CN115923290B - Stretching winding film for machine and preparation method thereof - Google Patents
Stretching winding film for machine 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 stretching winding film and a preparation method thereof. The machine stretching winding 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-wrapping film has the advantages of high tensile strength, high puncture resistance, excellent barrier property, good transparency and capability of preventing the inner layer film from being atomized.
Description
Technical Field
The application relates to the technical field of packaging materials, in particular to a machine stretching winding film and a preparation method thereof.
Background
The machine stretch winding film is a packaging film which is used for tightly wrapping goods and is convenient to transport and store by utilizing deformation stress generated by forced stretching of the film by a mechanical device at normal temperature, and is a packaging form which is very popular internationally at present. The stretch wrap film has the characteristics of good stretching performance, tear resistance, strong penetration resistance, high transparency, good self-adhesion, high retraction rate, tight package, no loosening and the like. The packaging cost of bulk goods transportation can be reduced by more than 30%, so that the packaging method is widely applied to the whole packaging of various products such as hardware, mineral products, chemical industry, medicines, foods, machinery and the like, and the packaging method is mainly used for three-dimensional storage by using a stretch wrapping film tray package in the field of warehouse storage in foreign countries so as to save space and occupied space.
The existing winding film is mostly prepared from low-density polyethylene through a tape casting or film blowing process, but because the winding film is single in component, the tensile strength and the tearing strength of the winding film material are low, when the winding package is carried out, if the tension is slightly large, a fracture phenomenon occurs, and the winding film cannot be well applied to a package product.
With respect to the related art described above, the inventors found that the wound stretched film has poor tensile strength in practical applications and that the puncture resistance is to be improved.
Disclosure of Invention
In order to improve the tensile strength and puncture resistance of a wound film, the application provides a machine-used tensile wound 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 winding 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.
Through adopting above-mentioned technical scheme, all adopt metallocene polyethylene and linear low density polyethylene to make in middle layer membrane, outer layer membrane and the inlayer membrane to linear low density polyethylene is main substrate, and it has higher softening temperature and melting temperature, and intensity is high, toughness is good, heat and cold resistance is excellent, still has good environmental stress crack resistance, and impact strength, tear strength are high grade advantage, adds metallocene polyethylene to it can show improvement winding film's stretch-proof front degree, puncture resistance and tear resistance.
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 linear low-density polyethylene dosage in the middle layer film is the sum of the linear low-density polyethylene dosage in the outer layer film and the linear low-density polyethylene dosage in the inner layer film.
By adopting the technical scheme, the dosage of the outer layer film and the dosage of the inner layer film are the same, the middle layer film is the sum of the dosage of the outer layer film and the dosage of the inner layer film, and the winding film with strong puncture resistance and excellent breaking force can be obtained.
Optionally, the outer layer film and the inner layer film also 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, 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 comprises transparent titanium dioxide and silicon dioxide in a mass ratio of 1:0.5-1.
Through adopting above-mentioned technical scheme, use silica and transparent titanium dioxide as the anti-reflection agent, silica and transparent titanium dioxide are after silane coupling agent KH570 handles, can mix with the macromolecular material in middle layer membrane, outer layer membrane and the inlayer membrane evenly, and regard as the nucleating agent in extrusion casting, improve the transparency of wound membrane, in addition silica and transparent titanium dioxide are under KH 570's effect, form organic coating on transparent titanium dioxide and silica, make both have hydrophobicity, promote the compatibility of both with inlayer membrane raw materials, thereby disperse evenly in the inlayer membrane, improve inlayer membrane's hydrophobicity and the barrier property to vapor, make the water droplet easily slide from the inlayer membrane, reach antifog effect, not only make the wound membrane be applicable to sea fortune, remote transportation, can also be applicable to fruit vegetables transportation, can prevent to produce steam because of fruit vegetables respiratory effect in the wound membrane, cause inlayer membrane surface fog, influence food quality, cause food spoilage.
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 dibutyl tin dilaurate, octyl tin maleate, dibasic lead stearate, dibasic lead phthalate and dibasic lead phosphite;
the anti-aging agent is one or more selected from anti-aging agent 2246, anti-aging agent A and anti-aging agent NDBC.
By adopting the technical scheme, the tensile strength and puncture resistance of the winding film can be further improved by using the plasticizer, the stabilizer and the anti-aging agent.
