CN114409995A - Multilayer-stacked degradable flame-retardant antirust heat shrinkable film and preparation method thereof - Google Patents
Multilayer-stacked degradable flame-retardant antirust heat shrinkable film and preparation method thereof Download PDFInfo
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- 229920006257 Heat-shrinkable film Polymers 0.000 title claims abstract description 68
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000003063 flame retardant Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000009413 insulation Methods 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 59
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- 229920000092 linear low density polyethylene Polymers 0.000 claims description 24
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 24
- 229920001684 low density polyethylene Polymers 0.000 claims description 22
- 239000004702 low-density polyethylene Substances 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 22
- 239000007822 coupling agent Substances 0.000 claims description 20
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- 229920001526 metallocene linear low density polyethylene Polymers 0.000 claims description 18
- 238000000137 annealing Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000010030 laminating Methods 0.000 claims description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002250 absorbent Substances 0.000 claims description 5
- 230000002745 absorbent Effects 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 239000004203 carnauba wax Substances 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- -1 polypropylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 10
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims 1
- 230000006750 UV protection Effects 0.000 abstract description 4
- 238000004806 packaging method and process Methods 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 3
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010096 film blowing Methods 0.000 description 6
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- 239000002184 metal Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 description 1
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- 238000009264 composting Methods 0.000 description 1
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Abstract
The invention relates to a multilayer superposed degradable flame-retardant antirust heat shrinkable film and a preparation method thereof, wherein the heat shrinkable film is a multilayer composite co-extruded film, and the heat shrinkable film comprises the following components from inside to outside: the coating comprises a tensile layer, an antirust layer, an internal heat shrinkage layer, a flame-retardant heat insulation layer, an external heat shrinkage layer and an ultraviolet-resistant layer. The heat shrinkable film can also prevent potential safety hazards caused by fire; moreover, the fertilizer can be degraded, and has no harm to the environment and soil; the heat shrinkable film has multiple functions of heat insulation, flame retardance, UV resistance and degradation. In the production process, six layers are overlapped and are laminated according to the inclination angle of 15-60 degrees in the traction direction, so that the strength of the heat shrinkable film is higher, and the heat shrinkable film has higher tensile, puncture and drop hammer resistant effects, has the tensile resistance, the penetration resistance, the impact resistance, the tear resistance and the stress cracking resistance, and can meet the packaging requirements of large-scale equipment with different shapes and specifications.
Description
Technical Field
The invention relates to a multilayer superposed degradable flame-retardant antirust heat shrinkable film and a preparation method thereof, belonging to the technical field of heat shrinkable films.
Background
The corrosion of metal is a global problem, the loss caused by corrosion is very large every year, and the loss in the aspects can be reduced to a great extent by applying antirust packaging materials in various industries such as automobiles, aerospace, nuclear power, rail transit, metal processing, machinery, electronic components and the like. With the development of the Chinese industry, the rust prevention and control become more and more important to the Chinese heavy equipment. The period from production to use of large-scale equipment is long, and the protective performance of the antirust packaging material is very important in the processes of storage and marine transportation of the large-scale equipment.
At present, the anti-rust film in the domestic market only has thermal shrinkage performance, but no method is available for simultaneously achieving multiple functions of heat insulation, flame retardance, UV resistance, degradation and the like. Therefore, for some equipment with different shapes and large specifications, the existing heat shrinkage film cannot meet the use requirement, in addition, the existing environment protection requirement is very high, the heat shrinkage film belongs to an easily-consumed product, and great environment protection pressure can be brought if good degradability cannot be realized.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a multilayer superposed degradable flame-retardant antirust heat shrinkable film and a preparation method thereof, wherein the heat shrinkable film can simultaneously give consideration to multiple functions of heat insulation, flame retardance, UV resistance and degradability, has better tensile, puncture and drop weight resistance effects, and can meet the packaging requirements of large-scale equipment with different shapes and specifications.
