDPE) is one of the grades 7042 of the Qilu petrochemical industry or 1820 of the Tianjun chemical industry; a hydrotalcite holding agent, preferably having a brand name of HTP manufactured by sakai chemical company, or any one of the brand names HT3 manufactured by dandong corporation; the coupling agent is any one of titanate or aluminate, and is produced by Linyi Feiteng chemical company; the lubricant is two or any one of zinc stearate or calcium stearate produced by Hebei Zhongshang chemical industry; the dispersing agent is polyethylene wax.
The preparation method of the blocking heat-insulation master batch comprises the following steps: adding low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), a hydrotalcite heat preservation agent, a coupling agent, a lubricant and a dispersant into an internal mixer according to a proportion, kneading and plasticizing, feeding into a single-screw extrusion granulator through an open mill, carrying out hot granulation, and carrying out air cooling drying to obtain the barrier heat preservation master batch.
Wherein: the temperature of the internal mixer is 125-140 ℃, the plasticizing time is 15-20 minutes, and the temperature of the single-screw extrusion granulator is 140-170 ℃.
The light conversion master batch comprises the following raw materials in percentage by mass: 42 to 52 percent of Low Density Polyethylene (LDPE), 36 to 45 percent of Linear Low Density Polyethylene (LLDPE), 6 to 12 percent of light conversion agent and 0.3 to 1.0 percent of antioxidant.
The Melt Index (MI) of Low Density Polyethylene (LDPE) in the light conversion master batch is 2.0g/10min, and preferably any one of the grades 2102TN00 of Qilu petrochemical production or 2426H of Daqing petrochemical production; the Linear Low Density Polyethylene (LLDPE) has a Melt Index (MI) of 2.0g/10min and is powder in appearance, and preferably, the Linear Low Density Polyethylene (LLDPE) is any one of the grade 7042 of the Qilu petrochemical production or 1820 of the Tian's chemical production; the light conversion agent is preferably an inorganic rare earth light conversion agent which is any one or a plurality of green-to-red GTR-650 II, green-to-red GTR-650 III, purple-to-blue VTB-440, purple-to-red VTR660, red-to-blue double-light-conversion RBI6545, purple-to-far-red VTFR700 or green-to-far-red GTFR708, and is manufactured by Hunan Xiville scientific and technical company; the antioxidant is a compound of hindered phenols and phosphites, preferably, the antioxidant is any one of B215 or B225; the manufacturers of B215 or B225 are all Tianjin Lianlong.
The principle of the preferred light conversion agents is: the excitation spectrum of the light conversion agent is matched with the spectrum of sunlight on the ground, and the emission spectrum is matched with the absorption spectrum of chlorophyll. According to the requirement of crops on light quality, chlorophyll a-mainly absorbs peaks of 418nm blue-violet light and 660nm red light; chlorophyll b-major absorption peaks at blue 454nm and red 643nm; beta-carotene-absorbs primarily bluish violet light 400-500 nm. Selecting one or more light conversion agents, converting ultraviolet light region 290nm-390nm and green light region 500nm-580nm which are difficult to be absorbed by crops into optimum growth effect spectrum blue-violet light region 400nm-500nm with high crop absorption rate, and emission spectrum main peak 440nm +/-30 nm; the red light area is 600nm-700nm, the main peak of the emission spectrum is 640nm +/-30 nm, and the converted blue-violet light and red light are radiated into the greenhouse as much as possible to adjust and improve the illumination environment in the greenhouse, improve the photosynthetic efficiency of crops and achieve the effects of improving the quality and increasing the yield.
The preparation method of the light conversion master batch comprises the following steps: adding low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), a light conversion agent and an antioxidant into an internal mixer according to a proportion, kneading and plasticizing, feeding into a single-screw extrusion granulator through an open mill, carrying out hot granulation, and carrying out air cooling and drying to prepare the light conversion master batch.
Wherein: the temperature of the internal mixer is 125-140 ℃, the plasticizing time is 15-20 minutes, and the temperature of the single-screw extrusion granulator is 140-170 ℃.
The coating type polyolefin light-conversion dustproof high-heat-insulation long-acting dripping fog-dissipation greenhouse film has the following advantages that the thickness ratio of an inner layer, a secondary inner layer, a middle layer, a secondary outer layer and an outer layer is 1 2 。
According to the coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dissipation shed film, the dustproof master batch and the anti-aging master batch are respectively added into the inner layer according to the layered additional function through formula adjustment, and the inner layer faces the outside of the shed after buckling the shed, so that the functions of self-cleaning, dust prevention, photo-thermal oxidative degradation resistance and aging resistance are achieved; the secondary inner layer adopts EVA resin to add hydrotalcite heat-insulating master batch and aging-resistant master batch, so that the heat-insulating function of blocking infrared radiation to the outside of the greenhouse at night and on cloudy days is achieved, and the secondary inner layer is also aging-resistant; the middle layer adopts high VA content EVA resin added with hydrotalcite insulation master batch and aging resistant master batch, which mainly has the functions of blocking the radiation of far infrared rays to the outside of the greenhouse at night, reducing the heat conductivity coefficient of the greenhouse film to achieve the effect of insulation at night, resisting photo-thermal oxidation degradation and improving aging resistance; the secondary outer layer is added with light conversion master batch and aging-resistant master batch, which mainly has the main functions of selecting one or more light conversion agents according to the light quality requirement of crops, converting ultraviolet light and green light which are difficult to be absorbed by the crops into blue light and red light with high crop absorption rate, meeting the optimal growth action spectrum, and enabling the converted red light and blue light to be radiated into the greenhouse as much as possible to adjust and improve the illumination environment in the greenhouse, improve the photosynthetic efficiency of the crops, reduce partial insect pests and enable the fruits and vegetables to increase the yield and have good precocity quality; the outer layer has the effect of resisting photo-thermal oxidative degradation and is bonded with the coating layer. The coating layer is a long-acting dripping fog-eliminating layer, and mainly has the functions of long-acting eliminating fog in the greenhouse, improving light transmittance, facilitating photosynthesis of crops and reducing crop diseases.
The preparation method of the coating type polyolefin light conversion dustproof high heat preservation long-acting dripping fog dispersal shed film comprises the following steps: the coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dissipation shed film is prepared by respectively mixing and stirring the component materials of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer uniformly, adding the mixture into a five-layer co-extrusion extruder, and carrying out melt plasticizing blow molding, cooling and shaping, traction, corona, coating liquid impregnation, drying, edge welding, seam cutting, code spraying and marking and folding.
Wherein: in the five-layer co-extrusion unit, the temperatures of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer are all 150-200 ℃, the temperature of a die head is 190-215 ℃, the temperature of an oven is 85-102 ℃, and the blow-up ratio is 1.5-2.5.
The coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dissipation greenhouse film is suitable for preparing agricultural covering materials.
Compared with the diffuse scattering polyethylene greenhouse film disclosed in the patent 2017113848794 and the preparation method thereof, the production process disclosed in the patent 2017113848794 is of an internal addition type, and the layering functions of the product are completely different from those of the diffuse scattering polyethylene greenhouse film disclosed in the patent 2017113848794. The greenhouse film has high haze, the haze is more than 50 percent, and the greenhouse film is designed for reducing the temperature in a greenhouse and avoiding burning crops; the production process of the product is a coating type greenhouse film with high light transmission and low haze, the haze is lower than 11.5 percent, and the production process is designed for improving the temperature in a greenhouse and aiming at the crops which are pleased with light and temperature. The two membranes have large functional differences and no comparability.
Compared with the coating type light-adjusting dustproof high-heat-preservation long-acting dripping fog-dispersing shed film disclosed in patent 202110191462.6 and the preparation method thereof, the difference of the invention is that: firstly, the production process adopted by the invention is a five-layer co-extrusion method (the published 202110191462.6 patent is a three-layer co-extrusion method), the functional thicknesses of all layers are different, wherein the functional layers are finely designed, and the negative synergistic effect of a heat insulating agent, a dust preventing agent, a coating liquid and a light conversion agent layer is completely avoided; the second is that the secondary inner layer and the middle layer adopt a composite synergistic scheme of ethylene-vinyl acetate copolymer resin (EVA) with high heat insulation performance and hydrotalcite heat insulation agent (the published patent 202110191462.6 adopts polyethylene resin), so that the infrared transmittance of the invention in the embodiment 1 is obviously reduced by more than 45 percent compared with the infrared transmittance of the invention in the comparative example 6 (the comparative example 6 in the application is the same as the essence content of the patent 202110191462.6 in the embodiment 1); thirdly, the content of the light conversion agent in the light conversion film designed by the invention is increased by more than 20 percent compared with the content in the film 202110191462.6, the light intensity ratio inside and outside the greenhouse is obviously improved, the photosynthesis of crops is promoted, the fruit quality is obviously improved, and the fruit ripening is early.
Compared with the prior art, the invention has the following beneficial effects:
(1) The coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dissipation greenhouse film has the specification width of more than 10m, the thickness of 0.08-0.15mm, the light transmittance of more than 92 percent and the haze of less than 11.5 percent; the infrared transmittance is less than 28 percent, and the heat-insulating property of the greenhouse at night is obviously improved; the intensity ratio of the light inside and outside the greenhouse is still larger than 88% at 600 days after film covering; the dustproof function ensures that the annual attenuation rate of the light transmittance is less than 1.1%; the duration of the dripping fog dissipation function is more than 7 years, the dripping fog dissipation function is synchronous with the service life of the greenhouse film, the requirements of farmers on various performance indexes of the greenhouse film in the service life of more than seven years can be completely met, the cost of buckling the greenhouse is saved, and the greenhouse film is lower in carbon and green and environment-friendly.
(2) The coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dispersal shed film has the functions of regulating and converting transmitted light waves and realizing the precise optimization of the illumination environment of crops, and chlorophyll a-main absorption wave peaks are 418nm of blue-violet light and 660nm of red light according to the requirements of the crops on light quality; chlorophyll b-major absorption peaks at blue 454nm and red 643nm; beta-carotene-absorbs primarily bluish violet light 400-500 nm. Preferably, the light conversion agents of green to red GTR-650, purple to blue VTB440 and purple to red VTR660 are compounded, so that the greenhouse film has the functions of converting part of green light excitation spectrum of 500-580nm into red light emission spectrum of 650nm which is more beneficial to plant growth, and simultaneously converting part of ultraviolet light excitation spectrum of 290-370nm into blue light emission spectrum of 440nm and red light emission spectrum of 660nm, thereby enhancing the irradiation intensity of blue light and red light, improving the illumination environment and light intensity ratio in the greenhouse and enhancing the photosynthetic efficiency; the dustproof master batch is added to reduce the friction coefficient of the film surface, so that the greenhouse film is bright as new after being blown by wind and rain. The composite of high heat insulating resin EVA and heat insulating mother material is optimized, so that the transmittance of infrared radiation in the greenhouse at night is low, the composite has excellent dripping and fog eliminating functions, fog in the greenhouse can be eliminated, the photosynthesis of crops is facilitated, the irradiation intensity of ultraviolet UVA is reduced, the plant diseases and insect pests of the crops are reduced, the using amount of pesticides is reduced, the fruits and vegetables can be matured early, the yield is increased, the quality is good, and the composite is suitable for covering and cultivating various crops.
(3) The preparation method of the coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dissipation shed film has scientific and reasonable layered layout function, avoids the negative synergistic effect of various functional master batches and coating liquid, and has stable and reliable quality and simple and easy operation.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dissipation greenhouse film described in the embodiment 1 comprises an inner layer, a secondary inner layer, a middle layer, a secondary outer layer, an outer layer and a coating layer; wherein the inner layer is a dustproof aging-resistant layer and consists of the following raw materials in percentage by mass: 15% of low-density polyethylene (LDPE), 67% of metallocene linear low-density polyethylene (mLLDPE), 10% of ageing-resistant master batch and 8% of dustproof master batch; the secondary inner layer is a heat-insulating and anti-aging layer and comprises the following raw materials in percentage by mass: 80% of ethylene-vinyl acetate copolymer resin (EVA), 10% of anti-aging master batch and 10% of barrier heat-insulation master batch; the middle layer is a high-heat-insulation barrier layer and comprises the following raw materials in percentage by mass: 75% of ethylene-vinyl acetate copolymer resin (EVA), 10% of anti-aging master batch and 15% of barrier heat-insulation master batch; the secondary outer layer is a light conversion layer and consists of the following raw materials in percentage by mass: 25% of low-density polyethylene (LDPE), 25% of linear low-density polyethylene (LLDPE), 35% of metallocene linear low-density polyethylene (mLLDPE), 12% of light conversion master batch and 3% of ageing-resistant master batch; the outer layer is an ageing-resistant layer and consists of the following raw materials in percentage by mass: 20% of low-density polyethylene (LDPE), 75% of metallocene linear low-density polyethylene (mLLDPE) and 5% of ageing-resistant master batch; the coating layer is a long-acting dripping fog-dissipation layer and consists of the following raw materials in percentage by mass: 8% of coating liquid stock solution and 92% of deionized water.
