CN115923290A - Machine-used stretch winding film and preparation method thereof - Google Patents
Machine-used stretch winding film and preparation method thereof Download PDFInfo
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Abstract
The application relates to the field of packaging materials, and particularly discloses a machine-used stretch wrapping film and a preparation method thereof. The machine stretch wrap film comprises an outer layer film, a middle layer film and an inner layer film which are sequentially attached; the outer layer film and the inner layer film comprise the following raw materials in parts by weight: 60-90 parts of metallocene polyethylene and 200-250 parts of linear low-density polyethylene; the middle layer film comprises the following raw materials in parts by weight: 120-180 parts of metallocene polyethylene and 400-500 parts of linear low-density polyethylene. The machine stretch winding film has the advantages of high tensile strength, high puncture resistance, excellent barrier property, high transparency and capability of preventing inner layer film atomization.
Description
Technical Field
The application relates to the technical field of packaging materials, in particular to a machine-used stretch wrapping film and a preparation method thereof.
Background
The machine stretch winding film is a packaging film which is used for tightly wrapping goods by utilizing deformation stress generated by forcibly stretching a film by a mechanical device at normal temperature and is convenient to transport and store, and is a very popular packaging form internationally at present. The stretch winding film has the characteristics of good tensile property, tearing resistance, strong penetration resistance, high transparency, good self-adhesion, high retraction rate, tight package, no looseness and the like. Because it can reduce the cost of bulk goods transportation and package by above 30%, it is widely used in the integral package of hardware, mineral products, chemical industry, medicine, food, machinery and other products, and in the field of warehouse storage, it also uses the stretch-wrap film tray package to make three-dimensional storage abroad, so as to save space and land occupation.
The existing winding film is mostly prepared from low-density polyethylene through a casting or film blowing process, but the winding film has relatively single component, so that the tensile strength and the tear strength of the winding film material are relatively low, when the winding film is wound and packaged, if the tensile force is slightly large, the phenomenon of fracture can occur, the winding film cannot be well applied to packaged products, in addition, the existing winding film mostly takes a single layer or double layers as the main part, the uniformity of the winding film is poor, the thickness error is relatively large, the longitudinal elongation of the winding film is low, the yield point is low, the transverse tear strength is poor, and the puncture resistance is poor.
In view of the above-mentioned related art, the inventors found that the wound stretch film has poor tensile strength in practical use and the puncture resistance is to be improved.
Disclosure of Invention
In order to improve the tensile strength and puncture resistance of the wrapping film, the application provides a machine stretch wrapping film and a preparation method thereof.
In a first aspect, the present application provides a machine stretch wrap film, which adopts the following technical scheme:
a machine stretch wrap film comprises an outer layer film, a middle layer film and an inner layer film which are sequentially attached; the outer layer film and the inner layer film comprise the following raw materials in parts by weight: 60-90 parts of metallocene polyethylene and 200-250 parts of linear low-density polyethylene;
the middle layer film comprises the following raw materials in parts by weight: 120-180 parts of metallocene polyethylene and 400-500 parts of linear low-density polyethylene.
By adopting the technical scheme, the middle layer film, the outer layer film and the inner layer film are all made of metallocene polyethylene and linear low-density polyethylene, the linear low-density polyethylene is used as a main base material, and the winding film has the advantages of higher softening temperature and melting temperature, high strength, good toughness, excellent heat and cold resistance, good environmental stress crack resistance, high impact strength, high tear strength and the like, and the tensile strength, the puncture resistance and the tear resistance of the winding film can be obviously improved by adding the metallocene polyethylene into the winding film.
Optionally, the amount of metallocene polyethylene in the middle layer film is the sum of the amounts of metallocene polyethylene in the outer layer film and the inner layer film;
the dosage of the linear low density polyethylene in the middle layer film is the sum of the dosages of the linear low density polyethylene in the outer layer film and the inner layer film.
By adopting the technical scheme, the outer layer film and the inner layer film have the same dosage, and the middle layer film is the sum of the dosages of the outer layer film and the inner layer film, so that the winding film with strong puncture resistance and excellent tensile strength can be obtained.
Optionally, the outer layer film and the inner layer film both further comprise 1.5-3.5 parts by weight of an anti-reflection agent, 1-3 parts by weight of a plasticizer, 2-6 parts by weight of a stabilizer and 0.6-1.2 parts by weight of an anti-aging agent;
the middle layer film also comprises 3-7 parts by weight of an anti-reflection agent, 2-6 parts by weight of a plasticizer, 4-12 parts by weight of a stabilizer and 1.2-2.4 parts by weight of an anti-aging agent.
By adopting the technical scheme, the components such as the anti-reflection agent, the plasticizer and the like are added into the outer layer film, the middle layer film and the inner layer film, so that the mechanical strength of the winding film can be further enhanced, and the transparency of the winding film can be improved.
Optionally, the anti-reflection agent is pretreated by a silane coupling agent KH570, and the anti-reflection agent comprises transparent titanium dioxide and silicon dioxide with the mass ratio of 1.