The technical scheme for solving the technical problems is as follows: a multilayer superposed degradable flame-retardant antirust heat shrinkable film is a multilayer composite co-extruded film, and the heat shrinkable film comprises the following components from inside to outside: the anti-rust coating comprises a tensile layer, an anti-rust layer, an internal heat shrinkage layer, a flame-retardant heat insulation layer, an external heat shrinkage layer and an ultraviolet-resistant layer;
the anti-rust coating comprises, by weight, 5-10 parts of LDPE (low density polyethylene), 10-20 parts of LLDPE (linear low density polyethylene), 20-30 parts of MLLDPE (metallocene polyethylene), 10-20 parts of VCI (vinyl chloride), 1-5 parts of dispersing agent, 1-5 parts of coupling agent, 1-5 parts of antioxidant, 0.1-1.5 parts of antistatic master batch and 0.5-1 part of biodegradable master batch;
the flame-retardant heat-insulating layer comprises, by weight, 5-10 parts of LDPE, 10-15 parts of LLDPE, 20-25 parts of MLLDPE, 10-15 parts of VCI antirust master batch, 1-5 parts of dispersant, 1-5 parts of coupling agent, 1-5 parts of antioxidant and 1-2 parts of flame-retardant master batch;
the ultraviolet resistant layer comprises, by weight, 5-10 parts of LDPE, 10-15 parts of LLDPE, 25-30 parts of MLLDPE, 10-15 parts of VCI antirust master batch, 1-5 parts of dispersant, 1-5 parts of coupling agent, 1-5 parts of antioxidant, 0.1-1 part of antistatic master batch and 1-5 parts of ultraviolet absorbent.
Further, the tensile layer comprises, by weight, 5-10 parts of LDPE, 15-20 parts of LLDPE, 25-30 parts of MLLDPE, 10-15 parts of VCI antirust master batch, 1-5 parts of dispersant, 1-5 parts of coupling agent, 1-5 parts of antioxidant, 1-1.5 parts of antistatic master batch and 0.5-1 part of biodegradable master batch;
according to the parts by weight, the anti-rust layer comprises 5-10 parts of LDPE, 10-15 parts of LLDPE, 20-25 parts of MLLDPE, 15-20 parts of VCI anti-rust master batch, 1-5 parts of dispersing agent, 1-5 parts of coupling agent, 1-3 parts of antioxidant, 0.1-1.0 part of antistatic master batch and 0.5-1 part of biodegradable master batch;
according to the parts by weight, the internal heat shrinkage layer comprises 8-10 parts of LDPE, 10-15 parts of LLDPE, 20-25 parts of MLLDPE, 10-15 parts of VCI antirust master batch, 1-5 parts of dispersing agent, 1-5 parts of coupling agent, 1-3 parts of antioxidant, 0.1-1.5 parts of antistatic master batch and 0.5-1 part of biodegradable master batch;
the outer heat-shrinkable layer comprises, by weight, 5-10 parts of LDPE, 12-15 parts of LLDPE, 25-30 parts of MLLDPE, 10-20 parts of VCI antirust master batch, 1-5 parts of dispersing agent, 1-5 parts of coupling agent, 1-5 parts of antioxidant, 0.1-1.5 parts of antistatic master batch and 0.5-1 part of biodegradable master batch;
the flame-retardant heat-insulating layer comprises, by weight, 5-10 parts of LDPE, 10-15 parts of LLDPE, 20-25 parts of MLLDPE, 10-15 parts of VCI antirust master batch, 1-5 parts of dispersing agent, 1-5 parts of coupling agent, 1-5 parts of antioxidant, 1-2 parts of flame-retardant master batch and 0.1-1 part of shading master batch;
the ultraviolet resistant layer comprises, by weight, 5-10 parts of LDPE, 10-15 parts of LLDPE, 25-30 parts of MLLDPE, 10-15 parts of VCI antirust master batch, 1-5 parts of dispersant, 1-5 parts of coupling agent, 1-5 parts of antioxidant, 0.1-1 part of antistatic master batch, 1-5 parts of ultraviolet absorbent and 5-8 parts of master batch. The addition of the color master batch can endow the heat shrinkable film with different colors, thereby being more beneficial to the aesthetic property of packaging.