The inner layer comprises the following raw materials: low Density Polyethylene (LDPE) has a Melt Index (MI) of 0.25g/10min, no. 2420D, made of Mediterranean Shell; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 1.0g/10min, manufactured by Exxon Mobil, no. 2010 MC; aging resistant masterbatch (self-made); the dustproof master batch is marked by EFT997, manufactured by Tianjin research and development company.
The anti-aging master batch in the inner layer comprises: 42% of low-density polyethylene (LDPE), 40% of powdery linear low-density polyolefin (LLDPE), 15% of light stabilizer and 3% of antioxidant; wherein: low Density Polyethylene (LDPE) designation 2102TN00, manufactured by zelworm petrochemical; powdered low density linear polyethylene (LLDPE) designation 7042, manufactured by zelworm petrochemical; the light stabilizer is available under the trade name HALS944 manufactured by BASF corporation; the antioxidant is B225, manufactured by Tianjin Lianlong.
The preparation method of the aging-resistant master batch comprises the following steps: accurately weighing low-density polyethylene (LDPE) 2102TN00, powdery linear low-density polyolefin (LLDPE) 7042, light stabilizer HALS944 and antioxidant B225, adding the materials into an internal mixer for kneading and plasticizing, feeding the materials into a single-screw extrusion granulator through an open mill, carrying out hot granulation, and carrying out air cooling drying to obtain the anti-aging master batch.
Wherein: the temperature of the internal mixer is 136 +/-1 ℃, the plasticizing time is 19 +/-1 minutes, and the temperatures of all sections of the open mill and the single-screw granulator are 140-170 ℃ (wherein the temperature of the first section is 170 ℃, the temperature of the second section is 160 ℃, and the temperature of the third section is 140 ℃).
The secondary inner layer is a heat-insulating aging-resistant layer, the ethylene-vinyl acetate copolymer resin (EVA) in the raw materials of the secondary inner layer has the VA content of 12 percent and the Melt Index (MI) of 0.5g/10min and the mark FL00012, produced by Exxon.
The raw material composition and the preparation method of the anti-aging master batch in the secondary inner layer are the same as those of the inner layer.
The blocking heat-insulation master batch in the secondary inner layer comprises the following raw materials in percentage by mass: 20% of low-density polyethylene (LDPE), 16% of linear low-density polyethylene (LLDPE), 60% of hydrotalcite heat preservation agent, 2.0% of coupling agent, 1.0% of lubricant and 1.0% of dispersant; wherein: the Melt Index (MI) of Low Density Polyethylene (LDPE) is 2.0g/10min, the designation 2102TN00 for Qilu petrochemical production; linear Low Density Polyethylene (LLDPE) has a Melt Index (MI) of 2.0g/10min, is powdery in appearance and is of the Qilu petrochemical trade mark 7042; a hydrotalcite heat retaining agent, having a brand name of HTP, manufactured by sakai chemical corporation; the coupling agent is aluminate, which is produced by Linyi Feiteng chemical company; the lubricant is a mixture of zinc stearate and calcium stearate which are produced in Hebei China by chemical industry and are compounded according to the mass ratio of 1; the dispersing agent is polyethylene wax.
The preparation method of the blocking heat-insulation master batch comprises the following steps:
accurately adding low-density polyethylene (LDPE) 2102TN00, linear low-density polyethylene (LLDPE) 7042, hydrotalcite heat-insulating agent HTP, aluminate coupling agent, zinc stearate and calcium stearate mixed lubricant and polyethylene wax dispersing agent into an internal mixer according to the measurement, kneading and plasticizing, feeding into a single-screw extrusion granulator through an open mill, carrying out hot granulation, and carrying out air cooling drying to prepare the blocking heat-insulating master batch for later use.
Wherein the temperature of the internal mixer is 137 +/-1 ℃, the plasticizing time is 19 +/-1 minutes, and the temperature of each section is 140-170 ℃ (wherein the temperature of the first section is 170 ℃, the temperature of the second section is 160 ℃, and the temperature of the third section is 140 ℃).
Ethylene-vinyl acetate copolymer resin (EVA) in the middle layer raw material, the VA content is 17.5%, the Melt Index (MI) is 0.37g/10min, the mark is FL00018, produced by Exxon Mobil; the raw material composition and the preparation method of the aging-resistant master batch in the middle layer are the same as those of the inner layer; the material composition and preparation method of the heat-insulating barrier master batch in the middle layer are the same as those of the secondary inner layer.
The secondary outer layer comprises the following raw materials: low Density Polyethylene (LDPE) has a Melt Index (MI) of 0.25g/10min, manufactured by seashell brand No. 2420D; the Melt Index (MI) of Linear Low Density Polyethylene (LLDPE) is 0.85g/10min, and the mark is 9085 Tianjin joint production; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min, manufactured by Exxon Mobil under the brand XP6026 ML.
The light conversion master batch in the secondary outer layer comprises the following raw materials in percentage by mass: 50% of Low Density Polyethylene (LDPE), 39.5% of Linear Low Density Polyethylene (LLDPE), 10% of light conversion agent and 0.5% of antioxidant; wherein: low Density Polyethylene (LDPE) 2102TN00 ziegler petrochemical; 7042, powdered Linear Low Density Polyethylene (LLDPE) petrochemical; the light conversion agent is prepared by compounding green-to-red GTR-650 II, GTR-650 III, purple-to-red VTR660 and purple-to-blue VTB440 according to a mass ratio (3.
The preparation method of the light conversion master batch comprises the following steps: accurately metering a compound of low-density polyethylene (LDPE) 2102TN00, powdery linear low-density polyethylene (LLDPE) 7042, light conversion agent green-to-red GTR-650 II and GTR-650 III, and a compound of purple-to-red VTR660 and purple-to-blue VTB440, and an antioxidant B225, adding the compound and the antioxidant into an internal mixer for kneading and plasticizing, feeding the mixture into a single-screw extrusion granulator through an open mill, carrying out hot granulation, and carrying out air cooling and drying to prepare a light conversion master batch for later use.
Wherein, the temperature of the internal mixer is 137 +/-1 ℃, the plasticizing time is 20 minutes, and the temperature of each section is 140-170 ℃ (170 ℃ in the first section, 160 ℃ in the second section and 140 ℃ in the third section).
The raw material composition and the preparation method of the anti-aging master batch in the secondary outer layer are the same as those of the inner layer.
The outer layer comprises the following raw materials: low Density Polyethylene (LDPE) has a Melt Index (MI) of 0.25g/10min, manufactured by seashell brand No. 2420D; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 1.0g/10min, a designation of 2010MA at 25% by mass, a Melt Index (MI) of 0.2g/10min, a designation of XP6026ML at 50% by mass, manufactured by Exxon Mobil; and (3) the anti-aging master batch (self-made) is the same as the inner layer in raw material composition and preparation method.
The coating layer is a coating liquid dry matter prepared from inorganic aluminum sol, silica sol and organic mixed glue solution.
The coating layer is prepared from a coating liquid stock solution with the brand number of TG-150, which is produced by Nippon bamboo grease Co.
Adding the weighed coating liquid stock solution into a stainless steel tank, adding deionized water, stirring uniformly, standing for 20 minutes, pumping into a liquid hanging tank for later use, wherein the dry matter content of the coating layer is 0.20g/m 2 。
The preparation method of the coating type polyolefin light conversion dustproof high-heat-preservation long-acting dripping fog dispersal shed film described in the embodiment 1 comprises the following steps: the coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog dispersal shed film is prepared by respectively mixing and stirring the component materials of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer uniformly, adding the mixture into a five-layer co-extrusion extruder, and carrying out melt plastication blow molding, cooling setting, traction, corona, coating liquid impregnation, drying, edge welding, seam cutting, code spraying identification and folding.
The specification of the prepared product is 12000/0.12mm; the layer thickness ratio of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer is 1; the blow-up ratio was 1.7. In the five-layer co-extrusion unit, the temperatures of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer extruder are all 150-200 ℃, and the temperatures of a machine neck, a die head bottom and a die ring are 200-215 ℃; the temperature of each zone of the oven is 85-102 ℃.
Table 1 example 1 preparative process conditions
The coating type light-dimming dust-proof high-heat-preservation long-acting dripping fog-dispersal shed film prepared in the embodiment 1 has the light transmittance of 92.3 percent, the haze of 10.7 percent and the dripping fog-dispersal dust-proof function duration of 7 years. Adding a light conversion agent GTR650, so that the greenhouse film has the function of converting part of green light excitation spectrum 580nm into red light emission spectrum 650nm which is more beneficial to plant growth, and the illumination environment in the greenhouse is improved, thereby improving the sugar content and vitamin C content quality of crops, having good coloring and high yield; the dustproof master batch is added to reduce the friction coefficient of the surface of the greenhouse film to 0.15, the greenhouse film is bright as new after being washed by wind and rain, and the reduction of the light transmittance is not obvious; the high heat-insulating resin EVA and the heat-insulating master batch are added, so that the transmittance of infrared rays radiated outwards in the greenhouse at night is low, and the lowest temperature at night is improved compared with the contrast ratio of 3-4. The greenhouse film prepared in example 1 has been applied to the field of agricultural and big test bases of Zhelu jiazhuang and Gaozhuang Shandong under Laiwu for 10 months in 2018, the yield of the planted strawberries (sweet treasure) is increased by 25.6%, the strawberries are picked 10 days in advance, and the quality of the fruits is good. The greenhouse film prepared in the example 1 is determined to be a film special for strawberries by expert production measurement and evaluation.
Example 2
The coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dispersal shed film described in the embodiment 2 comprises an inner layer, a secondary inner layer, a middle layer, a secondary outer layer, an outer layer and a coating layer; wherein the inner layer is a dustproof aging-resistant layer and consists of the following raw materials in percentage by mass: 25% of low-density polyethylene (LDPE), 60% of metallocene linear low-density polyethylene (mLLDPE), 10% of ageing-resistant master batch and 5% of dustproof master batch; the secondary inner layer is a heat-insulating and anti-aging layer and comprises the following raw materials in percentage by mass: 78% of ethylene-vinyl acetate copolymer resin (EVA), 10% of anti-aging master batch and 12% of barrier heat-insulation master batch; the middle layer is a high-heat-insulation barrier layer and consists of the following raw materials in percentage by mass: 85% of ethylene-vinyl acetate copolymer resin (EVA), 7% of anti-aging master batch and 8% of barrier heat-insulation master batch; the secondary outer layer is a light conversion layer and consists of the following raw materials in percentage by mass: 28% of low-density polyethylene (LDPE), 23% of linear low-density polyethylene (LLDPE), 36% of metallocene linear low-density polyethylene (mLLDPE), 10% of light conversion master batch and 3% of ageing-resistant master batch; the outer layer is an ageing-resistant layer and consists of the following raw materials in percentage by mass: 21% of low-density polyethylene (LDPE), 73% of metallocene linear low-density polyethylene (mLLDPE) and 6% of ageing-resistant master batch; the coating layer is a long-acting dripping fog-dissipation layer and consists of the following raw materials in percentage by mass: 8% of coating liquid stock solution and 92% of deionized water.