According to the technical scheme, the silicon dioxide and the transparent titanium dioxide are used as anti-reflection agents, the silicon dioxide and the transparent titanium dioxide can be uniformly mixed with high polymer materials in a middle-layer film, an outer-layer film and an inner-layer film after being treated by a silane coupling agent KH570, and can be used as nucleating agents during extrusion flow delay to improve the transparency of the winding film, in addition, the silicon dioxide and the transparent titanium dioxide form organic coating layers on the transparent titanium dioxide and the silicon dioxide under the action of the KH570, so that the silicon dioxide and the transparent titanium dioxide have hydrophobicity, the compatibility of the silicon dioxide and inner-layer film raw materials is improved, the dispersion in the inner-layer film is uniform, the hydrophobicity of the inner-layer film and the barrier property to water vapor are improved, water drops are easy to slide off from the inner-layer film, the anti-fog effect is achieved, the winding film is suitable for marine transportation and remote transportation, and can also be suitable for fruit and vegetable transportation, and can be used for preventing water vapor generation due to the respiration effect in the winding film, the inner-layer film, so that the surface of the inner-layer film is foggy, the food quality is influenced and the food spoilage is caused.
Optionally, the plasticizer is selected from one or more of epoxidized soybean oil, dioctyl phthalate and diisononyl phthalate;
the stabilizer is selected from one or more of dibutyltin dilaurate, octyltin maleate, dibasic lead stearate, dibasic lead phthalate and dibasic lead phosphite;
the anti-aging agent is selected from one or more of anti-aging agent 2246, anti-aging agent A and anti-aging agent NDBC.
By adopting the technical scheme, the tensile strength and the puncture resistance of the winding film can be further improved by using the plasticizer, the stabilizer and the anti-aging agent.
Optionally, the density of the metallocene polyethylene is 0.912-0.915g/cm 3 The melt index is 2-2.2g/10min; the linear low density polyethylene has a density of 0.92-0.935g/cm 3 The melt index is 2.0-2.3g/10min.
By adopting the technical scheme, the metallocene polyethylene has good comprehensive performance in the aspects of strength, flexibility, sealing performance and optical performance, the flexibility, low modulus, tearing strength and puncture resistance are superior to those of linear low density polyethylene, and the metallocene polyethylene can be blended with the linear low density polyethylene to improve the tearing strength and the stress cracking resistance of the winding film.
Optionally, the inner layer film further comprises 10-20 parts by weight of a barrier modifier, and the barrier modifier comprises the following components in parts by weight: 0.3-0.5 part of graphene oxide, 0.01-0.03 part of cellulose nanofibrils, 1-2 parts of cellulose nanofibril aerogel, 0.5-1 part of tridecafluorooctyl trimethoxysilane ethanol solution, 0.1-0.25 part of polyethyleneimine and 1-1.5 parts of deionized water.
By adopting the technical scheme, the cellulose nanofibril aerogel is a novel solid material with high porosity and high specific surface area, has a unique three-dimensional reticular porous structure, is excellent in flexibility and mechanical property, and can improve the tensile strength and the tear strength of the winding film; the cellulose nano-fibril serving as a novel nano-biomaterial has a large specific surface area, can be stably dispersed in a solvent system for a long time to form hydrogel, has numerous hydroxyl groups on the surface, has a strong adsorption effect with graphene oxide through hydrogen bonds, can be used as a dispersing agent of graphene oxide, obviously improves the dispersibility of the graphene oxide in water, disperses the graphene oxide into the nano-cellulose fibrils, can improve the mechanical property and the barrier property of the cellulose nano-fibril, can be uniformly dispersed with the cellulose nano-fibril aerogel under the condition that the cellulose nano-fibril serves as the dispersing agent, and can enhance the interface interaction between the cellulose nano-fibril aerogel and the graphene oxide, organize the swelling and the water absorption of the cellulose nano-fibril, improve the water resistance and the barrier property of the barrier modifier, so that the winding film is suitable for winding and packaging of marine transportation and remote transportation.
Optionally, the barrier modifier is prepared by the following method:
adding cellulose nanofibrils into deionized water, stirring uniformly to prepare a dispersion liquid, adding graphene oxide, dispersing uniformly by ultrasonic, adding cellulose nanofibrils aerogel and polyethyleneimine, mixing uniformly, drying, adding an ethanol solution of tridecafluorooctyltrimethoxysilane, mixing uniformly and drying.
