WO2024124817A1 - Hot-process aluminum-plastic composite film and preparation method therefor - Google Patents
Hot-process aluminum-plastic composite film and preparation method therefor Download PDFInfo
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- WO2024124817A1 WO2024124817A1 PCT/CN2023/097290 CN2023097290W WO2024124817A1 WO 2024124817 A1 WO2024124817 A1 WO 2024124817A1 CN 2023097290 W CN2023097290 W CN 2023097290W WO 2024124817 A1 WO2024124817 A1 WO 2024124817A1
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- Prior art keywords
- calcium carbonate
- aluminum
- plastic composite
- layer
- composite film
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- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000004033 plastic Substances 0.000 title claims abstract description 46
- 229920003023 plastic Polymers 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 182
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 91
- 239000010410 layer Substances 0.000 claims abstract description 67
- 229920001155 polypropylene Polymers 0.000 claims abstract description 48
- 239000004743 Polypropylene Substances 0.000 claims abstract description 47
- -1 polypropylene Polymers 0.000 claims abstract description 47
- 239000012793 heat-sealing layer Substances 0.000 claims abstract description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- 239000011888 foil Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000004677 Nylon Substances 0.000 claims abstract description 12
- 229920001778 nylon Polymers 0.000 claims abstract description 12
- 239000012790 adhesive layer Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 10
- 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
- 238000013329 compounding Methods 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 6
- 238000001816 cooling 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
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 238000007789 sealing Methods 0.000 abstract description 8
- 238000004080 punching Methods 0.000 abstract description 7
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 238000005266 casting Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 24
- 239000002985 plastic film Substances 0.000 description 9
- 229920006255 plastic film Polymers 0.000 description 9
- 238000004806 packaging method and process Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229920006284 nylon film Polymers 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001914 filtration 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
- 238000003475 lamination 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
- 239000002861 polymer material Substances 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 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
- 230000000630 rising effect Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
Definitions
- the present application relates to the technical field of aluminum-plastic composite films, and more specifically to a thermal aluminum-plastic composite film and a preparation method thereof.
- Aluminum-plastic composite film (also referred to as aluminum-plastic film) is generally used as a soft packaging film for lithium-ion batteries.
- the aluminum-plastic composite film includes nylon, aluminum foil and polypropylene film from the outside to the inside.
- the polypropylene film includes a heat-sealing layer, an adhesive layer and an intermediate layer between the heat-sealing layer and the adhesive layer.
- the adhesive layer is connected to the aluminum foil.
- dry aluminum-plastic film and hot aluminum-plastic film there are generally two preparation methods: dry aluminum-plastic film and hot aluminum-plastic film. The dry aluminum-plastic film is directly pressed by an adhesive on the aluminum foil and the polypropylene film.
- the advantage is good deep-drawing performance; the hot aluminum-plastic film is directly connected between the aluminum film and the polypropylene film by modified polypropylene, and is fixed by slowly heating and hot pressing.
- the advantage is good electrolyte and water resistance.
- polypropylene will produce heat shrinkage during the high temperature and high pressure compounding process, the problem of curling of the finished product will be caused, which will affect the production efficiency and yield rate of battery manufacturers.
- the present application provides a thermal aluminum-plastic composite film and a preparation method thereof, which can adjust the thermal shrinkage of the polypropylene film, effectively improve the curling problem after deep punching, and also improve the problem of uniform milky whiteness on the heat-sealed interface.
- the present application discloses a thermal aluminum-plastic composite film, comprising nylon, aluminum foil and polypropylene film, wherein the polypropylene film comprises a heat-sealing layer, an adhesive layer and an intermediate layer located between the heat-sealing layer and the adhesive layer, wherein the adhesive layer is connected to the aluminum foil,
- the raw material for preparing the heat sealing layer contains calcium carbonate, and the content of calcium carbonate accounts for 5%-15% of the total mass of the heat sealing layer;
- the raw material for preparing 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 shrinkage rate of the polypropylene film can be effectively improved.
- the aluminum-plastic composite film produced by using the polypropylene film has a good curling effect, which effectively improves the curling problem of the aluminum-plastic composite film after deep punching.
- the crystallization rate of polypropylene is changed, which greatly improves the whitening problem of the heat-sealing interface of the aluminum-plastic composite film.
- the calcium carbonate content accounts for 5%-15% of the total mass of the heat-sealing layer.
- 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 accounts for 5%-15% of the total mass of the intermediate layer.
- the calcium carbonate content may be but not limited to 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%. If the amount of calcium carbonate added is too little, the effect is not obvious.
- the heat resistance of calcium carbonate affects the packaging to a certain extent. It is necessary to control the appropriate content. When the content is too high, it will affect the packaging strength and packaging interface.
- the calcium carbonate is pretreated with a coupling agent, and the calcium carbonate treated with the coupling agent greatly improves its compatibility with other polymer materials, which is beneficial to extrusion granulation.
- the coupling agent is a titanate coupling agent.
- the raw materials for preparing the heat sealing layer include the calcium carbonate, random copolymer polypropylene and anti-blocking masterbatch in a mass ratio of 5-15:82-94.5:0.5-3.
- the raw materials for preparing the intermediate layer include calcium carbonate, homopolypropylene and polyolefin elastomer in a mass ratio of 5-15:82-94.5:0.5-3.
- the raw materials for preparing the adhesive layer include maleic anhydride grafted modified polypropylene and a nucleating agent in a mass ratio of 95-99:1-5.
- the selected calcium carbonate is light calcium carbonate with a mesh size of 1000 or more.