The Melt Index (MI) of the low-density polyethylene (LDPE) in the inner layer raw material is 0.25g/10min, and the mark is 2420D, and the middle sea shell is manufactured; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 1.0g/10min under the designation 2010MC, 30% by mass, manufactured by Exxon Mobil; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min, designation XP6026ML, 30% by mass, manufactured by Exxon; aging resistant master batch (self-made); the dustproof master batch is marked by EFT997, manufactured by Tianjin research and development company.
The raw material composition and preparation method of the anti-aging master batch in the inner layer are the same as those of the inner layer in example 1.
Ethylene-vinyl acetate copolymer resin (EVA) in the raw material of the secondary inner layer, the VA content is 12%, the Melt Index (MI) is 0.5g/10min, the mark FL00012, produced by Exon; the raw material composition and the preparation method of the anti-aging master batch in the secondary inner layer are the same as those of the inner layer in the example 1; the raw material components and the preparation method of the blocking and heat-insulating master batch in the secondary inner layer are the same as those of the secondary inner layer in the example 1.
Ethylene-vinyl acetate copolymer resin (EVA) in the middle layer raw material, the VA content is 17.5%, the Melt Index (MI) is 0.37g/10min, the mark is FL00018, produced by Exxon Mobil; the raw material composition and the preparation method of the anti-aging master batch are the same as those of the inner layer in the example 1; the raw material composition and the preparation method of the blocking heat-preservation master batch are the same as those of the inner layer of the second time in the embodiment 1.
The secondary outer layer is a light conversion layer, the Melt Index (MI) of Low Density Polyethylene (LDPE) in the secondary outer layer is 0.25g/10min, and the mark is 2420D made of sea shell; the Melt Index (MI) of Linear Low Density Polyethylene (LLDPE) is 0.85g/10min, the mark is 9085, and Tianjin combined production is carried out; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min, manufactured by Exxon Mobil under the brand XP6026 ML.
The light conversion master batch in the secondary outer layer comprises the following raw materials in percentage by mass: 50% of Low Density Polyethylene (LDPE), 39.5% of Linear Low Density Polyethylene (LLDPE), 10% of light conversion agent and 0.5% of antioxidant; wherein: low Density Polyethylene (LDPE) 2102TN00 ziegler petrochemical; powdered Linear Low Density Polyethylene (LLDPE) 7042, olearu petrochemical; the light conversion agent is green-to-red GTR-650 II and violet-to-blue VTB440 which are compounded according to the mass ratio (7).
The preparation method of the light conversion master batch comprises the following steps: accurately metering a compound of Low Density Polyethylene (LDPE) 2102TN00, powdery Linear Low Density Polyethylene (LLDPE) 7042, light conversion agent of green-to-red GTR-650 II and purple-to-blue VTB440 and antioxidant B225 into an internal mixer, kneading and plasticizing, feeding into a single-screw extrusion granulator through an open mill, carrying out hot granulation, and carrying out air cooling drying to obtain the light conversion master batch for later use.
Wherein the temperature of the internal mixer is 136 +/-1 ℃, the plasticizing time is 19 minutes, and the temperature of each section is 140-170 ℃ (170 ℃ in the first section, 160 ℃ in the second section and 140 ℃ in the third section).
The raw material components and preparation method of the anti-aging master batch in the secondary outer layer are the same as those of the inner layer in example 1.
The Melt Index (MI) of the Low Density Polyethylene (LDPE) in the outer layer is 0.25g/10min, and the mark is 2420D; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 1.0g/10min under the designation 2010MA at a mass ratio of 25%, and metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min under the designation XP6026ML at a mass ratio of 48%, manufactured by Exxon; an aging resistant masterbatch (self-made) having the same raw material composition and preparation method as the inner layer of example 1.
The coating layer is a dry coating solution prepared from inorganic aluminum sol, silica sol and organic mixed glue solution.
The coating layer is prepared from a coating liquid stock solution with the brand of TG-150, which is produced by Nippon bamboo grease Co.
Adding the weighed coating solution stock solution into a stainless steel tank, adding deionized water, stirring uniformly, standing for 20 minutes, and pumping into a liquid hanging tank for later use, wherein the dry matter content of the coating layer is 0.21g/m 2 。
The preparation method of the coating type polyolefin light conversion, dustproof, high-heat-preservation, long-acting dripping and defogging shed film described in the embodiment 2 comprises the following steps: the coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog dispersal shed film is prepared by respectively mixing and stirring the component materials of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer uniformly, adding the mixture into a five-layer co-extrusion extruder, and carrying out melt plastication blow molding, cooling setting, traction, corona, coating liquid impregnation, drying, edge welding, seam cutting, code spraying identification and folding.
The specification of the prepared product is 12000/0.12mm; 1, the layer thickness ratio of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer is 1; the blow-up ratio was 1.7. In the five-layer co-extrusion unit, the temperatures of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer extruder are all 150-200 ℃, and the temperatures of a machine neck, a die head bottom and a die ring are 200-215 ℃; the temperature of each zone of the oven is 85-102 ℃.
Example 2 the process conditions were the same as in example 1 of table 1.
The coated light-dimming dust-proof high-heat-preservation long-acting dripping fog-dissipation greenhouse film prepared in the embodiment 2 has the light transmittance of 92.6%, the haze of 10.3% and the lasting period of the dripping fog-dissipation dust-proof function of 7 years. Adding a light conversion agent green-red GTR-650 II and purple-blue VTB440 for compounding, so that the greenhouse film has the functions of converting part of green light excitation spectrum to 500-580nm into red light emission spectrum 650nm which is more beneficial to plant growth, and simultaneously converting part of ultraviolet light excitation spectrum to 290-370nm into blue emission spectrum 440nm, thereby improving the illumination environment in the greenhouse, and further improving the content of anthocyanin in the eggplant, good coloring and high yield; the dustproof master batch is added to ensure that the greenhouse film is bright as new after being washed by wind, blowing and rain, and the reduction of the light transmittance is not obvious. The high heat-insulating resin EVA and the heat-insulating master batch are added, so that the transmittance of infrared rays radiated outwards in the greenhouse at night is low, and the lowest temperature at night is improved compared with the contrast ratio of 3-4. The greenhouse film prepared in example 2 has been demonstrated in the field application of the agricultural big test base of Zhengu Jiazhuang and Gaozhuang Shandong under Laiwu in 2018, the yield of the planted eggplants ("black commander") is increased by 22.80%, the eggplants are picked in advance for 11 days, and the fruit quality is good. The greenhouse film prepared in the embodiment 2 is determined to be a film special for eggplants through expert production measurement and evaluation.
Example 3
The coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dispersal shed film described in the embodiment 3 comprises an inner layer, a secondary inner layer, a middle layer, a secondary outer layer, an outer layer and a coating layer; wherein the inner layer is a dustproof aging-resistant layer and consists of the following raw materials in percentage by mass: 20% of low-density polyethylene (LDPE), 65% of metallocene linear low-density polyethylene (mLLDPE), 9% of anti-aging master batch and 6% of dustproof master batch; the secondary inner layer is a heat-insulating and anti-aging layer and comprises the following raw materials in percentage by mass: 85% of ethylene-vinyl acetate copolymer resin (EVA), 8% of anti-aging master batch and 7% of heat-insulating master batch; the middle layer is a high-heat-insulation barrier layer and consists of the following raw materials in percentage by mass: 83% of ethylene-vinyl acetate copolymer resin (EVA), 8% of anti-aging master batch and 9% of heat-insulating master batch; the secondary outer layer is a light conversion layer and consists of the following raw materials in percentage by mass: 27% of low-density polyethylene (LDPE), 21% of linear low-density polyethylene (LLDPE), 40% of metallocene linear low-density polyethylene (mLLDPE), 8% of light conversion master batch and 4% of ageing-resistant master batch; the outer layer is an aging-resistant layer and comprises the following raw materials in percentage by mass: 25% of low-density polyethylene (LDPE), 67% of metallocene linear low-density polyethylene (mLLDPE) and 8% of ageing-resistant master batch; the coating layer is a long-acting dripping fog-dissipation layer and consists of the following raw materials in percentage by mass: 8% of coating liquid stock solution and 92% of deionized water.
The Melt Index (MI) of the Low Density Polyethylene (LDPE) in the inner layer is 0.25g/10min, and the mark is 2420D, and the middle sea shell is manufactured; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 1.0g/10min under the designation 2010MC, 30% by mass, manufactured by Exxon Mobil; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min and a designation XP6026ML, 35% by mass, manufactured by Exxon; aging resistant master batch (self-made); the dustproof master batch is marked by EFT997, manufactured by Tianjin research and development company.
The components and preparation method of the anti-aging master batch for the inner layer are the same as those of the inner layer in example 1.
Ethylene-vinyl acetate copolymer resin (EVA) in the secondary inner layer, the VA content is 12%, the Melt Index (MI) is 0.5g/10min, the mark is FL00012, produced by Exxon; the raw material composition and the preparation method of the anti-aging master batch in the secondary inner layer are the same as those of the inner layer in the example 1; the raw material composition and preparation method of the blocking and heat-insulating master batch in the secondary inner layer are the same as those of the secondary inner layer in the example 1.
Ethylene-vinyl acetate copolymer resin (EVA) in the middle layer, the VA content is 17.5%, the Melt Index (MI) is 0.37g/10min, the mark is FL00018, produced by Exxon Mobil; the raw material composition and the preparation method of the anti-aging master batch are the same as those of the inner layer in the example 1; the raw material composition and the preparation method of the barrier heat-insulation master batch are the same as those of the secondary inner layer in the example 1.
The Melt Index (MI) of the Low Density Polyethylene (LDPE) in the secondary outer layer is 0.25g/10min, and is manufactured by concha haliotidis in the mark 2420D; the Melt Index (MI) of Linear Low Density Polyethylene (LLDPE) is 0.85g/10min, and the mark is 9085 Tianjin combined production; metallocene linear low density polyethylene (m-LLDPE) has a Melt Index (MI) of 0.2g/10min, manufactured by Exxon Mobil under the trademark XP6026 ML.
The light conversion master batch in the secondary outer layer comprises the following raw materials in percentage by mass: 50% of Low Density Polyethylene (LDPE), 39.5% of Linear Low Density Polyethylene (LLDPE), 10% of light conversion agent and 0.5% of antioxidant; wherein: low Density Polyethylene (LDPE) 2102TN00 zilu petrochemical manufacture; powdered Linear Low Density Polyethylene (LLDPE) 7042, olearu petrochemical; the light conversion agent is green-to-red GTR-650 II, purple-to-blue VTB440 and purple-to-red VTR660 which are compounded according to the mass ratio (3.
The preparation method of the light conversion master batch comprises the following steps: accurately metering and adding low-density polyethylene (LDPE) 2102TN00, powdery linear low-density polyethylene (LLDPE) 7042, light conversion agent green-to-red GTR-650 II, purple-to-blue VTB440, purple-to-red VTR660 and antioxidant B225 into an internal mixer for kneading and plasticizing, feeding into a single-screw extrusion granulator through an open mill, carrying out hot granulation, and carrying out air cooling drying to prepare the light conversion master batch for later use.
Wherein, the temperature of the internal mixer is 137 +/-1 ℃, the plasticizing time is 20 minutes, and the temperature of each section is 140-170 ℃ (170 ℃ in the first section, 160 ℃ in the second section and 140 ℃ in the third section).
The raw material components and preparation method of the anti-aging master batch in the secondary outer layer are the same as those of the inner layer in the example 1.
The Melt Index (MI) of the Low Density Polyethylene (LDPE) in the outer layer is 0.25g/10min, and the mark is 2420D; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 1.0g/10min under the designation 2010MA at a mass ratio of 25%, and metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min under the designation XP6026ML at a mass ratio of 42%, manufactured by Exxon; an aging resistant masterbatch (self-made) having the same raw material composition and preparation method as the inner layer of example 1.
The coating layer is a coating liquid dry matter prepared from inorganic aluminum sol, silica sol and organic mixed glue solution.
The coating layer is prepared from a coating liquid stock solution with the brand of TG-150, which is produced by Nippon bamboo grease Co.