By adopting the technical scheme, the graphene oxide is added into the dispersion liquid, under the dispersion effect of the cellulose nano-fibrils, the graphene oxide can be uniformly dispersed, the dispersion uniformity of the graphene oxide and the cellulose nano-fibril aerogel and the polyethyleneimine is improved, the polyethyleneimine increases the interface acting force of the graphene oxide and the cellulose nano-fibril aerogel, the cellulose nano-fibril aerogel is attached to the graphene oxide, the barrier property of the cellulose nano-fibril aerogel to water vapor and oxygen is improved, in addition, the cellulose nano-fibril aerogel is subjected to hydrophobic treatment by using tridecafluorooctyl trimethoxysilane, the barrier property and the anti-fog effect of a barrier modifier to water vapor are improved, the compatibility of the cellulose nano-fibril aerogel and an inner layer film raw material can be improved, the mechanical strength is improved, in addition, the cellulose nano-fibril aerogel is added into the inner layer film after being coated on the graphene oxide, and the transparency of a winding film can be improved.
Optionally, the preparation method of the cellulose nanofibril aerogel is as follows:
dispersing 2-3 parts of cellulose nano-fibrils in deionized water by weight to prepare a suspension with the concentration of 1-2 wt%; mixing 0.6-0.9 part of montmorillonite, 0.3-0.6 part of boron nitride and 2.5-3 parts of xylose powder, ball-milling for 8-10h, adding deionized water, uniformly mixing, filtering and drying to obtain a nano filler;
mixing the nanofiller and the suspension, heating to 60-65 ℃, adding 0.01-0.02 part of sodium sulfite and 0.004-0.005 part of ammonium persulfate, stirring for 3-8min, adding 0.12-0.14 part of N, N-methylene bisacrylamide, uniformly mixing, precooling for 3-5h at the temperature of- (8-10), freeze-drying for 40-48h at the temperature of- (60-65), and crushing to obtain the cellulose nanofibril aerogel.
By adopting the technical scheme, the nano cellulose fibrils have high strength and high transparency, and the two-dimensional nano material montmorillonite and boron nitride are added into the one-dimensional cellulose nanofibrils, so that the barrier property, the strength and the toughness of the aerogel can be obviously improved; under the modification of the xylose powder, hydroxyl, amino agent xylose and other hydrophilic groups are introduced to the surfaces of the montmorillonite and the boron nitride, the dispersion uniformity of the montmorillonite and the boron nitride which are subjected to grinding dispersion and exist in the suspension in a single-chip form, the suspension is transparent and clear, the transparency of a winding film is not influenced, the single-layer montmorillonite and the boron nitride nanosheet can promote the aerogel to form an ordered structure, and the single-layer montmorillonite and the boron nitride nanosheet are orderly overlapped in the composite film in the transmission of external force and light, so that the force consumption and the light transmission are facilitated, and the mechanical strength and the optical performance can be improved; the single-layer montmorillonite and boron nitride nanosheets can be uniformly embedded into a cellulose nanofibril aerogel network to form a highly ordered structure, disordered stacking is reduced, the single-layer montmorillonite and boron nitride nanosheets in the cellulose nanofibril aerogel are uniform and ordered, and the anisotropic forms of the two-dimensional inorganic montmorillonite layers and the boron nitride nanosheets in the aerogel can prolong the diffusion path of gas, so that the permeation of the gas is hindered, the barrier property of the cellulose nanofibril aerogel to water vapor and oxygen is improved, the light transmittance is improved, and the transparency is improved.
In a second aspect, the application provides a method for preparing a machine stretch wrap film, which adopts the following technical scheme:
a preparation method of a machine-used stretch wrapping film comprises the following steps:
according to parts by weight, raw materials of the outer layer film, the inner layer film and the middle layer film are respectively put into a hopper, and the machine stretch winding film is prepared by casting extrusion, cooling and shaping and rolling.
By adopting the technical scheme, the formula of each layer of material of the stretch winding film is reasonable, and the three-layer co-extrusion process is adopted, so that the prepared winding film is uniform in thickness and high in transparency, and has excellent tensile strength and puncture resistance.
Optionally, the casting extrusion temperature is 170-210 ℃, the rotating speed of the extruder is 400-600r/min, the temperature of the cooling roller is 20-25 ℃, and the winding tension is 9-12kg.
In summary, the present application has the following beneficial effects:
1. because the linear low-density polyethylene is used as the main raw material of the middle layer film, the inner layer film and the outer layer film and is matched with the metallocene polyethylene, the two films have good transparency, high penetration resistance and tensile strength, and better environmental stress cracking resistance and high rupture strength.
2. In the application, components such as an anti-reflection agent, a plasticizer, an anti-aging agent and the like are preferably added into the inner layer film, the middle layer film and the outer layer film, the anti-reflection agent is prepared by pretreating transparent titanium dioxide and silicon dioxide through a silane coupling agent KH570, the transparency of the winding film can be improved, the barrier property of the winding film on water vapor and oxygen is improved, the hydrophobicity of the inner layer film in the winding film is improved, the anti-fog effect of the winding film is improved, and the mechanical strength of the winding film is further improved.
3. In the application, a blocking modifier is preferably added into the inner membrane, the preparation method of the blocking modifier is that the cellulose nanofibril aerogel is attached to graphene oxide under the action of polyethyleneimine, tridecafluorooctyl trimethoxy silane is used for improving the hydrophobicity of the cellulose nanofibril aerogel, and under the action of the graphene oxide, the blocking property of the cellulose nanofibril aerogel is improved, so that the inner membrane not only has a hydrophobic antifogging effect, but also has good blocking property, and the winding membrane is suitable for packaging in marine transportation and long-distance transportation.