- the present application also provides a method for preparing a thermal aluminum-plastic composite film, comprising the steps of:
- the material A, the material B and the raw materials for preparing the bonding layer are mixed and sucked into the corresponding hoppers, quantitatively conveyed by three screws, extruded and filtered by an extruder, cast from a T-shaped die head, cooled by a cooling roller, trimmed, rolled, and then slit to obtain a polypropylene film;
- the bright side of the aluminum foil is thermally laminated with a polypropylene film to obtain an aluminum-plastic composite film.
- the thermal compounding temperature is at least 160°C.
- step (2) an adhesive layer is coated on the matte surface of the aluminum foil, and then the nylon layer is adhered thereto, and then cured at 50-70° C. for 1-5 days.
- FIG. 1 is a schematic diagram of the structure of the thermal aluminum-plastic composite film of the present application.
- FIG. 2 is a diagram showing the uniform milky degree of the interfaces of the aluminum-plastic composite films of Examples 1-5 of the present application, wherein FIG. 2( a ) to FIG. 2( e ) correspond to Examples 1-5, respectively.
- FIG. 3 is a diagram showing the uniform milky degree of the interfaces of the aluminum-plastic composite films of comparative examples 1-5 of the present application, wherein FIG. 3( f ) to FIG. 3( j ) correspond to comparative examples 1-5, respectively.
- the thermal aluminum-plastic composite film of the present application includes, from outside to inside, a nylon layer 10, an adhesive layer 30, an aluminum foil 50 and a polypropylene film 70.
- the nylon layer 10 is located at the outermost layer and is wear-resistant and corrosion-resistant for protection.
- the adhesive layer 30 is used to bond and fix the nylon layer 10 and the aluminum foil 50.
- the adhesive layer 30 can use, but is not limited to, a two-component glue of polyurethane and isocyanate curing agent.
- the polypropylene film 70 includes an adhesive layer 71, a heat-sealing layer 75 and an intermediate layer 73 located between the heat-sealing layer 75 and the adhesive layer 71.
- the adhesive layer 71 is connected to the aluminum foil 50.
- the present application adds 5%-15% calcium carbonate to the heat-sealing layer 75 and the middle layer 73, respectively, and uses an extruder to cast the film, which can effectively improve the shrinkage rate of the polypropylene film 70.
- the aluminum-plastic composite film produced using the polypropylene film 70 has a good curling effect, which effectively improves the curling problem of the aluminum-plastic composite film after deep punching.
- the crystallization rate of polypropylene is changed, which greatly improves the whitening problem of the heat-sealing interface of the aluminum-plastic composite film.
- the aluminum-plastic composite film of the present application is further described below through several specific implementations, but this does not limit the protection scope of the present application.
- a method for preparing an aluminum-plastic composite film comprises the following steps:
- Calcium carbonate was baked at 120°C for 4 hours, added to a high-speed mixer, and then 2% titanate coupling agent was added, and mixed at high speed at 70°C for 3 hours, allowed to stand, filtered, and dried;
- the surface treated calcium carbonate, random copolymer polypropylene RP320M and anti-blocking masterbatch SAB-7203S are mixed in a mass ratio of 5:93:2, and then granulated by twin-screw extrusion, sheared into granules, and vacuum dried for standby use;
- the surface treated calcium carbonate, HP510M of CNOOC Shell, and propylene and ethylene copolymer elastomer (ExxonMobil 3000) were mixed in a mass ratio of 5:85:10, and then granulated by twin-screw extrusion, sheared into granules, and vacuum dried for standby use;
- the granulated heat-sealing layer material, the intermediate layer material and the mixed adhesive layer preparation raw materials are sucked into the corresponding hoppers respectively, and the thickness of the three layers are 7, 26 and 7 ⁇ m respectively, and the polypropylene film is obtained by quantitative conveying by a three-screw extruder, extruding and filtering by an extruder, casting from a T-shaped die head, cooling by a cooling roller, trimming, winding, and then slitting according to specifications, and the thickness of the polypropylene film is 40 ⁇ m;
- the polypropylene film is thermally laminated on the bright side of the aluminum foil at a lamination temperature of 160° C. to obtain an aluminum-plastic composite film.
- This embodiment is basically the same as Embodiment 1, except that, in this embodiment, the calcium carbonate content in the heat sealing layer accounts for 10%, and the calcium carbonate content in the middle layer accounts for 5%, while in Embodiment 1, the calcium carbonate content in the heat sealing layer accounts for 5%, and the calcium carbonate content in the middle layer accounts for 5%.
- the rest is the same as Embodiment 1 and will not be elaborated here.
- This embodiment is basically the same as Embodiment 1, except that, in this embodiment, the calcium carbonate content in the heat sealing layer accounts for 10%, and the calcium carbonate content in the middle layer accounts for 10%, while in Embodiment 1, the calcium carbonate content in the heat sealing layer accounts for 5%, and the calcium carbonate content in the middle layer accounts for 5%.
- the rest is the same as Embodiment 1 and will not be elaborated here.
- This embodiment is basically the same as Embodiment 1, except that, in this embodiment, the calcium carbonate content in the heat sealing layer accounts for 15%, and the calcium carbonate content in the middle layer accounts for 10%, while in Embodiment 1, the calcium carbonate content in the heat sealing layer accounts for 5%, and the calcium carbonate content in the middle layer accounts for 5%.
- the rest is the same as Embodiment 1 and will not be elaborated here.
- This embodiment is basically the same as Embodiment 1, except that, in this embodiment, the calcium carbonate content in the heat sealing layer accounts for 15%, and the calcium carbonate content in the middle layer accounts for 15%, while in Embodiment 1, the calcium carbonate content in the heat sealing layer accounts for 5%, and the calcium carbonate content in the middle layer accounts for 5%.
- the rest is the same as Embodiment 1 and will not be elaborated here.