Adding the weighed coating solution stock solution into a stainless steel tank, adding deionized water, stirring uniformly, standing for 20 minutes, and pumping into a liquid suspension tank for later use, wherein the dry matter content of the coating layer is 0.19g/m 2 。
The preparation method of the coating type polyolefin light conversion, dustproof, high-heat-preservation, long-acting dripping and fog dispersal greenhouse film described in the embodiment 3 comprises the following steps: the coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dissipation shed film is prepared by respectively mixing and stirring the component materials of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer uniformly, adding the mixture into a five-layer co-extrusion extruder, and carrying out melt plasticizing blow molding, cooling and shaping, traction, corona, coating liquid impregnation, drying, edge welding, seam cutting, code spraying and marking and folding.
The specification of the prepared product is 12000/0.12mm; the layer thickness ratio of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer is 1; the blow-up ratio was 1.7. In the five-layer co-extrusion unit, the temperatures of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer extruder are all 150-200 ℃, and the temperatures of a machine neck, a die head bottom and a die ring are 200-215 ℃; the temperature of each zone of the oven is 85-102 ℃.
Example 3 the process conditions were the same as in example 1 of table 1.
The coated light-dimming dust-proof high-heat-preservation long-acting dripping fog-dissipation greenhouse film prepared in the embodiment 3 has the light transmittance of 92.1%, the haze of 10.6% and the lasting period of the dripping fog-dissipation dust-proof function of 7 years. Adding light conversion agent of green-to-red GTR-650 II, purple-to-blue VTB440 and purple-to-red VTR660 for compounding, so that the greenhouse film has the functions of converting part of green light excitation spectrum to 500-580nm into red light emission spectrum 650nm which is more beneficial to plant growth, and converting part of ultraviolet light excitation spectrum to 290-370nm into blue light emission spectrum to 440nm and red light emission spectrum to 660nm, thereby enhancing the irradiation intensity of blue light and red light, improving the illumination environment in the greenhouse, improving the vitamin C content, being good in coloring and high in yield; the dustproof master batch is added to ensure that the greenhouse film is bright as new after being blown by wind and rain, and the reduction of the light transmittance is not obvious. High-heat-preservation resin EVA and heat-preservation master batch are added, so that the transmittance of infrared rays radiated outwards in the greenhouse at night is low, and the lowest temperature at night is improved compared with the contrast ratio of 3-4. The greenhouse film prepared in example 3 has been applied to the field of agricultural big test base of Odongtang and Odongtang in Chengkou under Laiwu in 2018, demonstrated that the yield of the planted tomatoes ("Xianfeng No. 4") is increased by 21.80%, the tomatoes are picked in advance for 11 days, and the taste and the quality of the fruits are good. The greenhouse film prepared in the embodiment 3 is determined to be a film special for tomatoes by expert evaluation.
Example 4
The coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dissipation greenhouse film described in the embodiment 4 comprises an inner layer, a secondary inner layer, a middle layer, a secondary outer layer, an outer layer and a coating layer; wherein the inner layer is a dustproof aging-resistant layer and consists of the following raw materials in percentage by mass: 23% of low-density polyethylene (LDPE), 65% of metallocene linear low-density polyethylene (mLLDPE), 8% of anti-aging master batch and 4% of dustproof master batch; the secondary inner layer is a heat-insulating and anti-aging layer and comprises the following raw materials in percentage by mass: 84% of ethylene-vinyl acetate copolymer resin (EVA), 8% of anti-aging master batch and 8% of barrier heat-insulation master batch; the middle layer is a high-heat-insulation barrier layer and comprises the following raw materials in percentage by mass: 80% of ethylene-vinyl acetate copolymer resin (EVA), 10% of anti-aging master batch and 10% of barrier heat-insulation master batch; the secondary outer layer is a light conversion layer and consists of the following raw materials in percentage by mass: 29% of Low Density Polyethylene (LDPE), 20% of Linear Low Density Polyethylene (LLDPE), 37% of metallocene linear low density polyethylene (mLLDPE), 9% of light conversion master batch and 5% of ageing-resistant master batch; the outer layer is an ageing-resistant layer and consists of the following raw materials in percentage by mass: 22% of low-density polyethylene (LDPE), 70% of metallocene linear low-density polyethylene (mLLDPE) and 8% of ageing-resistant master batch; the coating layer is a long-acting dripping fog-dissipation layer and consists of the following raw materials in percentage by mass: 8% of coating liquid stock solution and 92% of deionized water.
The Melt Index (MI) of the Low Density Polyethylene (LDPE) in the inner layer is 0.25g/10min, and the mark is 2420D, and the middle sea shell is manufactured; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 1.0g/10min, a designation 2010MC, 25% by mass, manufactured by Exxon Mobil; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min and a designation XP6026ML, mass ratio of 40%, manufactured by Exxon; aging resistant master batch (self-made); the dustproof master batch is marked by EFT997, manufactured by Tianjin research and development company.
The raw material composition and preparation method of the anti-aging master batch are the same as those of the inner layer in example 1.
Ethylene-vinyl acetate copolymer resin (EVA) in the secondary inner layer, the VA content is 12%, the Melt Index (MI) is 0.5g/10min, the mark is FL00012, produced by Exxon; the raw material composition and the preparation method of the anti-aging master batch in the secondary inner layer are the same as those of the inner layer in the example 1; the raw material composition and preparation method of the blocking and heat-insulating master batch in the secondary inner layer are the same as those of the secondary inner layer in the example 1.
Ethylene-vinyl acetate copolymer resin (EVA) in the middle layer, the VA content is 17.5%, the Melt Index (MI) is 0.37g/10min, the mark is FL00018, produced by Exxon Mobil; the raw material composition and the preparation method of the anti-aging master batch are the same as those of the inner layer in the example 1; the raw material composition and the preparation method of the blocking heat-preservation master batch are the same as those of the inner layer of the second time in the embodiment 1.
The Melt Index (MI) of the Low Density Polyethylene (LDPE) in the second outer layer is 0.25g/10min, made of concha Shell in the designation 2420D; the Melt Index (MI) of Linear Low Density Polyethylene (LLDPE) is 0.85g/10min, the mark is 9085, and Tianjin combined production is carried out; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min, manufactured by Exxon Mobil under the trademark XP6026 ML; the raw material composition and the preparation method of the light conversion master batch are the same as those of the outer layer of the time of the example 3; the raw material composition and preparation method of the anti-aging master batch are the same as those of the inner layer in example 1.
The Melt Index (MI) of the Low Density Polyethylene (LDPE) in the outer layer is 0.25g/10min, and the mark is 2420D; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 1.0g/10min under the designation 2010MA at a mass ratio of 25%, and metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min under the designation XP6026ML at a mass ratio of 45%, manufactured by Exxon; an aging resistant masterbatch (self-made) having the same raw material composition and preparation method as the inner layer of example 1.
The coating layer is a coating liquid dry matter prepared from inorganic aluminum sol, silica sol and organic mixed glue solution.
The coating liquid stock solution was TG-150, manufactured by Nippon bamboo fat Co.
Adding the weighed coating liquid stock solution into a stainless steel tank, adding deionized water, stirring uniformly, standing for 20 minutes, pumping into a liquid hanging tank for later use, wherein the dry matter content of the coating layer is 0.21g/m 2 。
The preparation method of the coating type polyolefin light conversion, dustproof, high-heat-preservation, long-acting dripping and defogging shed film described in the embodiment 4 comprises the following steps: the coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog dispersal shed film is prepared by respectively mixing and stirring the component materials of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer uniformly, adding the mixture into a five-layer co-extrusion extruder, and carrying out melt plastication blow molding, cooling setting, traction, corona, coating liquid impregnation, drying, edge welding, seam cutting, code spraying identification and folding.
The specification of the prepared product is 12000/0.12mm; the layer thickness ratio of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer is 1; the blow-up ratio was 1.7. In the five-layer co-extrusion unit, the temperatures of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer extruder are all 150-200 ℃, and the temperatures of a machine neck, a die head bottom and a die ring are 200-215 ℃; the temperature of each zone of the oven is 85-102 ℃.
Example 4 the process conditions were the same as in example 1 of table 1.
The coated light-dimming dust-proof high-heat-preservation long-acting dripping fog-dissipation greenhouse film prepared in the embodiment 4 has the light transmittance of 92.4%, the haze of 11.1% and the lasting period of the dripping fog-dissipation dust-proof function of 7 years. Adding light conversion agents which are green-to-red GTR-650 II, purple-to-blue VTB440 and purple-to-red VTR660 for compounding, so that the greenhouse film has the functions of converting part of green light excitation spectrum 500-580nm into red light emission spectrum 650nm which is more beneficial to plant growth, and converting part of ultraviolet light excitation spectrum 290-370nm into blue light emission spectrum 440nm and red light emission spectrum 660nm, thereby enhancing the irradiation intensity of blue light and red light, improving the illumination environment in the greenhouse, improving the vitamin C content, being good in coloring and high in yield; the dustproof master batch is added to ensure that the greenhouse film is bright as new after being blown by wind and rain, and the reduction of the light transmittance is not obvious. The high heat-insulating resin EVA and the heat-insulating master batch are added, so that the transmittance of infrared rays radiated outwards in the greenhouse at night is low, and the lowest temperature at night is improved compared with the contrast ratio of 3-4. The greenhouse film prepared in example 4 is applied to the field of agricultural and big test bases of Odongtungrana and Gaozhuangshandong under Laiwu in 2018, the yield of planted sweet peppers ("Katelin") is increased by 29.70%, the sweet peppers are picked in advance for 9 days, and the taste and the quality of the fruits are good. The greenhouse film prepared in the embodiment 4 is determined to be a film special for sweet peppers through expert evaluation.
Example 5
The coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dispersal shed film described in the embodiment 5 comprises an inner layer, a secondary inner layer, a middle layer, a secondary outer layer, an outer layer and a coating layer; wherein the inner layer is a dustproof aging-resistant layer and consists of the following raw materials in percentage by mass: 18% of low-density polyethylene (LDPE), 68% of metallocene linear low-density polyethylene (mLLDPE), 9% of anti-aging master batch and 5% of dustproof master batch; the secondary inner layer is a heat-insulating and anti-aging layer and comprises the following raw materials in percentage by mass: 83% of ethylene-vinyl acetate copolymer resin (EVA), 9% of anti-aging master batch and 8% of heat-insulating master batch; the middle layer is a high-heat-insulation barrier layer and comprises the following raw materials in percentage by mass: 77% of ethylene-vinyl acetate copolymer resin (EVA), 10% of anti-aging master batch and 13% of heat-insulating master batch; the secondary outer layer is a light conversion layer and consists of the following raw materials in percentage by mass: 27% of low-density polyethylene (LDPE), 21% of linear low-density polyethylene (LLDPE), 38% of metallocene linear low-density polyethylene (mLLDPE), 9% of light conversion master batch and 5% of ageing-resistant master batch; the outer layer is an ageing-resistant layer and consists of the following raw materials in percentage by mass: 25% of low-density polyethylene (LDPE), 68% of metallocene linear low-density polyethylene (mLLDPE) and 7% of ageing-resistant master batch; the coating layer is a long-acting dripping fog-dissipation layer and consists of the following raw materials in percentage by mass: 8% of coating liquid stock solution and 92% of deionized water.
The Melt Index (MI) of the Low Density Polyethylene (LDPE) in the inner layer is 0.25g/10min, and the mark is 2420D, and the middle sea shell is manufactured; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 1.0g/10min under the designation 2010MC, 30% by mass, manufactured by Exxon Mobil; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min, brand XP6026ML, 38% by mass, manufactured by Exxon; aging resistant master batch (self-made); the dustproof master batch is marked by EFT997, manufactured by Tianjin research and development company.
The raw material composition and preparation method of the anti-aging master batch are the same as those of the inner layer in example 1.
Ethylene-vinyl acetate copolymer resin (EVA) in the secondary inner layer, the VA content is 12%, the Melt Index (MI) is 0.5g/10min, the mark is FL00012, produced by Exxon; the raw material composition and the preparation method of the anti-aging master batch in the secondary inner layer are the same as those of the inner layer in the example 1; the raw material components and the preparation method of the blocking and heat-insulating master batch in the secondary inner layer are the same as those of the secondary inner layer in the example 1.