Further, the LDPE is Yanshan petrochemical LD 163; the LLDPE is a LLDPE with a medium petrochemical metallocene name DMDB-8916; the VCI antirust master batch is a RUST-X VCI antirust master batch.
Further, the dispersant is one or a mixture of polypropylene wax and palm wax; the coupling agent is a silane coupling agent, the flame-retardant master batch is a halogen-series PE flame-retardant master batch, and the antioxidant is a mixture of hindered phenol antioxidant and phosphite antioxidant.
Further, the silane coupling agent is selected from one or a mixture of more of gamma-methacryloxy triethoxysilane, gamma-aminopropyl trimethoxysilane, vinyl trimethoxysilane and gamma-aminopropyl triethoxysilane;
further, the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: 0.5 to 2;
the hindered phenol antioxidant is one or a mixture of an antioxidant 1010 and an antioxidant 1076, and the phosphite antioxidant is an antioxidant 168.
Further, the ultraviolet absorbent is one or a mixture of benzophenone, benzophenone derivatives, benzotriazole and benzotriazole derivatives.
Furthermore, the thickness of the tensile layer, the anti-rust layer, the internal heat shrinkage layer, the flame-retardant heat-insulating layer, the external heat shrinkage layer and the ultraviolet-resistant layer is 30-40 mu m, and the thickness of the heat shrinkage film is 150-250 mu m.
The invention also discloses a preparation method of the multilayer superposed degradable flame-retardant antirust heat shrinkable film, which comprises the following steps:
(1) adding corresponding raw materials into respective extruder hoppers according to the raw material proportion of each layer of the heat shrinkable film, and co-extruding and blowing the film through an extruder and a die head to form film bubbles of each layer;
(2) laminating the film bubbles of each layer in the sequence of a tensile layer, an antirust layer, an internal heat shrinkage layer, a flame-retardant heat insulation layer, an external heat shrinkage layer and an ultraviolet-resistant layer from inside to outside, clamping, drawing and self-bonding to form a film, and laminating the adjacent two layers of film bubbles in the drawing direction according to an inclination angle of 15-60 degrees;
(3) and heating, stretching, annealing, cooling and rolling the film formed by self-bonding to obtain the heat shrinkable film with the required thickness scale.
Further, the temperature set by the extruder is 200-250 ℃; the temperature for heating and stretching is 90-120 ℃; the annealing temperature is 95-100 ℃, and the cooling temperature is 30-40 ℃;
in the tensile layer, the antirust layer, the internal heat shrinkage layer, the flame-retardant heat insulation layer, the external heat shrinkage layer and the ultraviolet-resistant layer, every two adjacent layers of film bubbles are laminated at an angle of 45 degrees in the traction direction.
The invention has the beneficial effects that:
LDPE has good thermal shrinkage, MDLLPE can provide puncture resistance and flexibility of the thermal shrinkage film, and LLDPE can provide puncture resistance and stress cracking resistance of the thermal shrinkage film;
the heat shrinkable film wrapping equipment can insulate heat and prevent the wrapped equipment from being damaged by high temperature; the heat shrinkable film can also play a role in flame retardance, so that potential safety hazards of fire are prevented; in addition, the heat shrinkable film can be degraded after being used, and has no harm to the environment and soil; the heat shrinkable film simultaneously has multiple functions of heat insulation, flame retardance, UV resistance and degradation resistance;
in the production process of the heat shrinkable film, six layers are overlapped and laminated according to an inclination angle of 15-60 degrees in the traction direction, so that the strength of the heat shrinkable film is higher, the obtained heat shrinkable film has higher tensile, puncture and drop hammer resistant effects, and the heat shrinkable film has the advantages of tensile resistance, penetration resistance, impact resistance, tear resistance and stress cracking resistance, and can meet the packaging requirements of large-scale equipment with different shapes and specifications.