- the comparative example 1 is basically the same as the example 1, except that the heat sealing layer in the comparative example 1 does not contain calcium carbonate, and the middle layer does not contain calcium carbonate, while the calcium carbonate content in the heat sealing layer in the example 1 accounts for 5%, and the calcium carbonate content in the middle layer accounts for 5%, and the rest is the same as the example 1, which will not be elaborated here.
- the comparative example 2 is basically the same as the example 1, except that the heat sealing layer in the comparative example 2 does not contain calcium carbonate, and the calcium carbonate content in the middle layer accounts for 10%, while the calcium carbonate content in the heat sealing layer in the example 1 accounts for 5%, and the calcium carbonate content in the middle layer accounts for 5%.
- the rest is the same as the example 1 and will not be elaborated here.
- This comparative example 3 is basically the same as Example 1, except that in this comparative example 3, the content of calcium carbonate in the heat sealing layer accounts for 10%, and the middle layer does not contain calcium carbonate, while in Example 1, the content of calcium carbonate in the heat sealing layer accounts for 5%, and the content of calcium carbonate in the middle layer accounts for 5%. The rest is the same as Example 1 and will not be elaborated here.
- This comparative example 4 is basically the same as Example 1, except that in this comparative example 4, the calcium carbonate content in the heat sealing layer accounts for 20%, and the calcium carbonate content in the middle layer accounts for 5%, while in Example 1, the calcium carbonate content in the heat sealing layer accounts for 5%, and the calcium carbonate content in the middle layer accounts for 5%. The rest is the same as Example 1 and will not be elaborated here.
- the comparative example 5 is basically the same as the example 1, except that in the comparative example 5, the calcium carbonate content in the heat sealing layer accounts for 5%, and the calcium carbonate content in the middle layer accounts for 20%, while in the example 1, the calcium carbonate content in the heat sealing layer accounts for 5%, and the calcium carbonate content in the middle layer accounts for 5%.
- the rest is the same as the example 1 and will not be elaborated here.
- Test method for deep punching curl height cut the aluminum-plastic film into 110*120mm size, punch shell size 55*60mm, punch shell depth 5.0mm, put it flat on the table after punching, and measure the height of the nylon surface rising and the vertical height of the table as the deep punching curl height.
- Heat seal strength Test the heat seal strength of the aluminum-plastic film according to QB-T 2358-1998 test method for heat seal strength of plastic film packaging bags. Observe the heat seal interface after the test to see if it is uniformly milky white (as shown in Figures 2 and 3). The lower the uniform milky whiteness of the heat seal interface, the better the heat seal effect of the product.
- Thermal shrinkage rate According to the provisions of GB/T 12027-2004, the experimental conditions are (160 ⁇ 2)°C, the time is 5min, and the thermal shrinkage rates of the nylon film in the longitudinal direction (machine running direction) and the transverse direction (vertical to the machine running direction) are tested respectively.
- the calcium carbonate content in the middle layer exceeds a certain amount.
- the calcium carbonate content is too high, it will affect the compatibility, weaken the interlayer bonding strength, and further affect the heat sealing strength and packaging interface.
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Abstract
A hot-process aluminum-plastic composite film and a preparation method therefor. The hot-process aluminum-plastic composite film comprises nylon, an aluminum foil and a polypropylene film, wherein the polypropylene film comprises a heat-sealing layer, a bonding layer and a middle layer that is located between the heat sealing layer and the bonding layer. The bonding layer is connected to the aluminum foil; the preparation raw material of the heat-sealing layer comprises calcium carbonate, and the content of calcium carbonate is 5-15% of the total mass of the heat sealing layer; and the preparation raw material of the middle layer comprises calcium carbonate, and the content of calcium carbonate is 5-15% of the total mass of the middle layer. In the hot-process aluminum-plastic composite film provided in the present invention, the shrinkage rate of the polypropylene film can be effectively improved by adding 5-15% of calcium carbonate to each of the heat-sealing layer and the middle layer and casting the film by means of an extruder; and the aluminum-plastic composite film produced by using the polypropylene film has a relatively good curling effect, such that the curling problem of the aluminum-plastic composite film after deep punching is effectively improved; in addition, due to the addition of calcium carbonate, the crystallization rate of polypropylene is changed, and the problem of the heat-sealing interface of the aluminum-plastic composite film becoming white is well solved.
Description
本申请涉及铝塑复合膜技术领域，更具体地涉及一种热法铝塑复合膜及其制备方法。The present application relates to the technical field of aluminum-plastic composite films, and more specifically to a thermal aluminum-plastic composite film and a preparation method thereof.
锂离子电池广泛地应用于数码、交通工具、军事以及储能方面的新能源系统。当前，一般铝塑复合膜(也简称铝塑膜)作为锂离子电池的软包装膜。铝塑复合膜由外至内包括尼龙、铝箔和聚丙烯膜，聚丙烯膜包括热封层、粘结层及位于热封层和粘结层之间的中间层，粘结层与铝箔相连。在铝塑复合膜的制备过程中，一般包括干法铝塑膜和热法铝塑膜两种制备方法，干法铝塑膜是由铝箔与聚丙烯膜直接采用胶黏剂压合，优点是冲深性能好；热法铝塑膜是铝膜和聚丙烯膜之间直接采用改性聚丙烯连接，通过缓慢升温热压合固定，优点是耐电解液和抗水性较好。对于热法铝塑膜而言，由于聚丙烯经高温高压复合过程中会产生热收缩，造成成品冲深卷曲的问题，会影响电池厂家的生产效率及良品率。Lithium-ion batteries are widely used in new energy systems for digital, transportation, military and energy storage. At present, aluminum-plastic composite film (also referred to as aluminum-plastic film) is generally used as a soft packaging film for lithium-ion batteries. The aluminum-plastic composite film includes nylon, aluminum foil and polypropylene film from the outside to the inside. The polypropylene film includes a heat-sealing layer, an adhesive layer and an intermediate layer between the heat-sealing layer and the adhesive layer. The adhesive layer is connected to the aluminum foil. In the preparation process of aluminum-plastic composite film, there are generally two preparation methods: dry aluminum-plastic film and hot aluminum-plastic film. The dry aluminum-plastic film is directly pressed by an adhesive on the aluminum foil and the polypropylene film. The advantage is good deep-drawing performance; the hot aluminum-plastic film is directly connected between the aluminum film and the polypropylene film by modified polypropylene, and is fixed by slowly heating and hot pressing. The advantage is good electrolyte and water resistance. For hot aluminum-plastic film, since polypropylene will produce heat shrinkage during the high temperature and high pressure compounding process, the problem of curling of the finished product will be caused, which will affect the production efficiency and yield rate of battery manufacturers.