4. The montmorillonite and the boron nitride which are ground and dispersed by the xylose powder and the cellulose nanofibril dispersion liquid are preferably blended to prepare the aerogel, the blocking property of the aerogel can be improved by the single-layer montmorillonite and the boron nitride sheet, the light transmittance of the aerogel is improved, and the transparency of the winding film is improved.
Detailed Description
Preparation examples 1-9 of Barrier modifier
Preparation example 1: adding 0.03kg of cellulose nanofibrils into 1.5kg of deionized water, uniformly stirring to prepare a dispersion liquid, adding 0.5kg of graphene oxide, ultrasonically dispersing for 10min at 200w of power, adding 2kg of cellulose nanofibril aerogel and 0.25kg of polyethyleneimine, uniformly mixing, drying at 60 ℃ for 4h, adding 1kg of tridecafluorooctyl trimethoxysilane ethanol solution with the concentration of 80wt%, uniformly mixing and drying, wherein the preparation method of the cellulose nanofibril aerogel comprises the following steps: dispersing 2g of cellulose nanofibrils in deionized water to prepare a suspension with the concentration of 1wt%, adding 0.01g of anhydrous sodium sulfite and 0.004g of ammonium persulfate, magnetically stirring for 8min, adding 0.12N, N-methylene-bisacrylamide, uniformly mixing, precooling for 3h at-8 ℃, then drying for 48h in vacuum at-60 ℃, and crushing to 5 mu m;
preparation example 2: adding 0.01kg of cellulose nanofibrils into 1kg of deionized water, uniformly stirring to prepare a dispersion solution, adding 0.3kg of graphene oxide, ultrasonically dispersing for 15min at 150w of power, adding 1kg of cellulose nanofibril aerogel and 0.1kg of polyethyleneimine, uniformly mixing, drying at 60 ℃ for 4h, adding 0.5kg of tridecafluorooctyltrimethoxysilane ethanol solution with the concentration of 80wt%, uniformly mixing and drying, wherein the preparation method of the cellulose nanofibril aerogel comprises the following steps: dispersing 2g of cellulose nanofibrils in deionized water to prepare a suspension with the concentration of 1wt%, adding 0.01g of anhydrous sodium sulfite and 0.004g of ammonium persulfate, stirring for 8min by magnetic force, adding 0.12N, N-methylene-bisacrylamide, mixing uniformly, precooling for 3h at-8 ℃, then drying in vacuum at-60 ℃, and crushing to 5 mu m.
Preparation example 3: the difference from preparation example 1 is that ethanol solution of tridecafluorooctyltrimethoxysilane is not used.
Preparation example 4: the difference from preparation example 1 is that graphene oxide was not added.
Preparation example 5: the difference from preparation example 1 is that no polyethyleneimine is added.
Preparation example 6: the difference from preparation example 1 is that cellulose nanofibril aerogel was prepared by dispersing 2g of cellulose nanofibril in deionized water to make a suspension with a concentration of 1 wt%;
mixing 0.6g of montmorillonite, 0.3g of boron nitride and 2.5g of xylose powder, ball-milling at the rotating speed of 500r/min for 8 hours, adding 10g of deionized water, uniformly mixing, filtering and drying to obtain a nano filler;
mixing the nanofiller and the suspension, heating to 60 ℃, adding 0.01g of sodium sulfite and 0.004g of ammonium persulfate, stirring for 8min, adding 0.12g of N, N-methylene bisacrylamide, uniformly mixing, precooling for 3h at-8 ℃, freeze-drying for 40h at-60 ℃, and crushing to 5 mu m to obtain the cellulose nanofibril aerogel.
Preparation example 7: the difference from preparation example 6 is that xylose powder was not added.
Preparation example 8: the difference from preparation example 6 is that montmorillonite was not added.
Preparation example 9: the difference from preparation example 6 is that boron nitride was not added.
Examples
Example 1: the raw material dosage of the stretch winding film for the machine is shown in Table 1, and the density of the metallocene polyethylene in the Table 1 is 0.912g/cm 3 The melt index is 2g/10min; the linear low density polyethylene had a density of 0.92g/cm 3 The melt index is 2g/10min, and the thickness ratio of the middle layer film, the inner layer film and the outer layer film is 1.
A preparation method of a machine-used stretch wrapping film comprises the following steps:
according to the weight parts, raw materials of an outer layer film, an inner layer film and a middle layer film are respectively put into a hopper, and are subjected to tape casting extrusion, cooling and shaping, and rolling to prepare the machine-used stretch winding film, wherein the tape casting extrusion temperature is 210 ℃, the rotating speed of an extruder is 400r/min, the temperature of a cooling roller is 20 ℃, and the rolling tension is 9kg.