Drawings
FIG. 1 is a schematic view of the construction of a heat shrinkable film according to an embodiment;
in the figure, 1 a tensile layer, 2 an antirust layer, 3 an internal heat shrinkage layer, 4 a flame-retardant heat insulation layer, 5 an external heat shrinkage layer and 6 an ultraviolet-resistant layer.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
Table 1 table of raw materials for heat shrinkable film of example 1
The preparation method comprises the following steps:
(1) adding corresponding raw materials into respective extruder hoppers according to the raw material proportion of each layer of the heat shrinkable film in the table 1, setting the working temperature of an extruder to be 230 ℃, and performing coextrusion and film blowing through the extruder and a die head to form film bubbles of each layer;
(2) laminating the film bubbles of each layer from inside to outside according to a tensile layer 1, an antirust layer 2, an internal heat shrinkage layer 3, a flame-retardant heat insulation layer 4, an external heat shrinkage layer 5 and an ultraviolet-resistant layer 6, then clamping, pulling and self-bonding to form a film, and laminating the adjacent two layers of film bubbles in the pulling direction according to an angle of 45 degrees;
(3) heating and stretching, annealing, cooling and rolling a film formed by self-bonding, wherein the heating and stretching temperature is 100 ℃; the annealing temperature was 102 ℃ and the cooling temperature was 35 ℃ to obtain a heat shrinkable film of 200 μm thickness scale as shown in FIG. 1.
Example 2
Table 2 table of raw materials for heat shrinkable film of example 2
The preparation method comprises the following steps:
(1) adding corresponding raw materials into respective extruder hoppers according to the raw material proportion of each layer of the heat shrinkable film in the table 2, setting the working temperature of the extruder to be 240 ℃, and performing coextrusion and film blowing through the extruder and a die head to form film bubbles of each layer;
(2) laminating the film bubbles of each layer from inside to outside according to a tensile layer 1, an antirust layer 2, an internal heat shrinkage layer 3, a flame-retardant heat insulation layer 4, an external heat shrinkage layer 5 and an ultraviolet-resistant layer 6, then clamping, pulling and self-bonding to form a film, and laminating the adjacent two layers of film bubbles in the pulling direction according to an angle of 15 degrees;
(3) heating and stretching, annealing, cooling and rolling a film formed by self-bonding, wherein the heating and stretching temperature is 100 ℃; the annealing temperature was 105 ℃ and the cooling temperature was 40 ℃ to obtain a heat shrinkable film of 150 μm thickness scale.
Example 3
Table 3 table of raw materials for heat shrinkable film of example 3
The preparation method comprises the following steps:
(1) adding corresponding raw materials into respective extruder hoppers according to the raw material proportion of each layer of the heat shrinkable film in the table 3, setting the working temperature of the extruder to be 245 ℃, and performing coextrusion and film blowing through the extruder and a die head to form film bubbles of each layer;
(2) laminating the film bubbles of each layer from inside to outside according to a tensile layer 1, an antirust layer 2, an internal heat shrinkage layer 3, a flame-retardant heat insulation layer 4, an external heat shrinkage layer 5 and an ultraviolet-resistant layer 6, then clamping, pulling and self-bonding to form a film, and laminating the adjacent two layers of film bubbles in the pulling direction according to an angle of 60 degrees;
(3) heating and stretching, annealing, cooling and rolling a film formed by self-bonding, wherein the heating and stretching temperature is 100 ℃; the annealing temperature was 102 ℃ and the cooling temperature was 40 ℃ to obtain a heat shrinkable film of thickness scale 250 μm.
Example 4
Table 4 table of raw materials for heat shrinkable film of example 4
The preparation method comprises the following steps:
(1) adding corresponding raw materials into respective extruder hoppers according to the raw material proportion of each layer of the heat shrinkable film in the table 4, setting the working temperature of the extruder to be 235 ℃, and performing coextrusion and film blowing through the extruder and a die head to form film bubbles of each layer;
(2) laminating the film bubbles of each layer from inside to outside according to a tensile layer 1, an antirust layer 2, an internal heat shrinkage layer 3, a flame-retardant heat insulation layer 4, an external heat shrinkage layer 5 and an ultraviolet-resistant layer 6, then clamping, pulling and self-bonding to form a film, and laminating the adjacent two layers of film bubbles in the pulling direction according to an angle of 15 degrees;
(3) heating and stretching, annealing, cooling and rolling a film formed by self-bonding, wherein the heating and stretching temperature is 100 ℃; the annealing temperature was 102 ℃ and the cooling temperature was 40 ℃ to obtain a heat shrinkable film of 200 μm thickness scale.