申请内容Application Contents
为了克服现有技术的缺陷，本申请提供一种热法铝塑复合膜及其制备方法，可调整聚丙烯膜的热收缩性，有效地改善冲深后卷曲问题，还可以改善热封界面均匀乳白的问题。In order to overcome the defects of the prior art, the present application provides a thermal aluminum-plastic composite film and a preparation method thereof, which can adjust the thermal shrinkage of the polypropylene film, effectively improve the curling problem after deep punching, and also improve the problem of uniform milky whiteness on the heat-sealed interface.
为了实现上述目的，本申请公开了一种热法铝塑复合膜，包括尼龙、铝箔和聚丙烯膜，所述聚丙烯膜包括热封层、粘结层及位于所述热封层和所述粘结层之间的中间层，所述粘结层与所述铝箔相连，In order to achieve the above-mentioned purpose, the present application discloses a thermal aluminum-plastic composite film, comprising nylon, aluminum foil and polypropylene film, wherein the polypropylene film comprises a heat-sealing layer, an adhesive layer and an intermediate layer located between the heat-sealing layer and the adhesive layer, wherein the adhesive layer is connected to the aluminum foil,
所述热封层的制备原料含碳酸钙，且所述碳酸钙含量占所述热封层总质量的5％-15％；The raw material for preparing the heat sealing layer contains calcium carbonate, and the content of calcium carbonate accounts for 5%-15% of the total mass of the heat sealing layer;
所述中间层的制备原料含碳酸钙，且所述碳酸钙含量占所述中间层总质量的5％-15％。The raw material for preparing 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.
与现有技术相比，本申请提供的热法铝塑复合膜中，通过在热封层和中间层中各加入5％-15％的碳酸钙，通过挤出机流延制膜，可有效地改善聚丙烯膜的收缩率，采用该聚丙烯膜生产的铝塑复合膜具有较好的卷曲效果，有效地改善铝塑复合膜冲深后卷曲问题，同时因碳酸钙的加入，改变聚丙烯的结晶速率，很好地改善铝塑复合膜热封界面发白问题。Compared with the prior art, in the heat-process aluminum-plastic composite film provided by the present application, by adding 5%-15% of calcium carbonate to the heat-sealing layer and the middle layer respectively, and casting the film by an extruder, the shrinkage rate of the polypropylene film can be effectively improved. The aluminum-plastic composite film produced by using the polypropylene film has a good curling effect, which effectively improves the curling problem of the aluminum-plastic composite film after deep punching. At the same time, due to the addition of calcium carbonate, the crystallization rate of polypropylene is changed, which greatly improves the whitening problem of the heat-sealing interface of the aluminum-plastic composite film.
需要说明的是，碳酸钙含量占所述热封层总质量的5％-15％，示例地，碳酸钙含量可为但不限于5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％。碳酸钙含量占中间层总质量的5％-15％，示例地，碳酸钙含量可为但不限于5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％。若碳酸钙添加量过少，则效果不明显，碳酸钙含量超过一定量，虽然碳酸钙经过表面处理，但是碳酸钙的耐热性一定程度上影响封装，需要控制合适的含量，含量过高时会影响封装强度和封装界面。It should be noted that the calcium carbonate content accounts for 5%-15% of the total mass of the heat-sealing layer. 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 accounts for 5%-15% of the total mass of the intermediate layer. For example, the calcium carbonate content may be but not limited to 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%. If the amount of calcium carbonate added is too little, the effect is not obvious. If the calcium carbonate content exceeds a certain amount, although the calcium carbonate has been surface treated, the heat resistance of calcium carbonate affects the packaging to a certain extent. It is necessary to control the appropriate content. When the content is too high, it will affect the packaging strength and packaging interface.
较佳地，所述碳酸钙经偶联剂进行预处理，通过偶联剂处理后的碳酸钙大大提高其与其它高分子材料的相容性，有利于挤出造粒。Preferably, the calcium carbonate is pretreated with a coupling agent, and the calcium carbonate treated with the coupling agent greatly improves its compatibility with other polymer materials, which is beneficial to extrusion granulation.
较佳地，所述偶联剂为钛酸酯偶联剂。Preferably, the coupling agent is a titanate coupling agent.
较佳地，所述热封层的制备原料包括质量比为5-15：82-94.5：0.5-3的所述碳酸钙、无规共聚聚丙烯和抗粘连母料。Preferably, the raw materials for preparing the heat sealing layer include the calcium carbonate, random copolymer polypropylene and anti-blocking masterbatch in a mass ratio of 5-15:82-94.5:0.5-3.
较佳地，所述中间层的制备原料包括质量比为5-15：82-94.5：0.5-3的所述碳酸钙、均聚聚丙烯和聚烯烃弹性体。Preferably, the raw materials for preparing the intermediate layer include calcium carbonate, homopolypropylene and polyolefin elastomer in a mass ratio of 5-15:82-94.5:0.5-3.