Optionally, the metallocene polyethylene has a density of 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, and the flexibility, low modulus, tearing strength and puncture resistance are superior to those of the linear low-density polyethylene, and the tearing strength and stress cracking resistance of the winding film can be improved by blending the metallocene polyethylene with the linear low-density polyethylene.
Optionally, the inner layer film further comprises 10-20 parts by weight of a barrier modifier, wherein 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 nanofibril, 1-2 parts of cellulose nanofibril aerogel, 0.5-1 part of tridecyl trimethoxy silane ethanol solution, 0.1-0.25 part of polyethyleneimine and 1-1.5 parts of deionized water.
By adopting the technical scheme, the cellulose nanofibrillar aerogel is a novel solid material with high porosity and high specific surface area, has a unique three-dimensional reticular porous structure, has excellent flexibility and mechanical properties, and can improve the tensile resistance and tear strength of the winding film; the cellulose nanofibrils are used as novel nano biological materials, have larger specific surface area, can be stably dispersed in a solvent system for a long time to form hydrogel, have a plurality of hydroxyl groups on the surface, have strong adsorption effect with graphene oxide through hydrogen bonds, can be used as a dispersing agent of the graphene oxide, remarkably improve the dispersibility of the graphene oxide in water, disperse the graphene oxide into the nano cellulose nanofibrils, improve the mechanical property and barrier property of the cellulose nanofibrils, and can be uniformly dispersed with cellulose nanofibril aerogel under the condition that the cellulose nanofibrils are used as the dispersing agent, and the polyethylene imine can enhance interface interaction between the cellulose nanofibril aerogel and the graphene oxide, and can also organize swelling and water absorption of the cellulose nanofibril aerogel, so that the water resistance and barrier property of the barrier modifier are improved, and the winding film is suitable for winding packaging of maritime transportation and remote transportation.
Optionally, the barrier modifier is made by the following method:
adding cellulose nanofibrils into deionized water, stirring uniformly to prepare dispersion liquid, adding graphene oxide, dispersing uniformly by ultrasonic, adding cellulose nanofibril aerogel and polyethyleneimine, mixing uniformly, drying, adding ethanol solution of tridecafluorooctyl trimethoxy silane, mixing uniformly and drying.
According to the technical scheme, the graphene oxide is added into the dispersion liquid, the graphene oxide can be uniformly dispersed under the dispersion effect of the cellulose nanofibrils, the dispersion uniformity of the graphene oxide, the cellulose nanofibril aerogel and the polyethyleneimine is improved, the interfacial acting force of the graphene oxide and the cellulose nanofibril aerogel is increased by the polyethyleneimine, the cellulose nanofibril aerogel is attached to the graphene oxide, the barrier property of the cellulose nanofibril aerogel to water vapor and oxygen is improved, in addition, the cellulose nanofibril aerogel is subjected to hydrophobic treatment by using tridecyl trimethoxysilane, the barrier property and the antifogging effect of a barrier modifier to water vapor are improved, the compatibility of the cellulose nanofibril aerogel and an inner layer film raw material is improved, the mechanical strength is improved, in addition, after the cellulose nanofibril aerogel is coated on the graphene oxide, the cellulose nanofibril aerogel is added into an inner layer film, and the transparency of a winding film is improved.
Optionally, the preparation method of the cellulose nanofibrillar aerogel comprises the following steps:
dispersing 2-3 parts by weight of cellulose nanofibrils in deionized water 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 8-10 hours, adding deionized water, filtering after uniformly mixing, and drying to obtain 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, pre-cooling 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 nanofibrillar aerogel.
