CN115742489B - Thermal aluminum-plastic composite film and preparation method thereof - Google Patents
Thermal aluminum-plastic composite film and preparation method thereof Download PDFInfo
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- CN115742489B CN115742489B CN202211629188.7A CN202211629188A CN115742489B CN 115742489 B CN115742489 B CN 115742489B CN 202211629188 A CN202211629188 A CN 202211629188A CN 115742489 B CN115742489 B CN 115742489B
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- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 239000004033 plastic Substances 0.000 title claims abstract description 44
- 229920003023 plastic Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 186
- 239000010410 layer Substances 0.000 claims abstract description 94
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 93
- 229920001155 polypropylene Polymers 0.000 claims abstract description 47
- 239000004743 Polypropylene Substances 0.000 claims abstract description 46
- -1 polypropylene Polymers 0.000 claims abstract description 46
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011888 foil Substances 0.000 claims abstract description 26
- 239000012793 heat-sealing layer Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000004677 Nylon Substances 0.000 claims abstract description 12
- 229920001778 nylon Polymers 0.000 claims abstract description 12
- 238000005266 casting Methods 0.000 claims abstract description 7
- 239000012790 adhesive layer Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 238000013329 compounding Methods 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002667 nucleating agent Substances 0.000 claims description 3
- 229920005604 random copolymer Polymers 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 238000009966 trimming Methods 0.000 claims description 3
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 238000007789 sealing Methods 0.000 abstract description 9
- 238000004080 punching Methods 0.000 abstract description 8
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 230000002087 whitening effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 23
- 239000002985 plastic film Substances 0.000 description 8
- 229920006255 plastic film Polymers 0.000 description 8
- 238000001035 drying Methods 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920006284 nylon film Polymers 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a thermal aluminum-plastic composite film and a preparation method thereof, wherein the thermal aluminum-plastic composite film comprises nylon, aluminum foil and a polypropylene film, the polypropylene film comprises a heat sealing layer, a bonding layer and an intermediate layer positioned between the heat sealing layer and the bonding layer, the bonding layer is connected with the aluminum foil, the preparation raw material of the heat sealing layer contains calcium carbonate, and the content of the calcium carbonate accounts for 5-15% of the total mass of the heat sealing layer; the preparation raw material of the intermediate layer contains calcium carbonate, and the content of the calcium carbonate accounts for 5-15% of the total mass of the intermediate layer. According to the thermal aluminum-plastic composite film provided by the invention, 5-15% of calcium carbonate is added into the heat sealing layer and the middle layer respectively, and the film is prepared by casting through the extruder, so that the shrinkage rate of the polypropylene film can be effectively improved, the aluminum-plastic composite film produced by adopting the polypropylene film has a good curling effect, the curling problem of the aluminum-plastic composite film after deep punching is effectively improved, and meanwhile, the crystallization rate of polypropylene is changed due to the addition of calcium carbonate, so that the whitening problem of the heat sealing interface of the aluminum-plastic composite film is well improved.
Description
Technical Field
The invention relates to the technical field of aluminum-plastic composite films, in particular to a thermal aluminum-plastic composite film and a preparation method thereof.
Background
Lithium ion batteries are widely used in new energy systems in digital, vehicular, military, and energy storage applications. Currently, a general aluminum-plastic composite film (also referred to as an aluminum-plastic film for short) is used as a flexible packaging film of a lithium ion battery. The aluminum-plastic composite film comprises nylon, aluminum foil and a polypropylene film from outside to inside, wherein the polypropylene film comprises a heat sealing layer, a bonding layer and an intermediate layer positioned between the heat sealing layer and the bonding layer, and the bonding layer is connected with the aluminum foil. In the preparation process of the aluminum-plastic composite film, the aluminum-plastic composite film generally comprises two preparation methods of a dry-method aluminum-plastic film and a thermal-method aluminum-plastic film, wherein the dry-method aluminum-plastic film is formed by directly laminating an aluminum foil and a polypropylene film by adopting an adhesive, and has the advantages of good deep punching performance; the thermal aluminum plastic film is formed by directly connecting an aluminum film and a polypropylene film by adopting modified polypropylene, and is fixed by slow heating and hot pressing. For the thermal aluminum plastic film, the problem of deep punching and curling of the finished product is caused by heat shrinkage of polypropylene in the high-temperature and high-pressure compounding process, and the production efficiency and the yield of battery manufacturers are affected.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the thermal aluminum-plastic composite film and the preparation method thereof, which can adjust the thermal shrinkage of the polypropylene film, effectively improve the curling problem after deep drawing and can also improve the problem of even milky white heat sealing interface.