较佳地，所述粘接层的制备原料包括质量比为95-99：1-5的马来酸酐接枝改性聚丙烯和成核剂。
Preferably, the raw materials for preparing the adhesive layer include maleic anhydride grafted modified polypropylene and a nucleating agent in a mass ratio of 95-99:1-5.
较佳地，所选碳酸钙为1000目以上的轻质碳酸钙。Preferably, the selected calcium carbonate is light calcium carbonate with a mesh size of 1000 or more.
相应地，本申请还提供一种热法铝塑复合膜的制备方法，包括步骤：Accordingly, the present application also provides a method for preparing a thermal aluminum-plastic composite film, comprising the steps of:
(1)制备聚丙烯膜(1) Preparation of polypropylene film
1.1热封层造粒1.1 Heat seal layer granulation
将碳酸钙与热封层其它制备原料造粒得到物料A；Granulate calcium carbonate and other raw materials for preparing the heat seal layer to obtain material A;
1.2中间层造粒1.2 Intermediate layer granulation
将碳酸钙与中间层其它制备原料造粒得到物料B；Granulate calcium carbonate and other raw materials for the intermediate layer to obtain material B;
物料A、物料B和粘接层的制备原料分别混合后吸入到对应的料斗中，通过三螺杆定量输送、挤出机挤出及过滤、从T形模头流延经冷却辊冷却、切边、收卷、再分切，制得聚丙烯膜；The material A, the material B and the raw materials for preparing the bonding layer are mixed and sucked into the corresponding hoppers, quantitatively conveyed by three screws, extruded and filtered by an extruder, cast from a T-shaped die head, cooled by a cooling roller, trimmed, rolled, and then slit to obtain a polypropylene film;
(2)提供铝箔，在铝箔的哑面复合尼龙层；(2) providing an aluminum foil, and compounding a nylon layer on the matte surface of the aluminum foil;
(3)在铝箔的亮面热法复合聚丙烯膜，制得铝塑复合膜。(3) The bright side of the aluminum foil is thermally laminated with a polypropylene film to obtain an aluminum-plastic composite film.
较佳地，步骤(3)中，热法复合温度至少为160℃。Preferably, in step (3), the thermal compounding temperature is at least 160°C.
较佳地，步骤(2)中，在铝箔的哑面涂覆胶黏层，再贴合尼龙层，在50-70℃条件下固化1-5天。Preferably, in step (2), an adhesive layer is coated on the matte surface of the aluminum foil, and then the nylon layer is adhered thereto, and then cured at 50-70° C. for 1-5 days.
图1是本申请的热法铝塑复合膜的结构示意图。FIG. 1 is a schematic diagram of the structure of the thermal aluminum-plastic composite film of the present application.
图2是本申请实施例1-5铝塑复合膜的界面均匀乳白程度图，其中图2(a)-图2(e)分别对应实施例1-5。FIG. 2 is a diagram showing the uniform milky degree of the interfaces of the aluminum-plastic composite films of Examples 1-5 of the present application, wherein FIG. 2( a ) to FIG. 2( e ) correspond to Examples 1-5, respectively.
图3是本申请对比例1-5铝塑复合膜的界面均匀乳白程度图，其中图3(f)-图3(j)分别对应对比例1-5。FIG. 3 is a diagram showing the uniform milky degree of the interfaces of the aluminum-plastic composite films of comparative examples 1-5 of the present application, wherein FIG. 3( f ) to FIG. 3( j ) correspond to comparative examples 1-5, respectively.
为详细说明本申请的技术内容、构造特征、所实现目的及效果，以下结合实施方式详予说明。
In order to explain the technical content, structural features, achieved objectives and effects of the present application in detail, the following is a detailed description in conjunction with the implementation methods.
请参考图1，本申请的热法铝塑复合膜，由外至内，包括尼龙层10、胶黏层30、铝箔50和聚丙烯膜70，尼龙层10位于最外层，耐磨、耐腐蚀，作为保护之用；胶黏层30将尼龙层10和铝箔50进行粘结固定，例如，胶黏层30可采用但不限于聚氨酯和异氰酸酯固化剂的双组份胶水。其中，聚丙烯膜70包括粘结层71、热封层75及位于热封层75和粘结层71之间的中间层73，粘结层71与铝箔50相连。本申请在热封层75和中间层73中各加入5％-15％的碳酸钙，通过挤出机流延制膜，可有效地改善聚丙烯膜70的收缩率，采用该聚丙烯膜70生产的铝塑复合膜具有较好的卷曲效果，有效地改善铝塑复合膜冲深后卷曲问题，同时因碳酸钙的加入，改变聚丙烯的结晶速率，很好地改善铝塑复合膜热封界面发白问题。Please refer to FIG1 . The thermal aluminum-plastic composite film of the present application includes, from outside to inside, a nylon layer 10, an adhesive layer 30, an aluminum foil 50 and a polypropylene film 70. The nylon layer 10 is located at the outermost layer and is wear-resistant and corrosion-resistant for protection. The adhesive layer 30 is used to bond and fix the nylon layer 10 and the aluminum foil 50. For example, the adhesive layer 30 can use, but is not limited to, a two-component glue of polyurethane and isocyanate curing agent. The polypropylene film 70 includes an adhesive layer 71, a heat-sealing layer 75 and an intermediate layer 73 located between the heat-sealing layer 75 and the adhesive layer 71. The adhesive layer 71 is connected to the aluminum foil 50. The present application adds 5%-15% calcium carbonate to the heat-sealing layer 75 and the middle layer 73, respectively, and uses an extruder to cast the film, which can effectively improve the shrinkage rate of the polypropylene film 70. The aluminum-plastic composite film produced using the polypropylene film 70 has a good curling effect, which effectively improves the curling problem of the aluminum-plastic composite film after deep punching. At the same time, due to the addition of calcium carbonate, the crystallization rate of polypropylene is changed, which greatly improves the whitening problem of the heat-sealing interface of the aluminum-plastic composite film.