By adopting the technical scheme, the nano cellulose fibril has high strength and high transparency, and the barrier property, strength and toughness of the aerogel can be obviously improved by adding the two-dimensional nanomaterial montmorillonite and boron nitride into the one-dimensional cellulose fibril; under the modification of the xylose powder, hydrophilic groups such as hydroxyl, amino agent xylose and the like are introduced into the surfaces of the montmorillonite and the boron nitride, the dispersion uniformity of the suspension with cellulose nanofibrils is obviously improved, the milled and dispersed montmorillonite and boron nitride exist in the suspension in a single-piece form, the suspension is transparent and clear, the transparency of a winding film is not affected, the single-layer montmorillonite and the boron nitride nanosheets can promote the aerogel to form an ordered structure, and in the transmission of external force and light, the single-layer montmorillonite and the boron nitride nanosheets are orderly overlapped in a composite film, so that the consumption of force and the propagation of light are more facilitated, and the mechanical strength and the optical performance can be improved; the single-layer montmorillonite and the boron nitride nano-sheets can be uniformly embedded into a cellulose nanofibril aerogel network, a highly ordered structure is formed, disordered stacking is reduced, the single-layer montmorillonite and the boron nitride nano-sheets in the cellulose nanofibril aerogel are uniform and ordered, the anisotropism of the two-dimensional inorganic montmorillonite sheets and the boron nitride nano-sheets in the aerogel can lead to the extension of the diffusion path of gas, thereby blocking the permeation of gas, further improving the barrier property of the cellulose nanofibril aerogel to water vapor and oxygen, improving the light transmittance and improving the transparency.
In a second aspect, the application provides a method for preparing a machine stretch wrap film, which adopts the following technical scheme:
a method for preparing a machine stretch wrap film comprising the steps of:
according to the parts by weight, the raw materials of the outer layer film, the inner layer film and the middle layer film are respectively put into a hopper, and the stretching winding film for the machine is prepared through tape casting extrusion, cooling shaping and winding.
By adopting the technical scheme, the formula of each layer of material of the stretch-wrapping film is reasonable, and the three-layer coextrusion process is adopted, so that the prepared wrapping film has the advantages of uniform film thickness, high transparency, 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 application has the following beneficial effects:
1. the application adopts the linear low density polyethylene as the main raw materials of the middle layer film, the inner layer film and the outer layer film and is matched with the metallocene polyethylene, so that 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 in 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 by a silane coupling agent KH570, the transparency of the winding film can be improved, the barrier property of the winding film to water vapor and oxygen is increased, the hydrophobicity of the inner layer film in the winding film is improved, the anti-fog effect is improved, and the mechanical strength of the winding film is further improved.
3. According to the application, the blocking modifier is preferably added into the inner layer film, and the preparation method of the blocking modifier is that the cellulose nanofibrillar aerogel is attached to graphene oxide under the action of polyethyleneimine, and then tridecafluorooctyl trimethoxy silane is utilized to improve the hydrophobicity of the cellulose nanofibrillar aerogel, so that the blocking property of the cellulose nanofibrillar aerogel is improved under the action of graphene oxide, the inner layer film not only has a hydrophobic anti-fog effect, but also has good blocking property, and the winding film is suitable for packaging in sea transportation and long-distance transportation.
4. According to the application, the montmorillonite and boron nitride dispersed by grinding the xylose powder are preferably adopted to be blended with the cellulose nanofibrillar dispersion liquid to prepare the aerogel, and the single-layer montmorillonite and boron nitride sheet can improve the barrier property of the aerogel, improve the light transmittance of the aerogel and improve the transparency of the wound film.
Detailed Description
Preparation examples 1 to 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, performing ultrasonic dispersion for 10min at a power of 200w, adding 2kg of cellulose nanofibril aerogel and 0.25kg of polyethyleneimine, uniformly mixing, drying at 60 ℃ for 4h, adding 1kg of tridecafluorooctyl trimethoxy silane ethanol solution with a concentration of 80wt%, uniformly mixing, and drying, wherein the preparation method of the cellulose nanofibril aerogel is as follows: 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 into the suspension, magnetically stirring the mixture for 8min, adding 0.12N, N-methylenebisacrylamide into the mixture, uniformly mixing the mixture, pre-cooling the mixture at the temperature of minus 8 ℃ for 3h, vacuum-drying the mixture at the temperature of minus 60 ℃ for 48h, and crushing the mixture to 5 mu m;
preparation example 2: adding 0.01kg of cellulose nanofibril into 1kg of deionized water, uniformly stirring to prepare a dispersion liquid, adding 0.3kg of graphene oxide, performing ultrasonic dispersion for 15min at 150w of power, adding 1kg of cellulose nanofibril aerogel and 0.1kg of polyethyleneimine, uniformly mixing, drying for 4h at 60 ℃, adding 0.5kg of tridecafluorooctyl trimethoxy silane ethanol solution with the concentration of 80wt%, uniformly mixing, and drying, wherein the preparation method of the cellulose nanofibril aerogel is as follows: 2g of cellulose nanofibrils are dispersed in deionized water to prepare a suspension with the concentration of 1wt%, 0.01g of anhydrous sodium sulfite and 0.004g of ammonium persulfate are added into the suspension, magnetic stirring is carried out for 8min, 0.12N, N-methylene bisacrylamide is added, after uniform mixing, the mixture is precooled for 3h at the temperature of minus 8 ℃, then vacuum drying is carried out at the temperature of minus 60 ℃, and the mixture is crushed to 5 mu m.