In order to achieve the aim, the invention discloses a thermal aluminum-plastic composite film, which comprises nylon, aluminum foil and a polypropylene film, wherein the polypropylene film comprises a heat sealing layer, a bonding layer and an intermediate layer positioned between the heat sealing layer and the bonding layer, the bonding layer is connected with the aluminum foil,
the preparation raw material of the heat-sealing layer contains calcium carbonate, and the content of the calcium carbonate accounts for 5-15% of the total mass of the heat-sealing layer;
the preparation raw material of the intermediate layer contains calcium carbonate, and the content of the calcium carbonate accounts for 5-15% of the total mass of the intermediate layer.
Compared with the prior art, in the thermal aluminum-plastic composite film provided by the invention, 5% -15% of calcium carbonate is added into the heat sealing layer and the middle layer respectively, and the film is prepared by casting through an extruder, so that the shrinkage rate of the polypropylene film can be effectively improved, the aluminum-plastic composite film produced by adopting the polypropylene film has a good curling effect, the curling problem of the aluminum-plastic composite film after deep punching is effectively improved, and meanwhile, the crystallization rate of polypropylene is changed due to the addition of calcium carbonate, and the whitening problem of the heat sealing interface of the aluminum-plastic composite film is well improved.
It should be noted that the calcium carbonate content is 5% -15% of the total mass of the heat-seal layer, and for example, the calcium carbonate content may be, but not limited to, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%. The calcium carbonate content is 5% -15% of the total mass of the intermediate layer, and illustratively, the calcium carbonate content may be, but is not limited to, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%. If the amount of calcium carbonate added is too small, the effect is not obvious, the content of calcium carbonate exceeds a certain amount, although the calcium carbonate is subjected to surface treatment, the heat resistance of the calcium carbonate influences the encapsulation to a certain extent, the proper content needs to be controlled, and when the content is too high, the encapsulation strength and the encapsulation interface are influenced.
Preferably, the calcium carbonate is pretreated by the coupling agent, and the compatibility of the calcium carbonate and other high polymer materials is greatly improved by the calcium carbonate treated by the coupling agent, so that the calcium carbonate is favorable for extrusion granulation.
Preferably, the coupling agent is a titanate coupling agent.
Preferably, the preparation raw materials of the heat sealing layer comprise the following components in percentage by mass of 5-15:82-94.5:0.5-3 of said calcium carbonate, random copolymer polypropylene and antiblocking masterbatch.
Preferably, the preparation raw materials of the middle layer comprise the following components in percentage by mass of 5-15:82-94.5:0.5-3 of said calcium carbonate, homo-polypropylene and polyolefin elastomer.
Preferably, the adhesive layer is prepared from the following raw materials in percentage by mass: 1-5 of maleic anhydride grafted modified polypropylene and a nucleating agent.
Preferably, the selected calcium carbonate is light calcium carbonate of more than 1000 meshes.
Correspondingly, the invention also provides a preparation method of the thermal aluminum-plastic composite film, which comprises the following steps:
(1) Preparation of Polypropylene film
1.1 granulation of Heat seal layer
Granulating calcium carbonate and other preparation raw materials of the heat sealing layer to obtain a material A;
1.2 granulation of the intermediate layer
Granulating the calcium carbonate and other preparation raw materials of the middle layer to obtain a material B;
the preparation raw materials of the material A, the material B and the bonding layer are respectively mixed and then are sucked into corresponding hoppers, and the polypropylene film is prepared through quantitative conveying by three screws, extrusion and filtration by an extruder, casting from a T-shaped die, cooling by a cooling roller, trimming, rolling and re-cutting;
(2) Providing an aluminum foil, and compositing a nylon layer on a matte surface of the aluminum foil;
(3) And compounding the polypropylene film on the bright surface of the aluminum foil by a thermal method to prepare the aluminum-plastic composite film.
Preferably, in step (3), the thermal compounding temperature is at least 160 ℃.
Preferably, in the step (2), an adhesive layer is coated on the matte surface of the aluminum foil, then a nylon layer is attached, and the aluminum foil is cured for 1 to 5 days at the temperature of between 50 and 70 ℃.
Drawings
FIG. 1 is a schematic structural diagram of a thermal aluminum plastic composite film of the present invention.
FIG. 2 is a graph showing the degree of milky white uniformity of the interface of the aluminum-plastic composite films according to examples 1 to 5 of the present invention, wherein FIGS. 2 (a) to 2 (e) correspond to examples 1 to 5, respectively.