TABLE 1
Example 2: a machine-used stretch wrap film differing from example 1 in that the raw material amounts are as shown in table 1, and a production method comprising the steps of: according to the weight parts, raw materials of an outer layer film, an inner layer film and a middle layer film are respectively put into a hopper, and are subjected to tape casting extrusion, cooling and shaping, and rolling to prepare the machine-used stretch winding film, wherein the tape casting extrusion temperature is 170 ℃, the rotating speed of an extruder is 600r/min, the temperature of a cooling roller is 25 ℃, and the rolling tension is 12kg.
Examples 3 to 5: a machine-used stretch wrap film differs from example 1 in that the raw material amounts are shown in Table 1.
Examples 6 to 7: a machine stretch wrap film is different from example 1 in that the used amounts of raw materials of an inner layer film, an outer layer film and a middle layer film are shown in Table 2, wherein a plasticizer is epoxidized soybean oil, a stabilizer is dibutyltin dilaurate, and an anti-aging agent is an anti-aging agent 2246, and an anti-reflection agent is prepared by mixing transparent titanium dioxide and silicon dioxide according to the mass ratio of 1, adding the mixture into an ethanol solution of a silane coupling agent KH570 with the concentration of 3wt%, performing immersion treatment for 20min, and then washing and drying the mixture.
TABLE 2
Example 8: a machine stretch wrap film differing from example 6 in that the inner film further included 20kg of a barrier modifier made from preparation example 1.
Example 9: a machine stretch wrap film differing from example 6 in that the inner film further included 10kg of a barrier modifier made from preparative example 2.
Example 10: a machine stretch wrap film differing from example 8 in that the barrier modifier was made from preparative example 3.
Example 11: a machine stretch wrap film differing from example 8 in that the barrier modifier was made from preparative example 4.
Example 12: a machine stretch wrap film differing from example 8 in that the barrier modifier was made from preparative example 5.
Example 13: a machine stretch wrap film differing from example 8 in that the barrier modifier was made from preparative example 6.
Example 14: a machine stretch wrap film differing from example 8 in that the barrier modifier was made from preparative example 7.
Example 15: a machine stretch wrap film differing from example 8 in that a barrier modifier was made from preparation example 8.
Example 16: a machine stretch wrap film differing from example 8 in that the barrier modifier was made from preparative example 9.
Comparative example
Comparative example 1: a stretch wrap film for machine use, which is different from example 1 in that the outer layer film and the inner layer film are made of the following raw materials: 75kg of a 3518cb metallocene polyethylene, 50kg of a 5220G metallocene polyethylene and 175kg of a 7042N linear low density polyethylene; the raw materials of the middle layer film are as follows: 150kg of a 3518cb metallocene polyethylene, 100kg of a 5220G metallocene polyethylene and 350kg of a 7042N linear low density polyethylene.
Comparative example 2: a machine stretch wrap film differing from example 1 in that metallocene polyethylene of type 2012MA was used in an amount of 125kg and linear low density polyethylene of type 7042N was used in an amount of 175kg in the outer layer film and the inner layer film; in the middle layer film, the metallocene polyethylene with the model number of 2012MA is used in an amount of 250kg, and the linear low density polyethylene with the model number of 7042N is used in an amount of 350kg.
Comparative example 3: the PE stretch wrap film in the embodiment is formed by co-extruding three layers of materials, namely an outer layer material, a middle layer material and an inner layer material, wherein the mass ratio of the outer layer material to the middle layer material to the inner layer material is 1. The outer layer material comprises the following components in parts by mass: 68 parts of Linear Low Density Polyethylene (LLDPE), 4 parts of Linear Medium Density Polyethylene (LMDPE) and 8 parts of Metallocene (MPE); the middle layer material comprises the following components in parts by mass: 60 parts of Linear Low Density Polyethylene (LLDPE), 3 parts of Linear Medium Density Polyethylene (LMDPE) and 7 parts of Metallocene (MPE); the inner layer material comprises the following components in percentage by mass: 56 parts of linear low-density polyethylene (LLDPE), 2 parts of Metallocene (MPE) and 3 parts of tackifier, wherein the tackifier is Polyisobutylene (PIB).
The preparation process of the PE stretch winding film comprises the following steps:
s1, respectively adding the components in the outer layer material, the middle layer material and the inner layer material into three stirring containers according to corresponding proportions, and uniformly stirring and mixing;
s2, respectively carrying out high-temperature extrusion on the mixture obtained in the three stirring containers in the step S1 through a screw extruder to obtain outer-layer, middle-layer and inner-layer plastic particles; wherein the heating temperature in the screw extruder is 220 ℃;
and S3, respectively adding the outer layer plastic particles, the middle layer plastic particles and the inner layer plastic particles obtained in the step S2 into corresponding cavities of a casting machine, forming a film through casting, wherein the casting temperature is 250 ℃, the temperature of a casting cooling roller is 20 ℃, and then rolling and packaging to obtain the PE stretch winding film, wherein the rolling tension is not more than 10kg.