Ethylene-vinyl acetate copolymer resin (EVA) in the middle layer, the VA content is 17.5%, the Melt Index (MI) is 0.37g/10min, the mark is FL00018, produced by Exxon Mobil; the raw material composition and the preparation method of the anti-aging master batch are the same as those of the inner layer in the example 1; the raw material composition and the preparation method of the blocking heat-insulation master batch are the same as those of the inner layer of the second time in the embodiment 1.
The Melt Index (MI) of the Low Density Polyethylene (LDPE) in the second outer layer is 0.25g/10min, made of concha Shell in the designation 2420D; the Melt Index (MI) of Linear Low Density Polyethylene (LLDPE) is 0.85g/10min, the mark is 9085, and Tianjin combined production is carried out; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min, manufactured by Exxon Mobil under the brand XP6026 ML; the raw material composition and the preparation method of the light conversion master batch are the same as those of the outer layer of the time of the example 3; the raw material components and the preparation method of the anti-aging master batch are the same as those of the inner layer in the example 1.
The Melt Index (MI) of the Low Density Polyethylene (LDPE) in the outer layer is 0.25g/10min, and the mark is 2420D; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 1.0g/10min under the designation 2010MA at a mass ratio of 25%, and metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min under the designation XP6026ML at a mass ratio of 43%, manufactured by Exxon Mobil; an aging resistant masterbatch (self-made) having the same raw material composition and preparation method as the inner layer of example 1.
The coating layer is a coating liquid dry matter prepared from inorganic aluminum sol, silica sol and organic mixed glue solution.
The coating liquid stock solution was TG-150, manufactured by Nippon bamboo fat Co.
Adding the weighed coating liquid stock solution into a stainless steel tank, adding deionized water, stirring uniformly, standing for 20 minutes, pumping into a liquid hanging tank for later use, wherein the dry matter content of the coating layer is 0.20g/m 2 。
The preparation method of the coating type polyolefin light conversion, dustproof, high-heat-preservation, long-acting dripping and defogging shed film described in the embodiment 5 comprises the following steps: the coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dissipation shed film is prepared by respectively mixing and stirring the component materials of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer uniformly, adding the mixture into a five-layer co-extrusion extruder, and carrying out melt plasticizing blow molding, cooling and shaping, traction, corona, coating liquid impregnation, drying, edge welding, seam cutting, code spraying and marking and folding.
The specification of the prepared product is 12000/0.12mm; 1, the layer thickness ratio of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer is 1; the blow-up ratio was 1.7. In the five-layer co-extrusion unit, the temperatures of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer extruder are all 150-200 ℃, and the temperatures of a machine neck, a die head bottom and a die ring are 200-215 ℃; the temperature of each zone of the oven is 85-102 ℃.
Example 5 the process conditions were the same as in example 1 of table 1.
The coating type light-dimming dust-proof high-heat-preservation long-acting dripping fog-dispersal shed film prepared in the embodiment 5 has the light transmittance of 92.0%, the haze of 11.4% and the lasting period of the dripping fog-dispersal heat-preservation dust-proof function of 7 years. Adding light conversion agents which are green to red GTR-650, purple to blue VTB440 and purple to red VTR660 for compounding, so that the greenhouse film has the functions of converting part of green light excitation spectrum 500-580nm into red light emission spectrum 650nm which is more beneficial to plant growth, and converting part of ultraviolet light excitation spectrum 290-370nm into blue light emission spectrum 440nm and red light emission spectrum 660nm, thereby enhancing the irradiation intensity of blue light and red light, improving the illumination environment in the greenhouse, improving the vitamin C content, being good in coloring and high in yield; the dustproof master batch is added to ensure that the greenhouse film is bright as new after being blown by wind and rain, and the reduction of the light transmittance is not obvious. The high heat-insulating resin EVA and the heat-insulating master batch are added, so that the transmittance of infrared rays radiated outwards in the greenhouse at night is low, and the lowest temperature at night is improved compared with the contrast ratio of 3-4. The greenhouse film prepared in example 5 is applied to the field of the vegetable research institute experimental base of Ningxia Shizuishan academy of agricultural sciences in 2018 for 10 months and 2019 for 10 months, and the comparison between the field and the comparative example proves that the yield of the planted melons (the "sheep horn honey") is increased by 28.30%, the melons are picked 10-12 days in advance, the sugar degree of the fruits is 16.7-23.5%, and the taste quality is good. The greenhouse film prepared in the embodiment 5 is determined to be a special film for melons through expert evaluation.
Comparative example 1
The coating type polyolefin light-conversion high-heat-insulation long-acting dripping fog dispersal shed film described in the comparative example 1 comprises an inner layer, a secondary inner layer, a middle layer, a secondary outer layer, an outer layer and a coating layer; wherein the inner layer is an ageing-resistant layer and consists of the following raw materials in percentage by mass: 23% of low-density polyethylene (LDPE), 67% of metallocene linear low-density polyethylene (mLLDPE) and 10% of ageing-resistant master batch; the secondary inner layer is a heat-insulating and anti-aging layer and comprises the following raw materials in percentage by mass: 80% of ethylene-vinyl acetate copolymer resin (EVA), 10% of anti-aging master batch and 10% of barrier heat-insulation master batch; the middle layer is a high-heat-insulation barrier layer and comprises the following raw materials in percentage by mass: 75% of ethylene-vinyl acetate copolymer resin (EVA), 10% of anti-aging master batch and 15% of barrier heat-insulation master batch; the secondary outer layer is a light conversion layer and consists of the following raw materials in percentage by mass: 25% of low-density polyethylene (LDPE), 25% of linear low-density polyethylene (LLDPE), 35% of metallocene linear low-density polyethylene (mLLDPE), 12% of light conversion master batch and 3% of ageing-resistant master batch; the outer layer is an aging-resistant layer and comprises the following raw materials in percentage by mass: 20% of Low Density Polyethylene (LDPE), 75% of metallocene linear low density polyethylene (mLLDPE), and 5% of ageing-resistant master batch; the coating layer is a long-acting dripping fog-dissipation layer and consists of the following raw materials in percentage by mass: 8% of coating liquid stock solution and 92% of deionized water.
The inner layer is an ageing-resistant layer, and the inner layer comprises the following raw materials: low Density Polyethylene (LDPE) has a Melt Index (MI) of 0.25g/10min, designation 2420D, manufactured by Mediterranean Shell; metallocene linear low density polyethylene (m-LLDPE) with a Melt Index (MI) of 1.0g/10min, no. 2010MC, 30% by mass, manufactured by Exxon Mobil; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min, brand XP6026ML, mass fraction of 37%, manufactured by Exxon; aging resistant master batch (self-made); the raw material composition and preparation method of the aging-resistant master batch are the same as those of example 1 and are not described again.
Further, the raw material composition of the sub-inner layer, the middle layer, the sub-outer layer, the outer layer and the coating layer was the same as in example 1.
The preparation method of the coating type polyolefin light conversion high-heat-preservation long-acting dripping fog dispersal shed film in the comparative example 1 is the same as that of the example 1, and is not described again.
The difference between the comparative example 1 and the example 1 is that the dustproof master batch is not added to the inner layer, the greenhouse film does not have a dustproof function, dust is adsorbed on the surface of the greenhouse, the greenhouse film is not washed by rain and snow and is not clean, the light transmittance is obviously reduced due to direct influence, the light transmittance is reduced by 4.1 percent after 12 months, and other light conversion, high heat preservation, dripping and fog dissipation performances are equivalent.
The initial light transmission was 90.3%, the haze was 15.7%, and the light transmission at 24 months decreased by 7.9%. In the greenhouse film prepared in comparative example 1 and example 1, a splicing greenhouse control field application test is carried out at a Zhenlu Jiazhuang Shandong agricultural large test base below Laiwu for 10 months in 2018 years, yield is reduced by 4.73% in 3 months in 2019 years after strawberry (Tianbao) planting and compared with that in example 1, and picking period is prolonged by 3 days; the yield of the tomatoes planted in the second crop is reduced by 7.16 percent compared with that of the tomatoes planted in the example 1.
Comparative example 2
The coating type polyolefin dustproof high-heat-preservation long-acting dripping fog-dispersal shed film in the comparative example 2 comprises an inner layer, a secondary inner layer, a middle layer, a secondary outer layer, an outer layer and a coating layer; wherein the inner layer is a dustproof aging-resistant layer and consists of the following raw materials in percentage by mass: 25% of low-density polyethylene (LDPE), 60% of metallocene linear low-density polyethylene (mLLDPE), 10% of ageing-resistant master batch and 5% of dustproof master batch; the secondary inner layer is a heat-insulating and anti-aging layer and comprises the following raw materials in percentage by mass: 78% of ethylene-vinyl acetate copolymer resin (EVA), 10% of anti-aging master batch and 12% of barrier heat-insulation master batch; the middle layer is a high-heat-insulation barrier layer and consists of the following raw materials in percentage by mass: 85% of ethylene-vinyl acetate copolymer resin (EVA), 7% of anti-aging master batch and 8% of barrier heat-insulation master batch; the secondary outer layer is an aging-resistant layer, and the raw materials comprise polyethylene and an aging-resistant master batch; the outer layer is an ageing-resistant layer and consists of the following raw materials in percentage by mass: 21% of low-density polyethylene (LDPE), 73% of metallocene linear low-density polyethylene (mLLDPE) and 6% of ageing-resistant master batch; the coating layer is a long-acting dripping defogging layer and consists of the following raw materials in percentage by mass: 8% of coating liquid stock solution and 92% of deionized water.
The raw material composition of the inner layer, the secondary inner layer, the middle layer, the outer layer and the coating layer is the same as that of the embodiment 2.
The secondary outer layer is an anti-aging layer and consists of the following raw materials in percentage by mass: 30% of low-density polyethylene (LDPE), 25% of linear low-density polyethylene (LLDPE), 40% of metallocene linear low-density polyethylene (mLLDPE) and 5% of ageing-resistant master batch.
The raw materials of the secondary outer layer are as follows: low Density Polyethylene (LDPE) has a Melt Index (MI) of 0.25g/10min, manufactured under the designation 2420D seashell brand; the Melt Index (MI) of Linear Low Density Polyethylene (LLDPE) is 0.85g/10min, the mark is 9085, and Tianjin combined production is carried out; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min, manufactured by Exxon Mobil under the trademark XP6026 ML; the raw material composition and the preparation method of the aging-resistant master batch are the same as those of the example 1.
The preparation method of the coating type polyolefin dustproof high-heat-preservation long-acting dripping fog dispersal shed film in the comparative example 2 is the same as that of the example 1, and is not described again.
The coating type polyolefin dustproof high-heat-preservation long-acting dripping fog-dispersal shed film prepared in the comparative example 2 has the light transmittance of 90.2%, the haze of 15.8% and the dripping fog-dispersal dustproof high-heat-preservation function duration of 7 years.
The difference between the comparative example 2 and the example 2 is that no light conversion master batch is added, the light conversion function is not realized, and the illumination intensity ratio in the shed is obviously reduced. The comparative example 2 and the example 2 are made into a splicing shed, the field application demonstration is carried out in the Shandong agriculture big experiment base of the Zhengujiazhuang Shandong province below Laiwu in 2018 for 10 months, the yield of the planted eggplants (black commander) is reduced by 22.8 percent compared with that of the eggplant in the example 2, the picking period is delayed by 11 days, and the difference is obvious.
Comparative example 3
The coating type polyolefin light-conversion dustproof heat-preservation long-acting dripping fog-dissipation greenhouse film in the comparative example 3 comprises an inner layer, a secondary inner layer, a middle layer, a secondary outer layer, an outer layer and a coating layer; wherein the inner layer is a dustproof aging-resistant layer, and the raw materials comprise polyethylene, dustproof master batch and aging-resistant master batch; the secondary inner layer is a heat-insulating aging-resistant layer, and the raw materials comprise polyethylene resin, an aging-resistant master batch and a blocking heat-insulating master batch; the middle layer is a high-heat-insulation barrier layer, and the raw materials comprise polyethylene, an anti-aging master batch and a barrier heat-insulation master batch; the secondary outer layer is a light conversion layer, and the raw materials comprise polyethylene, light conversion master batch and anti-aging master batch; the outer layer is an ageing-resistant layer, and the raw materials comprise polyethylene and an ageing-resistant master batch; the coating layer is a long-acting dripping fog-eliminating layer.