Preparation example 3: the difference from preparation example 1 is that tridecafluorooctyltrimethoxysilane ethanol solution was 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 was added.
Preparation example 6: the difference from preparation example 1 is that the cellulose nanofibrillar aerogel was prepared by dispersing 2g of cellulose nanofibrillar in deionized water to prepare a suspension having a concentration of 1 wt%;
mixing 0.6g of montmorillonite, 0.3g of boron nitride and 2.5g of xylose powder, ball-milling for 8 hours at a rotating speed of 500r/min, adding 10g of deionized water, uniformly mixing, filtering and drying to obtain 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, pre-cooling for 3h at-8 ℃, then freeze-drying for 40h at-60 ℃, and crushing to 5 mu m to obtain the cellulose nanofibrillar aerogel.
Preparation example 7: the difference from preparation example 6 is that no xylose powder was 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: a machine stretch wrap film having a raw material content as shown in Table 1, the metallocene polyethylene in Table 1 having a density of 0.912g/cm 3 The melt index is 2g/10min; the density of the linear low density polyethylene was 0.92g/cm 3 The melt index was 2g/10min, and the thickness ratio of the middle film, the inner film and the outer film was 1:0.5:0.5.
A method for preparing a machine stretch wrap film comprising the steps of:
according to the parts by weight, the 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 stretching winding film is prepared by casting extrusion, cooling shaping and winding, wherein the casting extrusion temperature is 210 ℃, the rotating speed of an extruder is 400r/min, the temperature of a cooling roller is 20 ℃, and the winding tension is 9kg.
TABLE 1
Example 2: the machine stretch wrap film differs from example 1 in that the raw material amounts are shown in table 1, the method of preparation comprising the steps of: according to the parts by weight, the 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 stretching winding film is prepared by casting extrusion, cooling shaping and winding, wherein the casting extrusion temperature is 170 ℃, the rotating speed of an extruder is 600r/min, the temperature of a cooling roller is 25 ℃, and the winding tension is 12kg.
Examples 3 to 5: an machine stretch wrap film was distinguished from example 1 in that the raw material amounts are shown in table 1.
Examples 6 to 7: the difference between the machine stretch wrap film and the example 1 is that the raw materials of the inner film, the outer film and the middle film are shown in Table 2, wherein the plasticizer is epoxidized soybean oil, the stabilizer is dibutyl tin dilaurate, the anti-aging agent is anti-aging agent 2246, and the anti-reflection agent is prepared by mixing transparent titanium dioxide and silicon dioxide according to a mass ratio of 1:1, adding into an ethanol solution of a silane coupling agent KH570 with a concentration of 3wt%, immersing for 20min, washing and drying.
TABLE 2
Example 8: an organic stretch wrap film differs from example 6 in that the inner film also includes 20kg of a barrier modifier made from preparation 1.
Example 9: an organic stretch wrap film differs from example 6 in that the inner film also includes 10kg of a barrier modifier made from preparation 2.
Example 10: an organic stretch wrap film differs from example 8 in that the barrier modifier was made from preparation 3.
Example 11: an organic stretch wrap film differs from example 8 in that the barrier modifier was made from preparation 4.
Example 12: an organic stretch wrap film differs from example 8 in that the barrier modifier was made from preparation 5.
Example 13: an organic stretch wrap film differs from example 8 in that the barrier modifier was made from preparation 6.
Example 14: an organic stretch wrap film differs from example 8 in that the barrier modifier was made from preparation 7.
Example 15: an organic stretch wrap film differs from example 8 in that the barrier modifier was made from preparation 8.