Comparative example 4: a stretch winding film comprises the following raw materials in parts by weight: 40kg of linear low-density polyethylene, 1kg of pectin, 2kg of methyl cellulose, 3kg of acrylic acid, 5kg of polyethylene glycol, 10kg of reclaimed materials, 1kg of antioxidant, 0.5kg of nano titanium dioxide, 0.8kg of sodium phthalate, 1kg of calcium carbonate and 0.2kg of halogen-free flame retardant, wherein the reclaimed materials are redundant leftover materials in the process of preparing the stretching and winding film, and the antioxidant is a phenol antioxidant.
The preparation method of the stretch wrap film comprises the following steps:
(1) According to the mass ratio, melting the reclaimed materials, and uniformly mixing the melted reclaimed materials with the nano titanium dioxide and the calcium carbonate to obtain a mixture A;
(2) Uniformly mixing linear low-density polyethylene, pectin, methyl cellulose, acrylic acid, polyethylene glycol, an antioxidant, sodium phthalate and a halogen-free flame retardant, adding the mixture A into the mixture, and continuously stirring and mixing to obtain a mixture B;
(3) Carrying out double-screw extrusion granulation on the mixture B, wherein the rotating speed of an extruder is 250r/min, and the temperature is controlled at 170 ℃;
(4) And (4) feeding the particles obtained in the step (3) into a casting machine, wherein the film forming temperature is 230 ℃, the temperature of a cooling roller is controlled at 20 ℃, and the winding tension is 8kg, so as to obtain the stretch winding film.
Performance test
1. Winding films were prepared according to the methods in examples 1 to 16 and comparative examples 1 to 4, and performance tests were performed on the winding films with reference to the following methods, and the test results are recorded in table 3.
1. Tensile strength and elongation at break: the test is carried out according to GB/T13022 method for testing the tensile property of the plastic film.
2. Puncture resistance: according to GB/T37841-2019 method for testing puncture resistance of plastic films and sheets.
3. Water vapor transmission rate: according to GB/T26253-2010 Infrared Detector method for measuring Water vapor Transmission Rate of Plastic films and sheets, the measurements were carried out with a BASIC301 Water vapor Transmission Rate tester at a temperature of 23 ℃ and a relative humidity of 85%.
4. Oxygen transmission rate: the test was carried out using a VACV1 type oxygen transmission rate tester at a temperature of 23 ℃ and a relative humidity of 0%.
TABLE 3
As can be seen from the data in table 3, in examples 1 to 3, the wound film produced by using metallocene polyethylene having more excellent performance, having stronger breaking force and elongation at break and stronger puncture resistance, was obtained by using the same raw material for the outer layer film and the inner layer film and using the same amount of the raw material for the intermediate layer film as the total weight of the raw materials for the inner layer film and the outer layer film.
In example 4 and example 5, the amount of the raw material in the middle layer film was decreased and increased, respectively, and the tensile strength and puncture resistance of the wrap film were decreased as compared with example 1.
In examples 6 and 7, as compared with example 1, an anti-reflection agent, a plasticizer, a stabilizer and an anti-aging agent were further added to the middle layer film, the outer layer film and the inner layer film, and the wrap films prepared in examples 6 and 7 had an increased breaking force and slightly improved puncture resistance.
Compared with example 6, the barrier modifier is added in the inner layer film of examples 8 and 9, so that the tensile strength, elongation at break and puncture resistance of the winding film prepared in examples 8 and 9 are all improved remarkably, the permeability to oxygen and water vapor is reduced remarkably, and the barrier property is improved.
Example 10 using the barrier modifier made in preparative example 3 without treating the mixture of cellulose nanofibril aerogel and graphene oxide with a tridecafluorooctyl trimethoxysilane ethanol solution as compared to example 8, it is shown in table 3 that the wrapping film made in example 10 has a reduced barrier to water vapor.
Example 11 compared to example 8, using the barrier modifier from preparation 4 without graphene oxide added to preparation 4, table 3 shows that the stretch-break force and puncture resistance of the wrap film from example 11 are reduced and the barrier properties against water vapor and oxygen are reduced.
The barrier modifier prepared in preparation example 5, in which polyethyleneimine was not used, was used in example 12, and table 3 shows that the stretch force, elongation at break, and puncture resistance of the wrapping film were all reduced.
Example 13 compared to example 8, the winding film prepared in example 13 using the cellulose nanofibril aerogel prepared in preparation example 6 has significantly enhanced puncture resistance and improved barrier properties against water vapor and oxygen.
In example 14 using the barrier modifier of preparation example 7 in which montmorillonite and boron nitride were not dispersed in a single layer using xylose powder, the wrapping film prepared in example 14 had a reduced barrier property, a reduced breaking force and elongation at break, and a reduced puncture resistance, as compared to example 13.