FIG. 3 is a graph showing the degree of milky white uniformity of the interface of the aluminum-plastic composite films of comparative examples 1 to 5 according to the present invention, wherein FIGS. 3 (f) -3 (j) correspond to comparative examples 1 to 5, respectively.
Detailed Description
In order to describe the technical content, the structural features, the achieved objects and effects of the present invention in detail, the following description will explain the embodiments in detail.
Referring to fig. 1, the thermal aluminum-plastic composite film of the invention comprises a nylon layer 10, an adhesive layer 30, an aluminum foil 50 and a polypropylene film 70 from outside to inside, wherein the nylon layer 10 is positioned at the outermost layer and is wear-resistant and corrosion-resistant for protection; adhesive layer 30 adhesively secures nylon layer 10 and aluminum foil 50, for example, adhesive layer 30 may be a two-component glue of, but not limited to, polyurethane and isocyanate curing agents. Wherein the polypropylene film 70 comprises an adhesive layer 71, a heat seal layer 75 and an intermediate layer 73 between the heat seal layer 75 and the adhesive layer 71, the adhesive layer 71 being connected to the aluminum foil 50. According to the invention, 5% -15% of calcium carbonate is added into each of the heat sealing layer 75 and the middle layer 73, and the film is prepared by casting through an extruder, so that the shrinkage rate of the polypropylene film 70 can be effectively improved, the aluminum-plastic composite film produced by adopting the polypropylene film 70 has a good curling effect, the curling problem of the aluminum-plastic composite film after deep drawing is effectively solved, and meanwhile, the crystallization rate of polypropylene is changed due to the addition of calcium carbonate, so that the whitening problem of the heat sealing interface of the aluminum-plastic composite film is well improved.
The aluminum-plastic composite film of the present invention is further illustrated by the following several embodiments, but is not intended to limit the scope of the present invention.
Example 1
A preparation method of an aluminum-plastic composite film comprises the following steps:
(1) Preparing a polypropylene film:
baking calcium carbonate for 4 hours at 120 ℃, adding the calcium carbonate into a high-speed mixer, then adding 2% of titanate coupling agent, stirring and mixing for 3 hours at 70 ℃ at high speed, standing, filtering and drying;
1.1 granulation of Heat seal layer
Mixing the surface-treated calcium carbonate, the random copolymer polypropylene RP320M and the anti-adhesion master batch SAB-7203S according to the mass ratio of 5:93:2, extruding and granulating through a double screw, shearing into particles, and drying in vacuum for later use;
1.2 granulation of the intermediate layer
Mixing the surface-treated calcium carbonate, HP510M of the Zhonghai shell, propylene and ethylene copolymer elastomer (Exxon Mobil 3000) according to the mass ratio of 5:85:10, granulating by twin-screw extrusion, shearing into particles, and drying in vacuum for later use;
1.3 raw materials for preparing the adhesive layer
The maleic anhydride grafted modified polypropylene (Mitsui chemical QF 551) and the nucleating agent (Japanese Ai Dike NA-21) are uniformly mixed according to the mass ratio of 99:1 for standby;
respectively sucking the granulated heat sealing layer material, the intermediate layer material and the mixed raw materials for preparing the adhesive layer into corresponding hoppers, wherein the thickness of three layers is 7, 26 and 7 mu m respectively, quantitatively conveying through three screws, extruding and filtering through an extruder, casting from a T-shaped die head, cooling through a cooling roller, trimming, rolling and cutting according to the specification to obtain a polypropylene film with the thickness of 40 mu m;
(2) Providing 40 mu m aluminum foil of Henan Mintai, passivating the two sides of the aluminum foil, then compounding a layer of nylon film with a length of 25 mu m on the matte surface of the aluminum foil by adopting a dry type compounding process, and curing for 3 days at 60 ℃ to obtain a semi-finished product;
(3) And compounding the polypropylene film on the bright surface of the aluminum foil by a thermal method, wherein the compounding temperature is 160 ℃, and the aluminum-plastic composite film is prepared.
Example 2
This example is substantially the same as example 1 except that the heat-seal layer in this example has a calcium carbonate content of 10% and the intermediate layer has a calcium carbonate content of 5%, whereas the heat-seal layer in example 1 has a calcium carbonate content of 5% and the intermediate layer has a calcium carbonate content of 5%, and the remainder is the same as example 1 and is not described herein.
Example 3
This example is substantially identical to example 1 except that the heat-seal layer in this example has a calcium carbonate content of 10% and the intermediate layer has a calcium carbonate content of 10%, whereas the heat-seal layer in example 1 has a calcium carbonate content of 5% and the intermediate layer has a calcium carbonate content of 5%, and the remainder is identical to example 1 and is not described herein.