Example 16: an organic stretch wrap film differs from example 8 in that the barrier modifier was made from preparation 9.
Comparative example
Comparative example 1: the machine stretch wrap film differs from example 1 in that the outer and inner films are both: 75kg of a metallocene polyethylene of model 3518cb, 50kg of a metallocene polyethylene of model 5220G and 175kg of a linear low density polyethylene of model 7042N; the middle layer film comprises the following raw materials: 150kg of a metallocene polyethylene of model 3518cb, 100kg of a metallocene polyethylene of model 5220G and 350kg of a linear low density polyethylene of model 7042N.
Comparative example 2: the machine stretch wrap film differs from example 1 in that in the outer and inner films, the metallocene polyethylene of type 2012MA was used in an amount of 125kg and the linear low density polyethylene of type 7042N was used in an amount of 175kg; in the middle layer, the amount of metallocene polyethylene of type 2012MA was 250kg and the amount of linear low density polyethylene of type 7042N was 350kg.
Comparative example 3: the PE stretch-wrapping film in this embodiment is formed by co-extrusion of 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 1:3:1, and the thickness of the PE stretch-wrapping film is 24 μm. The outer layer material comprises the following components in parts by weight: 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 weight: 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 Polyisobutene (PIB).
The preparation process of the PE stretch-wrapping film comprises the following steps:
s1, respectively adding all components in an outer layer material, a middle layer material and an inner layer material into three stirring containers according to corresponding proportions, and stirring and mixing uniformly;
s2, respectively extruding the mixture obtained in the three stirring containers in the step S1 at high temperature 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, the middle layer and the inner layer of plastic particles obtained in the step S2 into corresponding chambers in a casting machine, and casting to form a film, 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, and the rolling tension is not more than 10kg.
Comparative example 4: the stretch-wrapping film comprises the following raw materials in parts by mass: 40kg of linear low density polyethylene, 1kg of pectin, 2kg of methylcellulose, 3kg of acrylic acid, 5kg of polyethylene glycol, 10kg of reclaimed materials, 1kg of antioxidants, 0.5kg of nano titanium dioxide, 0.8kg of sodium phthalate, 1kg of calcium carbonate and 0.2kg of halogen-free flame retardants, wherein the reclaimed materials are redundant leftover materials in the process of preparing a stretched wound film, and the antioxidants are phenolic antioxidants.
The preparation method of the stretch wrap film comprises the following steps:
(1) According to the mass ratio, the regenerated material is melted and then is uniformly mixed with nano titanium dioxide and calcium carbonate to obtain a mixture A;
(2) Uniformly mixing linear low-density polyethylene, pectin, methylcellulose, acrylic acid, polyethylene glycol, an antioxidant, sodium phthalate and a halogen-free flame retardant, then adding the mixture A into the mixture, and continuously stirring and mixing to obtain a mixture B;
(3) Carrying out twin-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 (3) feeding the particles obtained in the step (3) into a casting machine, wherein the film making temperature is 230 ℃, the temperature of a cooling roller is controlled at 20 ℃, and the winding tension is 8kg, so that the stretch winding film is obtained.
Performance test
1. Wound films were prepared according to the methods in examples 1 to 16 and comparative examples 1 to 4, and performance test was performed on the wound films with reference to the following methods, and the test results are recorded in table 3.
1. Tensile force and elongation at break: the test is carried out according to GB/T13022 test method for tensile Property of Plastic film.
2. Puncture resistance: according to GB/T37841-2019 test method for puncture resistance of Plastic films and sheets.
3. Water vapor transmission rate: the test was carried out according to GB/T26153-2010 method for infrared detector for determination of Water vapor Transmission of Plastic films and sheets using a BASIC301 Water vapor Transmission tester at a temperature of 23℃and a relative humidity of 85%.
4. Oxygen transmission rate: the test was performed using a VACV type 1 oxygen transmission tester at a temperature of 23 ℃ and a relative humidity of 0%.
TABLE 3 Table 3
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As can be seen from the data in Table 3, in examples 1 to 3, the materials of the outer layer film and the inner layer film were made the same, and the material amount of the middle layer film was the total weight of the materials of the inner layer film and the outer layer film, and the metallocene polyethylene having more excellent use properties was used, and the produced wound film had stronger breaking force and breaking elongation and also strong puncture resistance.