The raw material composition and the dosage relationship of the inner layer, the secondary outer layer, the outer layer and the coating layer are the same as those of the example 3.
The secondary inner layer is a blocking anti-aging layer and comprises the following raw materials in percentage by mass: 85% of polyethylene, wherein the Low Density Polyethylene (LDPE) accounts for 25%, the Linear Low Density Polyethylene (LLDPE) accounts for 20%, and the metallocene linear low density polyethylene (mLLDPE) accounts for 40%; 8% of ageing resistant master batch and 7% of barrier heat-insulation master batch; wherein: low Density Polyethylene (LDPE) has a Melt Index (MI) of 0.25g/10min, manufactured by seashell brand No. 2420D; the Melt Index (MI) of Linear Low Density Polyethylene (LLDPE) is 0.85g/10min, and the mark is 9085 Tianjin combined production; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min, manufactured by Exxon Mobil under the trademark XP6026 ML; the raw material composition and the preparation method of the anti-aging master batch are the same as those of the inner layer in the example 1; the raw material components and the preparation method of the blocking heat-insulation master batch are the same as those of the inner layer of the second time in the embodiment 1.
The middle layer is a heat insulation layer and consists of the following raw materials in percentage by mass: 83% of polyethylene, wherein 23% of Low Density Polyethylene (LDPE), 20% of Linear Low Density Polyethylene (LLDPE) and 40% of metallocene linear low density polyethylene (mLLDPE); 8% of an anti-aging master batch and 9% of a heat-insulating master batch; wherein: the Melt Index (MI) of Low Density Polyethylene (LDPE) is 0.25g/10min, manufactured by No. 2420D Mediterranean Shell, the Melt Index (MI) of Linear Low Density Polyethylene (LLDPE) is 0.85g/10min, the No. 9085 Tianjin combined production, metallocene linear low density polyethylene (m-LLDPE), the Melt Index (MI) is 0.2g/10min, manufactured by No. XP6026ML Exxon Mobil; the raw material composition and the preparation method of the anti-aging master batch are the same as those of the inner layer in the example 1; the raw material composition and the preparation method of the blocking heat-insulation master batch are the same as those of the inner layer of the second time in the embodiment 1.
The preparation method of the coating type polyolefin light conversion, dust prevention, heat preservation, long-acting dripping and fog dispersal shed film in the comparative example 3 is the same as that in the example 3, and the only difference is that the temperature of the extruder in the secondary layer and the middle layer is set to be 180-200 ℃ as same as that in the inner layer.
The coated light-dimming dust-proof heat-preserving long-acting dripping fog-dispersal shed film prepared in the comparative example 3 has the light transmittance of 90.8 percent, the haze of 17.8 percent and the dripping fog-dispersal dust-proof function duration of 7 years.
Compared with the example 3, the secondary inner layer and the middle layer adopt the polyethylene resin to replace EVA resin with good heat insulation performance, so that the transmittance of infrared rays radiated outwards in the greenhouse at night is high, the spliced greenhouse 3 and the example 3 is already applied to the field of agricultural large test bases of Odongtouzhu and Gaozhuang Shandong under Laiwu in 2018, the temperature of the planted tomatoes ('Xianfeng No. 4') in the greenhouse is reduced by 1.5-2.5 ℃ compared with the example 3, and the tomatoes are picked in 5 days after delay.
Comparative example 4
The coating type polyolefin light-conversion dustproof heat-preservation long-acting dripping fog-dissipation shed film comprises an inner layer, a secondary inner layer, a middle layer, a secondary outer layer, an outer layer and a coating layer, wherein the inner layer is a layer of a coating material; wherein the inner layer is a dustproof aging-resistant layer, and the raw materials comprise polyethylene, dustproof master batch and aging-resistant master batch; the secondary inner layer is an ageing-resistant layer, and is made of polyethylene resin and an ageing-resistant master batch; the middle layer is a barrier heat-insulation layer, and the raw materials comprise polyethylene, an anti-aging master batch and a barrier heat-insulation master batch; the secondary outer layer is a light conversion layer, and the raw materials comprise polyethylene, light conversion master batch and anti-aging master batch; the outer layer is an aging-resistant layer, and the raw materials comprise polyethylene and an aging-resistant master batch; the coating layer is a long-acting dripping fog-eliminating layer.
The raw material composition and dosage relationship of the inner layer, the outer layer and the coating layer are the same as those of example 4.
The secondary inner layer is an anti-aging layer and comprises the following raw materials in percentage by mass: 92% of polyethylene, wherein 25% of Low Density Polyethylene (LDPE), 27% of Linear Low Density Polyethylene (LLDPE), 40% of metallocene linear low density polyethylene (mLLDPE); 8% of an anti-aging master batch; wherein: low Density Polyethylene (LDPE) has a Melt Index (MI) of 0.25g/10min, manufactured by seashell brand No. 2420D; the Melt Index (MI) of Linear Low Density Polyethylene (LLDPE) is 0.85g/10min, and the mark is 9085 Tianjin joint production; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min, manufactured by Exxon Mobil under the brand XP6026 ML; the raw material composition and the preparation method of the aging-resistant master batch are the same as those of the inner layer in the example 1.
The middle layer is a heat insulation layer and consists of the following raw materials in percentage by mass: 80% of polyethylene, wherein the Low Density Polyethylene (LDPE) accounts for 25%, the Linear Low Density Polyethylene (LLDPE) accounts for 20%, and the metallocene linear low density polyethylene (mLLDPE) accounts for 35%; 10% of anti-aging master batch and 10% of barrier heat-insulation master batch; wherein: low Density Polyethylene (LDPE) has a Melt Index (MI) of 0.25g/10min, manufactured by seashell brand No. 2420D; the Melt Index (MI) of Linear Low Density Polyethylene (LLDPE) is 0.85g/10min, and the mark is 9085 Tianjin combined production; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min, manufactured by Exxon Mobil under the brand XP6026 ML; the raw material composition and the preparation method of the anti-aging master batch are the same as those of the inner layer in the example 1; the raw material composition and the preparation method of the barrier heat-preservation master batch are the same as those of the example 1.
The secondary outer layer is a light conversion layer and consists of the following raw materials in percentage by mass: 30% of low-density polyethylene (LDPE), 22% of linear low-density polyethylene (LLDPE), 37% of metallocene linear low-density polyethylene (mLLDPE), 4% of light conversion master batch and 7% of ageing-resistant master batch; wherein: low Density Polyethylene (LDPE) has a Melt Index (MI) of 0.25g/10min, manufactured by Shell in the designation 2420D; the Melt Index (MI) of Linear Low Density Polyethylene (LLDPE) is 0.85g/10min, and the mark is 9085 Tianjin combined production; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min, manufactured by Exxon Mobil under the brand XP6026 ML; the raw material composition and the preparation method of the light conversion master batch are the same as those of the example 4; the raw material composition and the preparation method of the aging-resistant master batch are the same as those of the example 4.
The preparation method of the coating type polyolefin light conversion dustproof heat preservation long-acting dripping fog dispersal shed film in the comparative example 4 is the same as that in the example 1, and the only difference is that: the extruder temperature of the secondary inner layer and the middle layer is set to be 180-200 ℃ as the inner layer.
The coated polyolefin light-conversion dustproof heat-preservation long-acting dripping fog-dissipation shed film prepared in the comparative example 4 has the light transmittance of 90.4%, the haze of 17.6% and the dripping fog-dissipation dustproof function duration of 7 years.
Compared with the embodiment 4, the secondary inner layer and the middle layer adopt the polyethylene resin to replace the EVA resin with good barrier and heat preservation performance; the secondary inner layer is not added with hydrotalcite heat-insulating master batch; the addition amount of the secondary outer layer light conversion master batch is reduced by 55.5 percent. In combination of the above factors, the barrier performance of infrared radiation to the outside in the greenhouse at night is reduced by 86.8% compared with that of example 4, the greenhouse 4 and example 4 are spliced to demonstrate that the greenhouse is applied to the field in agricultural test bases of Ougu Jiazhuang and Gaozhuang Shandong provinces under Laiwu within 2018 months, the temperature in the greenhouse at night is reduced by 2.5-3 ℃ compared with example 4, and the planted sweet pepper ("Katetlin") is picked after 7 days.
Comparative example 5
The internal addition type light-conversion dustproof high-heat-preservation dripping fog-dissipation greenhouse film prepared in the comparative example 5 comprises an inner layer, a secondary inner layer, a middle layer, a secondary outer layer, an outer layer and a coating layer; wherein the inner layer is a dripping antifogging layer, and the raw materials comprise 84.5% of polyolefin EVA, 12% of dripping anti-aging master batch and 3.5% of antifogging master batch; the secondary inner layer is a dripping anti-aging master batch storage layer, and the raw materials comprise 86% of polyolefin EVA and 14% of dripping anti-aging master batch; the middle layer is a dripping anti-aging master batch storage layer, and the raw materials comprise 84% of polyolefin EVA and 16% of dripping anti-aging master batch; the secondary outer layer is a light conversion layer, and the raw materials comprise 85% of polyethylene resin, 7% of anti-aging master batch and 8% of light conversion master batch; the outer layer is a dustproof aging-resistant layer, and the raw materials comprise 85% of polyethylene, 7% of aging-resistant master batch and 8% of dustproof master batch.
The inner layer is a dripping antifogging layer and comprises the following raw materials in percentage by mass: 84.5 percent of ethylene-vinyl acetate copolymer resin (EVA), 12 percent of dripping anti-aging master batch and 3.5 percent of fog dissipation master batch; wherein: ethylene-vinyl acetate copolymer resin (EVA) having a VA content of 9.5%, a Melt Index (MI) of 0.8g/10min and a brand number of 2040, produced in Korea; the dripping anti-aging master batch is EFT-638, the fog dispersal master batch is EFT-903, and is manufactured by Tianjin research and development company.
The secondary inner layer is a dripping anti-aging master batch storage layer and comprises the following raw materials in percentage by mass: 86% of ethylene-vinyl acetate copolymer resin (EVA) and 14% of dripping anti-aging master batch; wherein: ethylene-vinyl acetate copolymer resin (EVA) having a VA content of 12% and a Melt Index (MI) of 0.5g/10min, under the designation FL00012, available from Exxon; the dripping aging-resistant master batch is EFT-638 manufactured by Tianjin research and development company.
The middle layer is a dripping anti-aging master batch storage layer, and comprises the following raw materials in percentage by mass: 84% of ethylene-vinyl acetate copolymer resin (EVA) and 16% of dripping anti-aging master batch; wherein: ethylene-vinyl acetate copolymer resin (EVA) having a VA content of 14% and a Melt Index (MI) of 0.25g/10min, brand FL00014, manufactured by Exxon; the dripping anti-aging master batch is EFT-638 manufactured by Tianjin research and development company.
The secondary outer layer is a light conversion and aging resistant layer and comprises the following raw materials in percentage by mass: 25% of low-density polyethylene (LDPE), 20% of linear low-density polyethylene (LLDPE), 40% of metallocene linear low-density polyethylene, 7% of anti-aging master batch and 8% of light conversion master batch; wherein: low Density Polyethylene (LDPE) has a Melt Index (MI) of 0.25g/10min, manufactured under the designation 2420D seashell brand; the Melt Index (MI) of Linear Low Density Polyethylene (LLDPE) is 0.85g/10min, the mark is 9085, and Tianjin combined production is carried out; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.5g/10min, manufactured by Exxon Mobil, brand XP6056 ML; the raw material composition and the preparation method of the light conversion master batch are the same as those of the outer layer of example 1; the raw material components and the preparation method of the anti-aging master batch are the same as those of the inner layer in the example 1.