Example 4
This example is substantially identical to example 1 except that the heat-seal layer in this example has a calcium carbonate content of 15% and the intermediate layer has a calcium carbonate content of 10%, whereas the heat-seal layer in example 1 has a calcium carbonate content of 5% and the intermediate layer has a calcium carbonate content of 5%, and the remainder is identical to example 1 and is not described herein.
Example 5
This example is substantially the same as example 1 except that the heat-seal layer in this example has a calcium carbonate content of 15% and the intermediate layer has a calcium carbonate content of 15%, whereas the heat-seal layer in example 1 has a calcium carbonate content of 5% and the intermediate layer has a calcium carbonate content of 5%, and the remainder is the same as example 1 and is not described herein.
Comparative example 1
This comparative example 1 is substantially the same as example 1 except that the heat-seal layer of this comparative example 1 contains no calcium carbonate, the intermediate layer contains no calcium carbonate, the heat-seal layer of example 1 contains 5% calcium carbonate, the intermediate layer contains 5% calcium carbonate, and the remainder is the same as example 1, and is not described herein.
Comparative example 2
This comparative example 2 is substantially identical to example 1 except that the heat-seal layer of comparative example 2 does not contain calcium carbonate, the calcium carbonate content of the intermediate layer is 10% and the calcium carbonate content of the heat-seal layer of example 1 is 5% and the calcium carbonate content of the intermediate layer is 5% and the remainder is identical to example 1 and is not described herein.
Comparative example 3
This comparative example 3 is substantially identical to example 1 except that the heat-seal layer in this comparative example 3 has a calcium carbonate content of 10% and the intermediate layer does not contain calcium carbonate, whereas the heat-seal layer in example 1 has a calcium carbonate content of 5% and the intermediate layer has a calcium carbonate content of 5% and the remainder is identical to example 1 and is not described herein.
Comparative example 4
This comparative example 4 is substantially identical to example 1 except that the heat-seal layer in this comparative example 4 has a calcium carbonate content of 20% and the intermediate layer has a calcium carbonate content of 5%, whereas the heat-seal layer in example 1 has a calcium carbonate content of 5% and the intermediate layer has a calcium carbonate content of 5%, and the remainder is identical to example 1 and is not described herein.
Comparative example 5
This comparative example 5 is substantially identical to example 1 except that the heat-seal layer of comparative example 5 has a calcium carbonate content of 5% and the intermediate layer has a calcium carbonate content of 20%, whereas the heat-seal layer of example 1 has a calcium carbonate content of 5% and the intermediate layer has a calcium carbonate content of 5%, and the remainder is identical to example 1 and is not described herein.
The aluminum plastic composite films prepared in examples 1 to 5 and comparative examples 1 to 5 were subjected to performance test, and the results are shown in Table 1.
The test items and methods are as follows:
the deep-drawing curl height test method comprises the following steps: cutting an aluminum plastic film into 110 mm or 120mm, punching the shell with 55 mm or 60mm, punching the shell with 5.0mm of depth, horizontally placing the shell on a table top, and measuring the tilting height of the nylon surface and the vertical height of the table top to obtain the deep-punching curling height.
Heat seal strength: the heat seal strength of the plastic-aluminum film is tested according to the heat seal strength test method of the QB-T2358-1998 plastic film packaging bag, after the test, the heat seal interface is observed, whether the interface is even and milky (as shown in figures 2-3), and the lower the level of the even milky degree of the heat seal interface is, the better the heat seal effect of the product is.
Heat shrinkage rate: according to the specification of GB/T12027-2004, the heat shrinkage rates of the nylon film in the longitudinal direction (machine running direction) and the transverse direction (perpendicular to the machine running direction) were respectively tested under the experimental conditions (160+/-2) DEG C for 5 min.
Table 1 test results
As can be seen from the data in Table 1, the aluminum plastic composite films in examples 1 to 5 have slightly reduced heat seal strength, but the reduction is not large, and the reduction is within an acceptable range, but the interface milky white and the curling effect are significantly improved, and the aluminum plastic composite film has better deep drawing curling property and packaging performance. According to the invention, 5% -15% of calcium carbonate is added into the heat sealing layer and the middle layer respectively, and the film is prepared by casting through an extruder, so that the shrinkage rate of the polypropylene film can be effectively improved, the aluminum-plastic composite film produced by adopting the polypropylene film has a good curling effect, the curling problem of the aluminum-plastic composite film after deep punching is effectively solved, and meanwhile, the crystallization rate of polypropylene is changed due to the addition of calcium carbonate, so that the whitening problem of the heat sealing interface of the aluminum-plastic composite film is well improved.