下面，通过几个具体实施方式进一步阐述本申请的铝塑复合膜，但不是对本申请保护范围的限制。The aluminum-plastic composite film of the present application is further described below through several specific implementations, but this does not limit the protection scope of the present application.
实施例1Example 1
一种铝塑复合膜的制备方法，包括步骤：A method for preparing an aluminum-plastic composite film comprises the following steps:
(1)制备聚丙烯膜：(1) Preparation of polypropylene film:
将碳酸钙在120℃条件下烘烤4h后，加入高速混料机中，然后加入2％钛酸酯偶联剂，在70℃条件下，高速搅拌混合3h，静置、过滤、干燥；Calcium carbonate was baked at 120°C for 4 hours, added to a high-speed mixer, and then 2% titanate coupling agent was added, and mixed at high speed at 70°C for 3 hours, allowed to stand, filtered, and dried;
1.1热封层造粒1.1 Heat seal layer granulation
将表面处理后的碳酸钙、无规共聚聚丙烯RP320M、抗粘连母料SAB-7203S按照5:93:2的质量比混合，然后通过双螺杆挤出造粒、剪切成颗粒、真空干燥，待用；The surface treated calcium carbonate, random copolymer polypropylene RP320M and anti-blocking masterbatch SAB-7203S are mixed in a mass ratio of 5:93:2, and then granulated by twin-screw extrusion, sheared into granules, and vacuum dried for standby use;
1.2中间层造粒1.2 Intermediate layer granulation
将表面处理后的碳酸钙、中海壳牌的HP510M、丙烯和乙烯共聚物弹性体(埃克森美孚3000)按照5:85:10质量比混合，然后通过双螺杆挤出造粒、剪切成颗粒、真空干燥，待用；
The surface treated calcium carbonate, HP510M of CNOOC Shell, and propylene and ethylene copolymer elastomer (ExxonMobil 3000) were mixed in a mass ratio of 5:85:10, and then granulated by twin-screw extrusion, sheared into granules, and vacuum dried for standby use;
1.3粘接层的制备原料1.3 Raw materials for the preparation of the bonding layer
马来酸酐接枝改性聚丙烯(三井化学QF551)及成核剂(日本艾迪科NA-21)按99:1质量比混合均匀，待用；Maleic anhydride grafted modified polypropylene (Mitsui Chemicals QF551) and nucleating agent (Japan Aidico NA-21) were mixed uniformly at a mass ratio of 99:1 and set aside;
将造粒后的热封层材料、中间层材料及混合后的粘接层的制备原料分别吸入到对应的料斗中，三层厚度分别为7、26、7μm，通过三螺杆定量输送、挤出机挤出及过滤、从T形模头流延经冷却辊冷却、切边、收卷、再按规格分切即得聚丙烯膜，厚度40μm；The granulated heat-sealing layer material, the intermediate layer material and the mixed adhesive layer preparation raw materials are sucked into the corresponding hoppers respectively, and the thickness of the three layers are 7, 26 and 7 μm respectively, and the polypropylene film is obtained by quantitative conveying by a three-screw extruder, extruding and filtering by an extruder, casting from a T-shaped die head, cooling by a cooling roller, trimming, winding, and then slitting according to specifications, and the thickness of the polypropylene film is 40 μm;
(2)提供河南明泰40μm的铝箔，将铝箔双面钝化处理，然后在铝箔的哑面采用干式复合工艺复合一层长塑25μm的尼龙膜，在60℃固化3天，得到半成品；(2) providing Henan Mingtai 40 μm aluminum foil, passivating both sides of the aluminum foil, and then compounding a layer of 25 μm nylon film on the matte side of the aluminum foil by dry compounding process, and curing at 60° C. for 3 days to obtain a semi-finished product;
(3)在铝箔的亮面热法复合该聚丙烯膜，复合温度为160℃，制得铝塑复合膜。(3) The polypropylene film is thermally laminated on the bright side of the aluminum foil at a lamination temperature of 160° C. to obtain an aluminum-plastic composite film.
实施例2Example 2
该实施例与实施例1基本相同，不同在于，该实施例中热封层中碳酸钙含量占比为10％，中间层中碳酸钙含量占比为5％，而实施例1中热封层中碳酸钙含量占比为5％，中间层中碳酸钙含量占比为5％，其余与实施例1均相同，在此不进行阐述。This embodiment is basically the same as Embodiment 1, except that, in this embodiment, the calcium carbonate content in the heat sealing layer accounts for 10%, and the calcium carbonate content in the middle layer accounts for 5%, while in Embodiment 1, the calcium carbonate content in the heat sealing layer accounts for 5%, and the calcium carbonate content in the middle layer accounts for 5%. The rest is the same as Embodiment 1 and will not be elaborated here.
实施例3Example 3
该实施例与实施例1基本相同，不同在于，该实施例中热封层中碳酸钙含量占比为10％，中间层中碳酸钙含量占比10％，而实施例1中热封层中碳酸钙含量占比为5％，中间层中碳酸钙含量占比为5％，其余与实施例1均相同，在此不进行阐述。This embodiment is basically the same as Embodiment 1, except that, in this embodiment, the calcium carbonate content in the heat sealing layer accounts for 10%, and the calcium carbonate content in the middle layer accounts for 10%, while in Embodiment 1, the calcium carbonate content in the heat sealing layer accounts for 5%, and the calcium carbonate content in the middle layer accounts for 5%. The rest is the same as Embodiment 1 and will not be elaborated here.