In examples 15 and 16, the barrier modifiers prepared in preparative example 8 and preparative example 9 were used, respectively, and in preparative example 8 and preparative example 9, no montmorillonite and boron nitride were added, respectively, as compared to preparative example 6, and table 3 shows that the wrap films prepared in examples 15 and 16, both in terms of tensile strength, puncture resistance and barrier properties, are reduced compared to example 13.
In the outer layer film and the inner layer film in comparative example 1, two different types of metallocene polyethylenes are used, the amount of the metallocene polyethylene used is increased, the amount of the metallocene polyethylene used in the middle layer film is also increased correspondingly, and compared with example 1, the winding film prepared in comparative example 1 has reduced tensile strength and elongation at break and reduced puncture resistance.
In comparative example 2, compared with example 1, the amount of metallocene polyethylene in the outer layer film and the inner layer film was increased, the amount of linear low density polyethylene was decreased, and the puncture resistance and tensile strength of the resulting wrap film were decreased.
Comparative examples 3 and 4 are winding films prepared by the prior art, comparative example 3 is three layers, comparative example 4 is one layer, and table 3 shows that the winding films prepared by comparative examples 3 and 4 have less puncture resistance than example 1.
2. Winding films were prepared according to the methods of example 1 and examples 6 to 16, and the properties of the winding films were measured according to the following methods, and the measurement results are shown in table 4.
1. Transparency: the detection is carried out according to GB/T2410-1980 transparent plastic light transmittance and haze test method, and the detection wavelength is 500nm.
2. Contact angle of inner film with water: the inner film was fixed on a slide glass, and then 1. Mu.L of deionized water was dropped on the inner film by a syringe, and then measured 5 times at different places of the film by an IC2000D1 type contact angle tester, respectively, and then the average value was taken.
3. High-temperature antifogging property: according to GB4455-2006 polyethylene blow-molded greenhouse film for agriculture, 200ml of tap water is put into a disposable water cup, the disposable water cup is put into a water bath kettle, the disposable water cup is heated to a set temperature of 60 ℃, an inner layer film of a wound film faces to a cup opening, a rubber band is bound on the cup opening, the disposable water cup is placed in a constant-temperature water bath, the center of the surface of the film is pressed down, an angle between the film and the horizontal plane is kept at 15 degrees, and the fogging condition of the surface of the wound film is observed and recorded.
TABLE 4
Compared with example 1, the winding films prepared in examples 6 and 7, which are prepared by adding the antireflection agent in examples 6 and 7, have high transparency, large contact angle between the inner layer film and water and good antifogging effect.
Examples 8 and 9 also used a barrier modifier as compared to example 6, and it is shown in table 4 that the wrap films prepared in examples 8 and 9 further increased the contact angle with water, the transparency was improved, and the antifogging effect was increased.
Example 10 using the barrier modifier prepared in production example 3, the contact angle of the wrapping film with water was smaller than that of example 8 without adding tridecafluorooctyltrimethoxysilane ethanol solution, and the antifogging effect was reduced but the transparency was not changed much, compared to production example 1.
Example 11 compared to example 8, the barrier modifier prepared in preparation example 4 was used, graphene oxide was not added to preparation example 4, and the winding film prepared in example 11 was degraded in each property.
In example 12, the barrier modifier prepared in preparation example 5, in which polyethyleneimine is not used, transparency of the wrap film is decreased, and remaining properties are not greatly changed.
Example 13 using the cellulose nanofibril aerogel prepared in preparation example 6, as compared with example 8, it is shown in table 4 that the wrapping film prepared in example 13 has improved transparency, increased contact angle, and enhanced antifog effect.
In example 14, the barrier modifier prepared in preparation example 7 was used, wherein no xylose powder was used to disperse montmorillonite and boron nitride in a single layer, the transparency of the wound film was decreased, and the antifogging effect was reduced.
In example 15 and example 16, the barrier modifiers prepared in preparation example 8 and preparation example 9 were used, respectively, and in preparation example 8 and preparation example 9, compared with preparation example 6, montmorillonite and boron nitride were not added, respectively, and the wrapping films prepared in example 15 and example 16 were reduced in transparency and anti-fogging ability.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A machine stretch wrap film is characterized by comprising an outer layer film, a middle layer film and an inner layer film which are sequentially attached; the outer layer film and the inner layer film comprise the following raw materials in parts by weight: 60-90 parts of metallocene polyethylene and 200-250 parts of linear low-density polyethylene;
the middle layer film comprises the following raw materials in parts by weight: 120-180 parts of metallocene polyethylene and 400-500 parts of linear low-density polyethylene.
2. The machine stretch wrap film of claim 1, wherein:
the dosage of the metallocene polyethylene in the middle layer film is the sum of the dosages of the metallocene polyethylene in the outer layer film and the inner layer film;
the dosage of the linear low density polyethylene in the middle layer film is the sum of the dosages of the linear low density polyethylene in the outer layer film and the inner layer film.