In examples 4 and 5, the amount of the raw material in the middle layer film was decreased and increased, respectively, and the stretch breaking force and puncture resistance of the wound film were reduced as compared with example 1.
In examples 6 and 7, an antireflective agent, a plasticizer, a stabilizer and an anti-aging agent were further added to the middle film, the outer film and the inner film, and the wound films prepared in examples 6 and 7 had an increased stretch-break force and slightly improved puncture resistance, as compared with example 1.
Compared with example 6, example 8 and example 9 are also added with a barrier modifier, the stretch breaking force, the elongation at break and the puncture resistance of the wound films prepared in example 8 and example 9 are all obviously improved, the permeability to oxygen and water vapor is obviously reduced, and the barrier property is improved.
Example 10 compared to example 8, the barrier modifier prepared in preparation 3 was used, wherein the mixture of cellulose nanofibrillar aerogel and graphene oxide was not treated with tridecafluorooctyltrimethoxysilane ethanol solution, and the barrier properties to water vapor were reduced for the wound film prepared in example 10 as shown in table 3.
Example 11 the barrier modifier prepared in preparation example 4 was used, and graphene oxide was not added in preparation example 4, and it is shown in table 3 that the stretch breaking force and puncture resistance of the wound film prepared in example 11 were reduced and barrier properties against water vapor and oxygen were reduced, compared with example 8.
The barrier modifier prepared in preparation 5 was used in example 12, in which no polyethyleneimine was used, and it is shown in Table 3 that the tensile breaking force, elongation at break and puncture resistance of the wound film were all reduced.
Example 13 the wound film prepared in example 13 was significantly enhanced in puncture resistance and improved in barrier to water vapor and oxygen compared to example 8 using the cellulose nanofibrillar aerogel prepared in preparation example 6.
The barrier modifier of preparation example 7 was used in example 14, in which montmorillonite and boron nitride were not dispersed in a single layer using xylose powder, and the wound film of example 14 was reduced in barrier property, reduced in breaking force and elongation at break, and reduced in puncture resistance, as compared with example 13.
The barrier modifiers prepared in preparation examples 8 and 9 were used in examples 15 and 16, respectively, and montmorillonite and boron nitride were not added in preparation examples 8 and 9, respectively, as compared with preparation example 6, and the wound films prepared in examples 15 and 16 were reduced in tensile strength, puncture resistance, and barrier properties as compared with example 13, as shown in table 3.
In the outer layer film and the inner layer film of comparative example 1, two different types of metallocene polyethylenes are used, the amount of metallocene polyethylenes used is increased, the amount of metallocene polyethylenes used in the middle layer film is correspondingly increased, and the wound film prepared in comparative example 1 has lower breaking force and elongation at break and lower puncture resistance than those prepared in example 1.
Comparative example 2 the amount of metallocene polyethylene in the outer and inner films was increased and the amount of linear low density polyethylene was decreased, and the puncture resistance of the resulting wound film was decreased and the tensile strength was decreased, as compared with example 1.
Comparative example 3 and comparative example 4 are prior art wound films, comparative example 3 is three layers, comparative example 4 is one layer, and the puncture resistance of the wound films made in comparative example 3 and comparative example 4 is less than that of example 1, as shown in table 3.
2. A wound film was produced according to the method in example 1, examples 6 to 16, and the properties of the wound film were measured according to the following methods, and the measurement results are recorded in table 4.
1. Transparency: the detection is carried out according to GB/T2410-1980 test method for light transmittance and haze of transparent plastics, and the detection wavelength is 500nm.
2. Contact angle of inner film with water: the inner film was fixed on a glass slide, 1. Mu.L of deionized water was dropped on the inner film by a syringe, and then the film was measured 5 times at different places by an IC2000D1 type contact angle tester, respectively, and then an average value was taken.
3. High temperature anti-fog properties: referring to GB4455-2006 agricultural polyethylene blow molding greenhouse film, 200ml of tap water is placed in a disposable water cup, the disposable water cup is placed in a water bath kettle, after the disposable water cup is heated to the set temperature of 60 ℃, an inner layer film of a winding film faces to a cup opening, a rubber band is used for binding the winding film to the cup opening, the winding film is placed in a constant-temperature water bath, then the center of a film surface is pressed down, the film and a horizontal plane are kept to form an angle of 15 degrees, and the surface fogging condition of the winding film is observed and recorded.