实施例4Example 4
该实施例与实施例1基本相同，不同在于，该实施例中热封层中碳酸钙含量占比为15％，中间层中碳酸钙含量占比10％，而实施例1中热封层中碳酸钙含量占比为5％，中间层中碳酸钙含量占比为5％，其余与实施例1均相同，在此不进行阐述。This embodiment is basically the same as Embodiment 1, except that, in this embodiment, the calcium carbonate content in the heat sealing layer accounts for 15%, and the calcium carbonate content in the middle layer accounts for 10%, while in Embodiment 1, the calcium carbonate content in the heat sealing layer accounts for 5%, and the calcium carbonate content in the middle layer accounts for 5%. The rest is the same as Embodiment 1 and will not be elaborated here.
实施例5Example 5
该实施例与实施例1基本相同，不同在于，该实施例中热封层中碳酸钙含量占比为15％，中间层中碳酸钙含量占比15％，而实施例1中热封层中碳酸钙含量占比为5％，中间层中碳酸钙含量占比为5％，其余与实施例1均相同，在此不进行阐述。This embodiment is basically the same as Embodiment 1, except that, in this embodiment, the calcium carbonate content in the heat sealing layer accounts for 15%, and the calcium carbonate content in the middle layer accounts for 15%, while in Embodiment 1, the calcium carbonate content in the heat sealing layer accounts for 5%, and the calcium carbonate content in the middle layer accounts for 5%. The rest is the same as Embodiment 1 and will not be elaborated here.
对比例1Comparative Example 1
该对比例1与实施例1基本相同，不同在于，该对比例1中热封层中不含碳酸钙，中间层中不含碳酸钙，而实施例1中热封层中碳酸钙含量占比为5％，中间层中碳酸钙含量占比为5％，其余与实施例1均相同，在此不进行阐述。The comparative example 1 is basically the same as the example 1, except that the heat sealing layer in the comparative example 1 does not contain calcium carbonate, and the middle layer does not contain calcium carbonate, while the calcium carbonate content in the heat sealing layer in the example 1 accounts for 5%, and the calcium carbonate content in the middle layer accounts for 5%, and the rest is the same as the example 1, which will not be elaborated here.
对比例2Comparative Example 2
该对比例2与实施例1基本相同，不同在于，该对比例2中热封层中不含碳酸钙，中间层中碳酸钙含量占比为10％，而实施例1中热封层中碳酸钙含量占比为5％，中间层中碳酸钙含量占比为5％，其余与实施例1均相同，在此不进行阐述。The comparative example 2 is basically the same as the example 1, except that the heat sealing layer in the comparative example 2 does not contain calcium carbonate, and the calcium carbonate content in the middle layer accounts for 10%, while the calcium carbonate content in the heat sealing layer in the example 1 accounts for 5%, and the calcium carbonate content in the middle layer accounts for 5%. The rest is the same as the example 1 and will not be elaborated here.
对比例3Comparative Example 3
该对比例3与实施例1基本相同，不同在于，该对比例3中热封层中碳酸钙含量占比为10％，中间层中不含碳酸钙，而实施例1中热封层中碳酸钙含量占比为5％，中间层中碳酸钙含量占比为5％，其余与实施例1均相同，在此不进行阐述。This comparative example 3 is basically the same as Example 1, except that in this comparative example 3, the content of calcium carbonate in the heat sealing layer accounts for 10%, and the middle layer does not contain calcium carbonate, while in Example 1, the content of calcium carbonate in the heat sealing layer accounts for 5%, and the content of calcium carbonate in the middle layer accounts for 5%. The rest is the same as Example 1 and will not be elaborated here.
对比例4Comparative Example 4
该对比例4与实施例1基本相同，不同在于，该对比例4中热封层中碳酸钙含量占比为20％，中间层中碳酸钙含量占比为5％，而实施例1中热封层中碳酸钙含量占比为5％，中间层中碳酸钙含量占比为5％，其余与实施例1均相同，在此不进行阐述。This comparative example 4 is basically the same as Example 1, except that in this comparative example 4, the calcium carbonate content in the heat sealing layer accounts for 20%, and the calcium carbonate content in the middle layer accounts for 5%, while in Example 1, the calcium carbonate content in the heat sealing layer accounts for 5%, and the calcium carbonate content in the middle layer accounts for 5%. The rest is the same as Example 1 and will not be elaborated here.
对比例5Comparative Example 5
该对比例5与实施例1基本相同，不同在于，该对比例5中热封层中碳酸钙含量占比为5％，中间层中碳酸钙含量占比为20％，而实施例1中热封层中碳酸钙含量占比为5％，中间层中碳酸钙含量占比为5％，其余与实施例1均相同，在此不进行阐述。The comparative example 5 is basically the same as the example 1, except that in the comparative example 5, the calcium carbonate content in the heat sealing layer accounts for 5%, and the calcium carbonate content in the middle layer accounts for 20%, while in the example 1, the calcium carbonate content in the heat sealing layer accounts for 5%, and the calcium carbonate content in the middle layer accounts for 5%. The rest is the same as the example 1 and will not be elaborated here.
将实施例1-5和对比例1-5制得铝塑复合膜进行性能检测，结果如表1所示。The aluminum-plastic composite films prepared in Examples 1-5 and Comparative Examples 1-5 were tested for performance, and the results are shown in Table 1.
测试项目与方法如下：The test items and methods are as follows:
冲深卷曲高度测试方法：将铝塑膜裁切为110*120mm大小，冲壳尺寸55*60mm，冲壳深度5.0mm，冲壳后平放在桌面上，测量尼龙面翘起高度与桌面的垂直高度作为冲深卷曲高度。Test method for deep punching curl height: cut the aluminum-plastic film into 110*120mm size, punch shell size 55*60mm, punch shell depth 5.0mm, put it flat on the table after punching, and measure the height of the nylon surface rising and the vertical height of the table as the deep punching curl height.