The outer layer is a dustproof ageing-resistant layer, and comprises the following raw materials in percentage by mass: 25% of low-density polyethylene (LDPE), 60% of metallocene linear low-density polyethylene (mLLDPE), 7% of ageing-resistant master batch and 8% of dustproof master batch; wherein: low Density Polyethylene (LDPE) has a Melt Index (MI) of 0.25g/10min, no. 2420D, made of Mediterranean Shell; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 1.0g/10min, trade name 2010MA, manufactured by Exxon Mobil, in a mass ratio of 30%; metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 0.2g/10min, brand XP6026ML, manufactured by Exxon Mobil, in a mass ratio of 30%; the raw material composition and the preparation method of the anti-aging master batch are the same as those of the example 1; the dustproof master batch is marked by EFT997, manufactured by Tianjin research and development company.
The preparation method of the polyolefin internal addition type light conversion dust-proof dripping fog dispersal shed film in the comparative example 5 comprises the following steps: after weighing the materials and the master batch of the components of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer, respectively mixing and stirring uniformly, adding the mixture into a five-layer co-extrusion extruder, and obtaining the polyolefin internal-addition type light-conversion dust-proof flow-drop fog-dissipation greenhouse film through melting, plasticizing, blow molding, traction, cooling and shaping, edge welding, seam cutting, code spraying and folding.
The specification of the prepared sample is 12000/0.12mm; 1, the layer thickness ratio of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer is 1; the blow-up ratio was 1.7. In a five-layer co-extrusion unit, the temperatures of the inner layer extruder, the secondary inner layer extruder and the middle layer extruder are all 150-175 ℃; the temperatures of the secondary outer layer and the outer layer extruder are both 180-200 ℃, and the temperatures of the machine neck, the die head bottom and the die ring are 200-215 ℃. The light transmittance of the sample is 88.3 percent, the haze is 18.6 percent, and the flow drop fog dissipation period is only 6 months.
The difference between the comparative example 5 and the example 1 is that the internal addition type preparation is adopted, and the coating type preparation is different from the coating type preparation without a coating layer, and the difference between the comparative example 5 and the example 1 is that the preparation process reduces the procedures of corona, dipping and drying. The greenhouse film without a coating layer has the dripping fog dissipation function, dripping master batch and fog dissipation master batch must be added into the film, the surfactant gradually migrates to reach the dripping fog dissipation function through the concentration gradient of the master batch in the film, the comparative example belongs to an internal addition type, an inner laminar droplet fog dissipation layer faces to the interior of the greenhouse when the greenhouse is buckled, the dripping effective period of the greenhouse film is only 180 days, the cost performance is relatively low, the greenhouse film needs to be replaced every year, the greenhouse buckling cost is high, and the requirement of modern high-efficiency agricultural development cannot be met.
Comparative example 6
Comparative example 6 differs from example 1 in that: firstly, the process method adopts a coating type three-layer co-extrusion blow molding method, secondly, the high-insulation layer only has a middle layer, and the high-insulation layer does not adopt the high-insulation far infrared EVA resin, so that the far infrared transmittance reaches 48.9%, the far infrared transmittance of the coating is reduced by 81.7% compared with that of the coating in example 1, and the heat insulation performance is obviously reduced.
The coated light-dimming dust-proof high-heat-preservation long-acting dripping fog-dispersal shed film described in the comparative example 6 comprises an inner layer, a middle layer, an outer layer and a coating layer; the inner layer is a dustproof aging-resistant layer, and the raw materials comprise polyethylene, dustproof master batch and aging-resistant master batch; the middle layer is a high-heat-insulation barrier layer, and the raw materials comprise polyethylene, an anti-aging master batch and a heat-insulation barrier master batch; the outer layer is a light-adjusting and light-converting layer, and the raw materials comprise polyethylene, light-converting master batch and anti-aging master batch; the coating layer is a long-acting dripping fog-eliminating layer.
The inner layer comprises the following raw materials: 21.3 percent of Low Density Polyethylene (LDPE), 21.3 percent of Linear Low Density Polyethylene (LLDPE), 42.6 percent of metallocene linear low density polyethylene (mLLDPE), 5.0 percent of ageing-resistant master batch and 9.8 percent of dustproof master batch.
The inner layer comprises the following raw materials in parts by weight: 25 parts of low-density polyethylene (LDPE), 25 parts of linear low-density polyethylene (LLDPE), 50 parts of metallocene linear low-density polyethylene, 5.9 parts of anti-aging master batch and 11.5 parts of dustproof master batch.
Low Density Polyethylene (LDPE) has a Melt Index (MI) of 0.2-0.3g/10min, no. 2420D, manufactured by Mediterranean shell, 25 parts; linear Low Density Polyethylene (LLDPE) has a Melt Index (MI) of 0.8-1.0g/10min, a designation of 9085, manufactured by Tianjin carbon-Linked, 25 parts.
Metallocene linear low density polyethylene (m-LLDPE) having a Melt Index (MI) of 1.0g/10min under the trademark 2010MC manufactured by Exxon Mobil, 50 parts; 5.9 parts of an anti-aging master batch; the dustproof master batch is marked by EFT995, manufactured by Tianjin research and development, 11.5 parts.
The raw material components and the preparation method of the anti-aging master batch are the same as those of the example 1.
The middle layer is a high-heat-insulation barrier layer and comprises the following raw materials: 21.3 percent of Low Density Polyethylene (LDPE), 21.3 percent of Linear Low Density Polyethylene (LLDPE), 42.6 percent of metallocene linear low density polyethylene (mLLDPE), 5.0 percent of ageing-resistant master batch and 9.8 percent of barrier heat-preservation master batch.
The middle layer comprises the following raw materials in parts by weight: 25 parts of low-density polyethylene (LDPE), 25 parts of linear low-density polyethylene (LLDPE), 50 parts of metallocene linear low-density polyethylene, 5.9 parts of anti-aging master batch and 11.5 parts of barrier heat-insulating master batch.
Low Density Polyethylene (LDPE) has a Melt Index (MI) of 0.2-0.3g/10min, no. 2420D, manufactured by Mediterranean shell, 25 parts; the Linear Low Density Polyethylene (LLDPE) has a Melt Index (MI) of 0.8-1.0g/10min, a mark number of 9085, manufactured by Tianjin carbon-linked method, of 25 parts; the metallocene linear low density polyethylene (m-LLDPE) has a Melt Index (MI) of 1.0g/10min under the designation 1018MA, manufactured by Exxon Mobil, of 50 parts; 5.9 parts of an anti-aging master batch; wherein the component content and the preparation method of the anti-aging master batch and the inner layer are not described; 11.5 parts of barrier heat-insulation master batch, wherein the raw material components and the preparation method of the barrier heat-insulation master batch are the same as those in the embodiment 1.
The outer layer is a light-adjusting and light-converting layer and comprises the following raw materials: 23% of Low Density Polyethylene (LDPE), 23% of Linear Low Density Polyethylene (LLDPE), 46% of metallocene linear low density polyethylene (mLLDPE), 5.0% of ageing-resistant master batch and 3.0% of light conversion master batch.
The outer layer comprises the following raw materials in parts by weight: 25 parts of Low Density Polyethylene (LDPE), 25 parts of powdery Linear Low Density Polyethylene (LLDPE), 50 parts of metallocene linear low density polyethylene (mLLDPE), 5.4 parts of ageing-resistant master batch and 3.3 parts of light conversion master batch.
Low Density Polyethylene (LDPE) has a Melt Index (MI) of 0.2-0.3g/10min, no. 2420D, manufactured by Mediterranean shell, 25 parts; the Linear Low Density Polyethylene (LLDPE) has a Melt Index (MI) of 0.8-1.0g/10min, a mark number of 9085, manufactured by Tianjin carbon-Linked, 25 parts.
The metallocene linear low density polyethylene (mLLDPE) has a Melt Index (MI) of 1.0g/10min, no. 2010MC, manufactured by Exxon Mobil, of 50 parts; 5.4 parts of an anti-aging master batch; the component content and the preparation method of the aging-resistant master batch and the inner layer are not described; and 3.3 parts of light conversion master batch.
The components and preparation method of the light conversion master batch are the same as those of example 1.
The coating layer comprises the following raw materials: 8% of coating liquid stock solution and 92% of deionized water. The coating liquid was rated TG-150, manufactured by Nippon bamboo grease Co.
Adding the weighed coating liquid stock solution into a stainless steel tank, adding deionized water in proportion, stirring uniformly, standing for 20 minutes, and pumping into a liquid hanging tank for later use, wherein the dry matter content of the coating layer is 0.2g/m 2 。
The preparation method of the coating type light-conversion dustproof high-heat-preservation long-acting dripping fog-dispersal shed film in the comparative example 6 comprises the following steps: the coating type light-dimming dust-proof high-heat-preservation long-acting dripping fog-dispersing greenhouse film is prepared by respectively mixing and stirring the component materials and the master batch of the inner layer, the middle layer and the outer layer uniformly, adding the mixture into a three-layer co-extrusion extruder, and carrying out melt plastification blow molding, traction, cooling setting, corona, coating liquid impregnation, drying, edge welding, seam cutting, code spraying and folding.
The specification of the prepared product is 12000/0.12mm; the layer thickness ratio of the inner layer, the middle layer and the outer layer is 1:1:1; the blow-up ratio was 1.8. In the three-layer co-extrusion unit, the temperatures of the inner layer, the middle layer and the outer layer are all 170-215 ℃, and the temperatures of a machine neck and a die head are 190-235 ℃; the oven temperature is 85-102 ℃.
Table 2 comparative example 6 process conditions
The coating type light-dimming dust-proof high-heat-preservation long-acting dripping fog-dispersal shed film prepared in the comparative example 6 has the light transmittance of 91.2 percent, the fog degree of 14.5 percent and the service life of 5 years. The greenhouse films prepared in the comparative example 6 and the example 1 are applied to greenhouse field covering in the agricultural test base of the Zhelu jiazhuang and the Gaozhuangshandong under Laiwu, the temperature is reduced at night in the case of planting the strawberries in the comparative example 6 compared with that in the example 1, and the flowering and fruit ripening picking period is 7 days later.
The mechanical property, optical property and infrared transmittance of the sample are tested according to national standard GB/T20202-2019[ agricultural ethylene-vinyl acetate copolymer (EVA) blow-molded greenhouse film ], the dripping property is tested according to line standard QB/T4475-2013[ coating type persistent dripping polyethylene greenhouse film ], and the result is shown in Table 2, and the product specification is 12M 0.12mm.
TABLE 3 results of various property tests on the samples
The test results reflected by the table 3 show that the data of the mechanical properties, the optical properties and the infrared transmittance of the examples 1 to 5 and the comparative examples 1 to 6 are all superior to the national standard index requirements, and can meet the most basic requirements of greenhouse coverage application. In comparative examples 3, 4 and 6, no EVA resin is adopted, so that the infrared transmittance is improved by more than 81%, the thermal insulation performance is obviously reduced, the flowering phase is influenced, and the maturation phase is delayed.
Table 4 drip defogging performance water bath experiment
Table 4 testing of dripping fog dispersal performance according to the specification of 4.6 dripping performance test in the standard "coating type durable dripping polyethylene greenhouse film" standard QB/T4475-2013, the 1-year film experiment time is 30d, the 2-year film experiment time is 45 days, the 3-year film experiment time is 60 days, the 4-year film experiment time is 75 days, the 5-year film experiment time is 90 days, the 6 years are 105 days, and the 7-year is 120 days.
The test data of the dripping and defogging performances of the examples 1-5, the comparative examples 1-4 and the comparative example 6 in the table 3 show that the lasting period of the dripping and defogging function of the greenhouse film prepared by the coating process can be synchronized with the service life of the greenhouse film. Comparative example 5 belongs to a greenhouse film prepared by an internal addition type process, and the test standard is according to the specification of 6.8 dripping performance in GB/T20202-2019.
The difference of the two types of droplet performance test time is enough to illustrate the good and bad effect of the effective period of the droplet fog dissipation function. As a covering material of an overwintering greenhouse, the dripping fog dissipation performance of the greenhouse film is an important key functional index, the dripping fog dissipation functional period of the comparative example 5 is short, the service life of the greenhouse film is one year, and the cost performance is low. Especially, in winter, the temperature difference between the indoor part and the outdoor part of the greenhouse is large, fog drops and water drops can be generated on the greenhouse film, sunlight transmission is blocked, photosynthesis is weakened, crop growth is affected, moisture can rise due to dew formation and water drops in the greenhouse, and crop downy mildew and plant diseases and insect pests are bred due to the fact that the water drops drop on crops, so that yield is reduced. The flow drop fog dissipation function of the greenhouse film is to reduce the formation of fog drops on the inner surface of the greenhouse film, change the water drops into a water film and flow down along the film surface, and simultaneously reduce and eliminate the fog in the greenhouse and enhance the illumination effect of crops.