TABLE 4 Table 4
Compared with example 1, the anti-reflection agent is added in example 6 and example 7, the winding films prepared in example 6 and example 7 have high transparency, the contact angle of the inner layer film with water is large, and the anti-fog effect is good.
In examples 8 and 9, a barrier modifier was also used as compared with example 6, and it is shown in table 4 that the wound films prepared in examples 8 and 9 have further increased contact angle with water, improved transparency, and increased antifogging effect.
In example 10, the barrier modifier prepared in preparation example 3 was used, and the contact angle of the wound film with water was smaller than that in example 8, but the transparency was not changed much, as compared with preparation example 1, without adding tridecafluorooctyltrimethoxysilane ethanol solution.
In example 11, the properties of the wound film prepared in example 11 were reduced compared to example 8, using the barrier modifier prepared in preparation example 4, without graphene oxide added in preparation example 4.
The barrier modifier prepared in preparation 5 was used in example 12, where the polyethylene imine was not used, the transparency of the wound film was somewhat reduced, and the remaining properties were not changed much.
In example 13, the cellulose nanofibrillar aerogel prepared in preparation example 6 was used, and it is shown in table 4 that the transparency of the wound film prepared in example 13 was improved, and the contact angle was increased and the antifogging effect was enhanced, compared with example 8.
In example 14, the barrier modifier prepared in preparation example 7 was used, in which montmorillonite and boron nitride were not dispersed in a single layer using xylose powder, the transparency of the wound film was lowered, and the antifogging effect was reduced.
The barrier modifiers prepared in preparation examples 8 and 9 were used in examples 15 and 16, respectively, and montmorillonite and boron nitride were not added in preparation examples 8 and 9, respectively, and the transparency of the wound films prepared in examples 15 and 16 was lowered and the antifogging ability was lowered, respectively, as compared with preparation example 6.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (6)
1. The machine stretching winding 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;
the using amount of the metallocene polyethylene in the middle layer film is the sum of the using amounts of the metallocene polyethylene in the outer layer film and the inner layer film;
the linear low-density polyethylene dosage in the middle layer film is the sum of the linear low-density polyethylene dosage in the outer layer film and the linear low-density polyethylene dosage in the inner layer film;
the inner layer film also comprises 10-20 parts by weight of a barrier modifier, wherein 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 ethanol solution of tridecafluorooctyl trimethoxysilane with concentration of 80wt%, 0.1-0.25 part of polyethyleneimine and 1-1.5 parts of deionized water;
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 nanofibril aerogel and polyethyleneimine, mixing uniformly, drying, adding ethanol solution of tridecafluorooctyl trimethoxy silane, mixing uniformly, and drying;
the preparation method of the cellulose nanofibrillar aerogel comprises the following steps:
dispersing 2-3 parts by weight of cellulose nanofibrils in deionized water 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 8-10 hours, adding deionized water, filtering after uniformly mixing, and drying to obtain 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, pre-cooling 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 nanofibrillar aerogel.
2. The stretch-wrap film for a machine according to claim 1, wherein the outer and inner films each further comprise 1.5 to 3.5 parts by weight of an antireflective agent, 1 to 3 parts by weight of a plasticizer, 2 to 6 parts by weight of a stabilizer, 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.
3. The machine stretch wrap film of claim 2, wherein: the anti-reflection agent is pretreated by a silane coupling agent KH570, and comprises transparent titanium dioxide and silicon dioxide in a mass ratio of 1:0.5-1.
4. The machine stretch wrap film of claim 1 wherein said 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.
5. The method for producing a machine stretch wrap film of claim 1, comprising the steps of:
according to the parts by weight, the raw materials of the outer layer film, the inner layer film and the middle layer film are respectively put into a hopper, and the stretching winding film for the machine is prepared through tape casting extrusion, cooling shaping and winding.
6. The method for producing a stretch-wrap film for machine use according to claim 5, wherein the casting extrusion temperature is 170 to 210 ℃, the extruder rotation speed is 400 to 600r/min, the cooling roll temperature is 20 to 25 ℃, and the winding tension is 9 to 12kg.
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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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