Comparative example 1
Table 5 table of raw materials for heat shrinkable film of example 5
The preparation method comprises the following steps:
(1) adding corresponding raw materials into respective extruder hoppers according to the raw material proportion of each layer of the heat shrinkable film in the table 5, setting the working temperature of the extruder to be 230 ℃, and performing coextrusion and film blowing through the extruder and a die head to form film bubbles of each layer;
(2) laminating the film bubbles of each layer from inside to outside according to a tensile layer 1, an antirust layer 2, an internal heat shrinkage layer 3, a flame-retardant heat insulation layer 4, an external heat shrinkage layer 5 and an ultraviolet-resistant layer 6, then clamping, pulling and self-bonding to form a film, and laminating the adjacent two layers of film bubbles in the pulling direction according to an angle of 45 degrees;
(3) heating and stretching, annealing, cooling and rolling a film formed by self-bonding, wherein the heating and stretching temperature is 100 ℃; the annealing temperature was 102 ℃ and the cooling temperature was 35 ℃ to obtain a heat shrinkable film of 200 μm thickness scale.
Comparative example 2
(1) Adding corresponding raw materials into respective extruder hoppers according to the raw material proportion of each layer of the heat shrinkable film in the table 1, setting the working temperature of an extruder to be 230 ℃, and performing coextrusion and film blowing through the extruder and a die head to form film bubbles of each layer;
(2) laminating the film bubbles of each layer in parallel from inside to outside according to the sequence of a tensile layer, an antirust layer, an internal heat shrinkage layer, a flame-retardant heat insulation layer, an external heat shrinkage layer and an ultraviolet-resistant layer, and then clamping, pulling and self-bonding to form a film;
(3) heating and stretching, annealing, cooling and rolling a film formed by self-bonding, wherein the heating and stretching temperature is 100 ℃; the annealing temperature was 102 ℃ and the cooling temperature was 35 ℃ to obtain a heat shrinkable film of 200 μm thickness scale.
Tensile strength and elongation at break were measured by the method of ASTM D882-02, drop weight test by the method of ASTM1709AGf, VCI salt spray test by the method of ASTM B117, and degradability was measured by seal composting for 180 days of the obtained heat-shrinkable films, wherein the property test data of the heat-shrinkable films obtained in examples 1 to 4 and comparative examples 1 to 2 are shown in the following Table 6:
TABLE 6 data of property test of heat shrinkable films of examples 1 to 4 and comparative examples 1 to 2
The raw material ratio of the heat shrinkable film of the comparative example 2 is completely the same as that of the heat shrinkable film of the example 1, except that in the preparation method, the layers in the comparative example 2 are drawn after being stacked in parallel, and the layers in the example 1 are drawn after being stacked in an angle, and as can be seen from the comparison of the relevant data of the tensile strength, the drop weight test and the tear strength, the heat shrinkable film of the example 1 is obviously superior to that of the comparative example 2, thereby showing that in the preparation process, the layers in the heat shrinkable film are stacked in an angle, so that the performance of the heat shrinkable film can be effectively improved. In addition, in the technical scheme of the invention, the biodegradable master batch is added in the example 1, but the biodegradable master batch is not added in the comparative example 1, and the data comparison in the table 6 shows that the heat shrinkable film obtained by the technical scheme of the invention has better biodegradability.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The multilayer superposed degradable flame-retardant antirust heat shrinkable film is characterized by being a multilayer composite co-extruded film, and the heat shrinkable film comprises the following components from inside to outside: the anti-rust coating comprises a tensile layer, an anti-rust layer, an internal heat shrinkage layer, a flame-retardant heat insulation layer, an external heat shrinkage layer and an ultraviolet-resistant layer;
according to parts by weight, the tensile layer, the antirust layer, the internal heat shrinkage layer and the external heat shrinkage layer respectively comprise 5-10 parts of LDPE, 10-20 parts of LLDPE, 20-30 parts of MLLDPE, 10-20 parts of VCI antirust master batch, 1-5 parts of dispersing agent, 1-5 parts of coupling agent, 1-5 parts of antioxidant, 0.1-1.5 parts of antistatic master batch and 0.5-1 part of biodegradable master batch;
the flame-retardant heat-insulating layer comprises, by weight, 5-10 parts of LDPE, 10-15 parts of LLDPE, 20-25 parts of MLLDPE, 10-15 parts of VCI antirust master batch, 1-5 parts of dispersant, 1-5 parts of coupling agent, 1-5 parts of antioxidant and 1-2 parts of flame-retardant master batch;
the ultraviolet resistant layer comprises, by weight, 5-10 parts of LDPE, 10-15 parts of LLDPE, 25-30 parts of MLLDPE, 10-15 parts of VCI antirust master batch, 1-5 parts of dispersant, 1-5 parts of coupling agent, 1-5 parts of antioxidant, 0.1-1 part of antistatic master batch and 1-5 parts of ultraviolet absorbent.