TABLE 5 light conversion effect indoor and outdoor light intensity ratio detection result
The test data of the light conversion effect shed indoor and outdoor light intensity ratio listed in table 5 is a detection result acquired by buckling a shed film on the spot in the town agricultural test base below Laiwu by using a handheld portable fluorescence spectrometer and a luminometer. The test data in table 4 show that the indoor and outdoor light intensity ratios of examples 1 to 5 are reduced in a small range along with the increase of the greenhouse-covering time, the indoor and outdoor light intensity ratio of 20 months greenhouse covering is maintained at 88% or more, and the light conversion effect is obviously better than that of the light conversion effect recorded in the prior art, and is maintained at 88% or more in 8 months. The light intensity ratio plays a key role in enhancing the photosynthetic efficiency of crops, promoting the growth of crops, increasing the early maturity and the yield and improving the quality.
TABLE 6 test results of dust test
In Table 6: the light transmittance is excellent when the light transmittance is more than or equal to 85 percent, good when the light transmittance is more than or equal to 80 percent, common when the light transmittance is more than or equal to 80 percent, and poor when the light transmittance is less than 75 percent. The dustproof master batch greatly reduces the friction coefficient of the surface of the greenhouse film (0.1-0.15), dust is not easy to attach to the film surface, the film is bright as new after being blown by wind and drenched by rain, the annual attenuation rate of the light transmittance is obviously reduced and is only below 1.01 percent, the annual attenuation rate is improved by 30.8-32.7 percent compared with the prior art in the agricultural film industry, the annual attenuation rate of the light transmittance is 1.46-1.5 percent, and the low annual attenuation rate of the light transmittance is a necessary condition for long-term use of the greenhouse film.
The weather resistance of the greenhouse films prepared in examples 1 to 5 was tested, and the experimental equipment used a xenon weathering chamberTesting according to a GB/T16422.2-2014 plastic laboratory light source exposure experimental method; irradiation method A, irradiance is narrow-band (340 nm) 0.51W/(m) 2 Nm), carrying out an aging test at a black mark temperature of 65 ℃, spraying for 18min, stopping for 102min, and completing 60 spraying cycle periods until 7200 hours. The test items are tensile strength retention and elongation at break retention.
TABLE 7 tensile Strength test results
TABLE 8 tensile Strength Retention test results
| Experiment time/h | Measurement results | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| 0 | Tensile Strength Retention/% | 100 | 100 | 100 | 100 | 100 |
| 7200 | Tensile strength retention% | 62.12 | 60.90 | 62.73 | 61.31 | 60.80 |
TABLE 9 elongation at break test results
TABLE 10 retention of elongation at break test results
The experimental data prove that the aging resistance of the greenhouse film sample prepared by the invention is reliable and completely meets the technical requirements specified in GB/T20202-2019.
Claims (10)
1. The utility model provides a coating type polyolefin changes dustproof high long-term stream of keeping warm of light fog dispersal canopy membrane which characterized in that: comprises an inner layer, a secondary inner layer, a middle layer, a secondary outer layer, an outer layer and a coating layer; wherein the inner layer is a dustproof aging-resistant layer and consists of the following raw materials in percentage by mass: 15-25% of low-density polyethylene, 60-70% of metallocene linear low-density polyethylene, 6-12% of anti-aging master batch and 3-8% of dustproof master batch; the secondary inner layer is a heat-insulating and anti-aging layer and comprises the following raw materials in percentage by mass: 78-87% of ethylene-vinyl acetate copolymer resin, 5-10% of anti-aging master batch and 6-12% of barrier heat-insulation master batch; the middle layer is a high-heat-insulation barrier layer and comprises the following raw materials in percentage by mass: 75-85% of ethylene-vinyl acetate copolymer resin, 5-10% of anti-aging master batch and 8-15% of barrier heat-insulation master batch; the secondary outer layer is a light conversion layer and consists of the following raw materials in percentage by mass: 25% -31% of low-density polyethylene, 20% -25% of linear low-density polyethylene, 30% -40% of metallocene linear low-density polyethylene, 6% -12% of light conversion master batch and 3% -5% of ageing-resistant master batch; the outer layer is an ageing-resistant layer and consists of the following raw materials in percentage by mass: 20% -28% of low-density polyethylene, 65% -75% of metallocene linear low-density polyethylene and 5% -8% of ageing-resistant master batch; the coating layer is a long-acting dripping defogging layer.
2. The coating type polyolefin light conversion dustproof high heat preservation long-acting dripping fog dispersal greenhouse film as claimed in claim 1, which is characterized in that: the VA content of the ethylene-vinyl acetate copolymer resin in the raw material of the secondary inner layer is 12%, and the melt index is 0.5g/10min.
3. The coating type polyolefin light conversion dustproof high heat preservation long-acting dripping fog dispersal greenhouse film as claimed in claim 1, which is characterized in that: the VA content of the ethylene-vinyl acetate copolymer resin in the middle layer raw material is 14-18%, and the melt index is 0.25-0.37g/10min.
4. The coating type polyolefin light conversion dustproof high heat preservation long-acting dripping fog dispersal greenhouse film as claimed in claim 1, which is characterized in that: the coating layer comprises the following raw materials in percentage by mass: 6-8% of coating liquid stock solution and 92-90% of deionized water; the coating liquid stock solution is any one of TG-150 or TF-820G; wherein the TG-150 was manufactured by Nippon bamboo fat Co., ltd, and the TF-820G was manufactured by Loran Green Source Ltd.
5. The coating type polyolefin light conversion dustproof high heat preservation long-acting dripping fog dispersal greenhouse film as claimed in claim 1, which is characterized in that: the specific parameters of the raw materials adopted by the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer are as follows:
low density poly (arylene sulfide)The density of the ethylene is 0.920-0.923g/cm 3 The melt index is 0.2-1.0g/10min;
the linear low density polyethylene has a density of 0.918-0.926g/cm 3 The melt index is 0.8-1.0g/10min;
the metallocene linear low density polyethylene has a density of 0.916 to 0.922g/cm 3 The melt index is 0.2-1.0g/10min;
the dustproof master batch is a commercial product EFT997 produced by Tianjin research corporation; or maleic anhydride grafted dustproof master batch, wherein the manufacturer is Jilin Baien plastic science and technology company and the brand is BE-10F.
6. The coating type polyolefin light-conversion dustproof high-heat-insulation long-acting dripping fog-dispersal shed film as defined in claim 1, which is characterized in that: the anti-aging master batch comprises the following raw materials in percentage by mass: 42-45% of low-density polyethylene, 37-40% of linear low-density polyolefin, 12-15% of light stabilizer and 2-3% of antioxidant;
wherein: the melt index of the low-density polyethylene in the aging-resistant master batch is 2.0g/10min; the melt index of the linear low-density polyethylene is 2.0g/10min, and the appearance is powder; the light stabilizer is a hindered amine light stabilizer, and the hindered amine light stabilizer is at least one of HALS944, HS-625, T-69 or XT-100; the antioxidant is a compound type of hindered phenols and phosphites, and is any one of B215 or B225;
the preparation method of the aging-resistant master batch comprises the following steps: adding low-density polyethylene, linear low-density polyethylene, a light stabilizer and an antioxidant into an internal mixer according to a proportion, kneading and plasticizing, feeding into a single-screw extrusion granulator through an open mill, carrying out hot granulation, and carrying out air-cooled drying to obtain an anti-aging master batch;
wherein: the temperature of the internal mixer is 125-140 ℃, the plasticizing time is 15-20 minutes, and the temperature of the single-screw extrusion granulator is 140-170 ℃.
7. The coating type polyolefin light conversion dustproof high heat preservation long-acting dripping fog dispersal greenhouse film as claimed in claim 1, which is characterized in that: the blocking and heat-insulating master batch comprises the following raw materials in percentage by mass: 18 to 25 percent of low-density polyethylene, 15 to 20 percent of linear low-density polyethylene, 50 to 60 percent of hydrotalcite heat preservation agent, 1.0 to 3.0 percent of coupling agent, 0.5 to 1.5 percent of lubricant and 0.5 to 1.5 percent of dispersant;
wherein: the melt index of the low-density polyethylene in the barrier heat-insulation master batch is 2.0g/10min; the melt index of the linear low-density polyethylene is 2.0g/10min, and the appearance is powder; a hydrotalcite holding agent having a trade name of HTP manufactured by Sakai chemical company, or any of the trade names HT3 manufactured by Dandong-Co.Ltd; the coupling agent is any one of titanate or aluminate; the lubricant is two or any one of zinc stearate or calcium stearate; the dispersing agent is polyethylene wax;
the preparation method of the barrier heat-insulation master batch comprises the following steps: adding low-density polyethylene, linear low-density polyethylene, a hydrotalcite heat preservation agent, a coupling agent, a lubricant and a dispersing agent into an internal mixer according to a proportion, kneading and plasticizing, feeding into a single-screw extrusion granulator through an open mill, carrying out hot granulation, and carrying out air-cooling drying to obtain a blocking heat preservation master batch;
wherein: the temperature of the internal mixer is 125-140 ℃, the plasticizing time is 15-20 minutes, and the temperature of the single-screw extrusion granulator is 140-170 ℃.
8. The coating type polyolefin light conversion dustproof high heat preservation long-acting dripping fog dispersal greenhouse film as claimed in claim 1, which is characterized in that: the light conversion master batch comprises the following raw materials in percentage by mass: 42 to 52 percent of low-density polyethylene, 36 to 45 percent of linear low-density polyethylene, 6 to 12 percent of light conversion agent and 0.3 to 1.0 percent of antioxidant;
the melt index of the low-density polyethylene in the light conversion master batch is 2.0g/10min; the linear low density polyethylene has a melt index of 2.0g/10min; the light conversion agent is an inorganic rare earth light conversion agent, and the inorganic rare earth light conversion agent is any one or more of green-to-red GTR-650 II, green-to-red GTR-650 III, purple-to-blue VTB-440, purple-to-red VTR660, red-to-blue double-light-conversion RBI6545, purple-to-far-red VTFR700 or green-to-far-red GTFR 708; the antioxidant is a compound type of hindered phenols and phosphites, and is any one of B215 or B225;
the preparation method of the light conversion master batch comprises the following steps: adding low-density polyethylene, linear low-density polyethylene, a light conversion agent and an antioxidant into an internal mixer according to a proportion, kneading and plasticizing, feeding into a single-screw extrusion granulator through an open mill, carrying out hot granulation, and carrying out air cooling and drying to prepare a light conversion master batch;
wherein: the temperature of the internal mixer is 125-140 ℃, the plasticizing time is 15-20 minutes, and the temperature of the single-screw extrusion granulator is 140-170 ℃.
9. The coating type polyolefin light-conversion dustproof high-heat-insulation long-acting dripping fog-dispersal shed film as defined in claim 1, which is characterized in that: the thickness ratio of the inner layer to the secondary inner layer to the middle layer to the secondary outer layer to the outer layer is 1 2 。
10. A preparation method of the coating type polyolefin light conversion dustproof high heat preservation long-acting dripping fog dispersal shed film of claim 1, which is characterized by comprising the following steps: respectively mixing and stirring the component materials of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer uniformly, adding the mixture into a five-layer co-extrusion extruder, and obtaining the coating type polyolefin light-conversion dustproof high-heat-preservation long-acting dripping fog-dissipation shed film after melting, plasticizing, blow molding, cooling and shaping, traction, corona, coating liquid impregnation, drying, edge welding, seam cutting, code spraying and folding;
wherein: in the five-layer co-extrusion unit, the temperatures of the inner layer, the secondary inner layer, the middle layer, the secondary outer layer and the outer layer are all 150-200 ℃, the die head temperature is 190-215 ℃, the oven temperature is 85-102 ℃, and the blow-up ratio is 1.5-2.5.
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