3. The machine-used stretch wrap film according to claim 1, wherein each of the outer film and the inner film further comprises 1.5 to 3.5 parts by weight of an anti-reflection agent, 1 to 3 parts by weight of a plasticizer, 2 to 6 parts by weight of a stabilizer, and 0.6 to 1.2 parts by weight of an anti-aging agent;
the middle layer film also comprises 3-7 parts by weight of an anti-reflection agent, 2-6 parts by weight of a plasticizer, 4-12 parts by weight of a stabilizer and 1.2-2.4 parts by weight of an anti-aging agent.
4. The machine stretch wrap film of claim 3, wherein: the anti-reflection agent is pretreated by a silane coupling agent KH570, and the anti-reflection agent comprises transparent titanium dioxide and silicon dioxide with the mass ratio of 1.
5. The machine stretch wrap film of claim 1, wherein the metallocene polyethylene has a density of 0.912 to 0.915g/cm 3 The melt index is 2-2.2g/10min;
the linear low density polyethylene has a density of 0.92-0.935g/cm 3 The melt index is 2.0-2.3g/10min.
6. The machine stretch wrap film of claim 1, wherein the inner film further comprises 10-20 parts by weight of a barrier modifier, the barrier modifier comprising the following components in parts by weight: 0.3-0.5 part of graphene oxide, 0.01-0.03 part of cellulose nanofibrils, 1-2 parts of cellulose nanofibril aerogel, 0.5-1 part of tridecafluorooctyl trimethoxysilane ethanol solution, 0.1-0.25 part of polyethyleneimine and 1-1.5 parts of deionized water.
7. The machine-use stretch wrap film of claim 6, wherein the barrier modifier is formed by a method comprising:
adding cellulose nanofibrils into deionized water, stirring uniformly to prepare a dispersion liquid, adding graphene oxide, dispersing uniformly by ultrasonic, adding cellulose nanofibrils aerogel and polyethyleneimine, mixing uniformly, drying, adding an ethanol solution of tridecafluorooctyltrimethoxysilane, mixing uniformly and drying.
8. The machine stretch wrap film of claim 7, wherein the cellulose nanofibril aerogel is prepared by:
dispersing 2-3 parts of cellulose nano-fibrils in deionized water by weight to prepare a suspension with the concentration of 1-2 wt%;
mixing 0.6-0.9 part of montmorillonite, 0.3-0.6 part of boron nitride and 2.5-3 parts of xylose powder, ball-milling for 8-10h, adding deionized water, uniformly mixing, filtering and drying to obtain a nano filler;
mixing the nanofiller and the suspension, heating to 60-65 ℃, adding 0.01-0.02 part of sodium sulfite and 0.004-0.005 part of ammonium persulfate, stirring for 3-8min, adding 0.12-0.14 part of N, N-methylene bisacrylamide, uniformly mixing, precooling for 3-5h at the temperature of- (8-10), freeze-drying for 40-48h at the temperature of- (60-65), and crushing to obtain the cellulose nanofibril aerogel.
9. The method for producing a machine-stretch wrapping film of claim 1, comprising the steps of:
according to parts by weight, raw materials of the outer layer film, the inner layer film and the middle layer film are respectively put into a hopper, and the machine-used stretch wrap film is prepared by casting extrusion, cooling and shaping and rolling.
10. The method for preparing the machine-used stretch wrapping film according to claim 9, wherein the casting extrusion temperature is 170-210 ℃, the rotation speed of the extruder is 400-600r/min, the temperature of the cooling roller is 20-25 ℃, and the winding tension is 9-12kg.
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| CN116787891A (en) * | 2023-06-21 | 2023-09-22 | 青岛泰博聚合标签有限公司 | Stretch wrap film and method of making the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111057298A (en) * | 2019-12-25 | 2020-04-24 | 郑州市祥泰塑业有限公司 | PE (polyethylene) winding film and preparation method thereof |
| CN111346577A (en) * | 2020-03-30 | 2020-06-30 | 浙江晶鑫特种纸业有限公司 | Preparation method and application of high-elasticity layered graphene oxide composite aerogel |
| CN112848585A (en) * | 2019-11-26 | 2021-05-28 | 上海礼煦机电设备有限公司 | PE (polyethylene) stretching and winding film and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112848585A (en) * | 2019-11-26 | 2021-05-28 | 上海礼煦机电设备有限公司 | PE (polyethylene) stretching and winding film and preparation process thereof |
| CN111057298A (en) * | 2019-12-25 | 2020-04-24 | 郑州市祥泰塑业有限公司 | PE (polyethylene) winding film and preparation method thereof |
| CN111346577A (en) * | 2020-03-30 | 2020-06-30 | 浙江晶鑫特种纸业有限公司 | Preparation method and application of high-elasticity layered graphene oxide composite aerogel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116787891A (en) * | 2023-06-21 | 2023-09-22 | 青岛泰博聚合标签有限公司 | Stretch wrap film and method of making the same |
| CN116787891B (en) * | 2023-06-21 | 2024-03-29 | 青岛泰博聚合标签有限公司 | Stretch wrap film and method of making the same |
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