2. The multilayer-superposed degradable flame-retardant antirust heat shrinkable film of claim 1, wherein the tensile layer comprises, by weight, 5-10 parts of LDPE, 15-20 parts of LLDPE, 25-30 parts of MLLDPE, 10-15 parts of VCI antirust masterbatch, 1-5 parts of dispersant, 1-5 parts of coupling agent, 1-5 parts of antioxidant, 1-1.5 parts of antistatic masterbatch, and 0.5-1 part of biodegradable masterbatch;
according to the parts by weight, the anti-rust layer comprises 5-10 parts of LDPE, 10-15 parts of LLDPE, 20-25 parts of MLLDPE, 15-20 parts of VCI anti-rust master batch, 1-5 parts of dispersing agent, 1-5 parts of coupling agent, 1-3 parts of antioxidant, 0.1-1.0 part of antistatic master batch and 0.5-1 part of biodegradable master batch;
according to the parts by weight, the internal heat shrinkage layer comprises 8-10 parts of LDPE, 10-15 parts of LLDPE, 20-25 parts of MLLDPE, 10-15 parts of VCI antirust master batch, 1-5 parts of dispersing agent, 1-5 parts of coupling agent, 1-3 parts of antioxidant, 0.1-1.5 parts of antistatic master batch and 0.5-1 part of biodegradable master batch;
the outer heat-shrinkable layer comprises, by weight, 5-10 parts of LDPE, 12-15 parts of LLDPE, 25-30 parts of MLLDPE, 10-20 parts of VCI antirust master batch, 1-5 parts of dispersing agent, 1-5 parts of coupling agent, 1-5 parts of antioxidant, 0.1-1.5 parts of antistatic master batch and 0.5-1 part of biodegradable master batch;
the flame-retardant heat-insulating layer comprises, by weight, 5-10 parts of LDPE, 10-15 parts of LLDPE, 20-25 parts of MLLDPE, 10-15 parts of VCI antirust master batch, 1-5 parts of dispersing agent, 1-5 parts of coupling agent, 1-5 parts of antioxidant, 1-2 parts of flame-retardant master batch and 0.1-1 part of shading master batch;
the ultraviolet resistant layer comprises, by weight, 5-10 parts of LDPE, 10-15 parts of LLDPE, 25-30 parts of MLLDPE, 10-15 parts of VCI antirust master batch, 1-5 parts of dispersant, 1-5 parts of coupling agent, 1-5 parts of antioxidant, 0.1-1 part of antistatic master batch, 1-5 parts of ultraviolet absorbent and 5-8 parts of master batch.
3. The multilayer-stacked degradable flame-retardant antirust heat shrinkable film as claimed in claim 2, wherein the LDPE is Yanshan petrochemical LD 163; the LLDPE is a LLDPE with a medium petrochemical metallocene name DMDB-8916; the VCI antirust master batch is a RUST-X VCI antirust master batch.