In comparative example 1, the heat-sealing layer contains no calcium carbonate, the middle layer contains no calcium carbonate, when the polypropylene and the aluminum foil are compounded at high temperature, the polypropylene heat shrinkage is caused by the heat shrinkage of the polypropylene, the shrinkage stress of the polypropylene film is insufficient to resist the stress of the nylon film surface, the curling is obvious, and the heat-sealing interface performance is also obviously poor.
In comparative example 2, although the addition of calcium carbonate to the intermediate layer improved the deep drawing curl performance, the heat seal interface effect was not improved.
In comparative example 3, although the heat seal interface effect was improved by adding calcium carbonate to the heat seal layer, the deep drawing curling property was not improved.
In comparative example 4, the heat resistance of calcium carbonate in the heat-sealing layer affects the sealing property to some extent, and when the calcium carbonate content is too high, the heat-sealing strength and the sealing interface are affected.
In comparative example 5, the calcium carbonate content in the intermediate layer exceeds a certain amount, and when the calcium carbonate content is too high, compatibility is affected, and interlayer adhesive strength is weakened, so that heat seal strength and a packaging interface are affected.
The foregoing description of the preferred embodiments of the present invention is not intended to limit the scope of the claims, which follow, as defined in the claims.
Claims (5)
1. A thermal aluminum-plastic composite film comprises nylon, aluminum foil and polypropylene film, and is characterized in that the polypropylene film comprises a heat sealing layer, a bonding layer and an intermediate layer positioned between the heat sealing layer and the bonding layer, the bonding layer is connected with the aluminum foil,
the preparation raw material of the heat-sealing layer contains calcium carbonate, and the content of the calcium carbonate accounts for 5-15% of the total mass of the heat-sealing layer;
the preparation raw material of the middle layer contains calcium carbonate, and the content of the calcium carbonate accounts for 5-15% of the total mass of the middle layer; the calcium carbonate is pretreated by a coupling agent, wherein the coupling agent is a titanate coupling agent;
the heat-sealing layer is prepared from the following raw materials in mass ratio of 5-15:82-94.5:0.5-3 of said calcium carbonate, random copolymer polypropylene and antiblocking masterbatch;
the preparation raw materials of the intermediate layer comprise the following raw materials in mass ratio of 5-15:82-94.5:0.5-3 of said calcium carbonate, homo-polypropylene and polyolefin elastomer;
the adhesive layer is prepared from the following raw materials in percentage by mass: 1-5 of maleic anhydride grafted modified polypropylene and a nucleating agent.
2. The thermal aluminum-plastic composite film according to claim 1, wherein the calcium carbonate is light calcium carbonate of 1000 mesh or more.
3. A method for preparing the thermal aluminum-plastic composite film according to any one of claims 1 to 2, comprising the steps of:
(1) Preparation of Polypropylene film
1.1 granulation of Heat seal layer
Granulating calcium carbonate and other preparation raw materials of the heat sealing layer to obtain a material A;
1.2 Granulation of the intermediate layer
Granulating the calcium carbonate and other preparation raw materials of the middle layer to obtain a material B;
the preparation raw materials of the material A, the material B and the bonding layer are respectively mixed and then are sucked into corresponding hoppers, and the polypropylene film is prepared through quantitative conveying by three screws, extrusion and filtration by an extruder, casting from a T-shaped die, cooling by a cooling roller, trimming, rolling and re-cutting;
(2) Providing an aluminum foil, and compositing a nylon layer on a matte surface of the aluminum foil;
(3) And compounding the polypropylene film on the bright surface of the aluminum foil by a thermal method to prepare the aluminum-plastic composite film.
4. The method of claim 3, wherein in the step (3), the thermal compounding temperature is at least 160 ℃.
5. The method for preparing a thermal aluminum-plastic composite film according to claim 3, wherein in the step (2), an adhesive layer is coated on the matte surface of the aluminum foil, then a nylon layer is attached, and the aluminum-plastic composite film is cured for 1-5 days at 50-70 ℃.
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| CN202211629188.7A CN115742489B (en) | 2022-12-15 | 2022-12-15 | Thermal aluminum-plastic composite film and preparation method thereof |
| PCT/CN2023/097290 WO2024124817A1 (en) | 2022-12-15 | 2023-05-31 | Hot-process aluminum-plastic composite film and preparation method therefor |
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| CN202211629188.7A CN115742489B (en) | 2022-12-15 | 2022-12-15 | Thermal aluminum-plastic composite film and preparation method thereof |
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