4. The multilayer superimposed degradable flame-retardant antirust heat shrinkable film according to claim 2, wherein the dispersant is one or a mixture of polypropylene wax and palm wax; the coupling agent is a silane coupling agent, the flame-retardant master batch is a halogen-series PE flame-retardant master batch, and the antioxidant is a mixture of hindered phenol antioxidant and phosphite antioxidant.
5. The multilayer stacked degradable flame retardant antirust heat shrinkable film according to claim 4, wherein the silane coupling agent is one or a mixture of more of gamma-methacryloxy triethoxysilane, gamma-aminopropyl trimethoxysilane, vinyl trimethoxysilane and gamma-aminopropyl triethoxysilane.
6. The multilayer stacked degradable flame-retardant antirust heat shrinkable film according to claim 4, wherein the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: 0.5 to 2;
the hindered phenol antioxidant is one or a mixture of an antioxidant 1010 and an antioxidant 1076, and the phosphite antioxidant is an antioxidant 168.
7. The multilayer superimposed degradable flame-retardant antirust heat shrinkable film according to claim 2, wherein the ultraviolet absorber is one or a mixture of benzophenone, benzophenone derivatives, benzotriazole and benzotriazole derivatives.
8. The multilayer-stacked degradable flame-retardant antirust heat shrinkable film according to any one of claims 1 to 7, wherein the thickness of the tensile layer, the antirust layer, the internal heat shrinkable layer, the flame-retardant heat-insulating layer, the external heat shrinkable layer and the ultraviolet-resistant layer is 30 to 40 μm, and the thickness of the heat shrinkable film is 150 to 250 μm.
9. A method for preparing a multilayer stacked degradable flame retardant antirust heat shrinkable film according to any one of claims 1 to 8, wherein the method comprises the following steps:
(1) adding corresponding raw materials into respective extruder hoppers according to the raw material proportion of each layer of the heat shrinkable film, and co-extruding and blowing the film through an extruder and a die head to form film bubbles of each layer;
(2) laminating the film bubbles of each layer in the sequence of a tensile layer, an antirust layer, an internal heat shrinkage layer, a flame-retardant heat insulation layer, an external heat shrinkage layer and an ultraviolet-resistant layer from inside to outside, clamping, drawing and self-bonding to form a film, and laminating the adjacent two layers of film bubbles in the drawing direction at an angle of 15-60 degrees;
(3) and heating, stretching, annealing, cooling and rolling the film formed by self-bonding to obtain the heat shrinkable film with the required thickness scale.
10. The method for preparing a multilayer stacked degradable flame retardant antirust heat shrinkable film as claimed in claim 9, wherein the temperature set by the extruder is 200-250 ℃; the temperature for heating and stretching is 90-120 ℃; the annealing temperature is 95-100 ℃, and the cooling temperature is 30-40 ℃;
in the tensile layer, the antirust layer, the internal heat shrinkage layer, the flame-retardant heat insulation layer, the external heat shrinkage layer and the ultraviolet-resistant layer, every two adjacent layers of film bubbles are laminated at an angle of 45 degrees in the traction direction.
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| DE102015114782A1 (en) * | 2015-09-03 | 2017-03-09 | Maria Soell High Technology Films Gmbh | Thermoformable shrink film and method of making the same |
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| CN113302057A (en) * | 2019-01-10 | 2021-08-24 | 东洋纺株式会社 | Laminated film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101318392A (en) * | 2008-07-03 | 2008-12-10 | 大连华诺塑料科技有限公司 | Trilaminar co-extrusion thermal contraction resin film, manufacturing method and application method thereof |
| CN102029755A (en) * | 2010-09-27 | 2011-04-27 | 沈阳防锈包装材料有限责任公司 | Flame-retardant shrinkable anticorrosive packaging film and manufacturing method thereof |
| DE102015114782A1 (en) * | 2015-09-03 | 2017-03-09 | Maria Soell High Technology Films Gmbh | Thermoformable shrink film and method of making the same |
| CN113302057A (en) * | 2019-01-10 | 2021-08-24 | 东洋纺株式会社 | Laminated film |
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