热封强度：按QB-T 2358-1998塑料薄膜包装袋热合强度试验方法测试制成铝塑膜后的热封强度，测试后观察热封界面，界面是否均匀乳白(如图2-图3所示)，热封界面均匀乳白程度等级越低，产品热封效果越好。Heat seal strength: Test the heat seal strength of the aluminum-plastic film according to QB-T 2358-1998 test method for heat seal strength of plastic film packaging bags. Observe the heat seal interface after the test to see if it is uniformly milky white (as shown in Figures 2 and 3). The lower the uniform milky whiteness of the heat seal interface, the better the heat seal effect of the product.
热收缩率：按照GB/T 12027-2004的规定，实验条件(160±2)℃，时间5min，分别测试尼龙膜纵向(机器运行方向)、横向(与机器运行垂直方向)的热收缩率。
Thermal shrinkage rate: According to the provisions of GB/T 12027-2004, the experimental conditions are (160±2)℃, the time is 5min, and the thermal shrinkage rates of the nylon film in the longitudinal direction (machine running direction) and the transverse direction (vertical to the machine running direction) are tested respectively.
表1测试结果
Table 1 Test results
Table 1 Test results
由表1的数据可知，实施例1-5中的铝塑复合膜较对比例1而言，虽然热封强度略有下降，但下降幅度不大，且在可接受范围内，但界面乳白及卷曲效果明显得到改善，具有较好的冲深卷曲性和封装性能。主要是因本申请通过在热封层和中间层中各加入5％-15％的碳酸钙，通过挤出机流延制膜，可有效地改善聚丙烯膜的收缩率，采用该聚丙烯膜生产的铝塑复合膜具有较好的卷曲效果，有效地改善铝塑复合膜冲深后卷曲问题，同时因碳酸钙的加入，改变聚丙烯的结晶速率，很好地改善铝塑复合膜热封界面发白问题。It can be seen from the data in Table 1 that, compared with Comparative Example 1, the heat seal strength of the aluminum-plastic composite films in Examples 1-5 is slightly reduced, but the reduction is not large and is within an acceptable range, but the interface milky white and curling effects are significantly improved, and the film has good deep-drawing curling and packaging performance. This is mainly because the present application can effectively improve the shrinkage rate of the polypropylene film by adding 5%-15% calcium carbonate to the heat seal layer and the middle layer, and the aluminum-plastic composite film produced by the polypropylene film has a good curling effect, effectively improving the curling problem of the aluminum-plastic composite film after deep-drawing. At the same time, due to the addition of calcium carbonate, the crystallization rate of polypropylene is changed, which greatly improves the whitening problem of the heat seal interface of the aluminum-plastic composite film.
对比例1中因热封层中不含碳酸钙，中间层中不含碳酸钙，在聚丙烯与铝箔经过高温复合时，因聚丙烯本身的热收缩性，造成聚丙烯热收缩，聚丙烯膜的收缩应力不足以抵挡尼龙膜面的应力，卷曲明显，热封界面性能也明显较差。In Comparative Example 1, since the heat sealing layer does not contain calcium carbonate and the middle layer does not contain calcium carbonate, when the polypropylene and the aluminum foil are compounded at high temperature, the polypropylene shrinks due to its own thermal shrinkage. The shrinkage stress of the polypropylene film is not enough to withstand the stress of the nylon film surface, resulting in obvious curling and significantly poor heat sealing interface performance.
对比例2中，虽然在中间层中加入碳酸钙，改善了冲深卷曲性能，但未能改善热封界面效果。In Comparative Example 2, although calcium carbonate was added to the middle layer to improve the deep-drawing curling performance, the heat-sealing interface effect was not improved.
对比例3中，虽然在热封层中加入碳酸钙，改善了热封界面效果，但未能改善冲深卷曲性能。In Comparative Example 3, although calcium carbonate was added to the heat-sealing layer to improve the heat-sealing interface effect, the deep-drawing curling performance was not improved.
对比例4中热封层中碳酸钙含量超过一定量，碳酸钙的耐热性在一定程度上会影响封装性，碳酸钙含量过高时会影响热封强度和封装界面。In Comparative Example 4, the calcium carbonate content in the heat-sealing layer exceeds a certain amount. The heat resistance of calcium carbonate will affect the packaging properties to a certain extent. When the calcium carbonate content is too high, it will affect the heat-sealing strength and the packaging interface.
对比例5中，中间层中碳酸钙含量超过一定量，碳酸钙含量过高时会影响相容性，层间粘合强度减弱，进而会影响热封强度和封装界面。In Comparative Example 5, the calcium carbonate content in the middle layer exceeds a certain amount. When the calcium carbonate content is too high, it will affect the compatibility, weaken the interlayer bonding strength, and further affect the heat sealing strength and packaging interface.
以上所揭露的仅为本申请的优选实施例而已，当然不能以此来限定本申请之权利范围，因此依本申请专利范围所作的等同变化，仍属本申请所涵盖的范围。
The above disclosure is only the preferred embodiment of the present application, which certainly cannot be used to limit the scope of rights of the present application. Therefore, equivalent changes made according to the patent scope of the present application are still within the scope covered by the present application.
Claims (10)
- 一种热法铝塑复合膜，包括尼龙、铝箔和聚丙烯膜，其特征在于，所述聚丙烯膜包括热封层、粘结层及位于所述热封层和所述粘结层之间的中间层，所述粘结层与所述铝箔相连，A thermal aluminum-plastic composite film comprises nylon, aluminum foil and polypropylene film, wherein the polypropylene film comprises a heat-sealing layer, an adhesive layer and an intermediate layer between the heat-sealing layer and the adhesive layer, the adhesive layer is connected to the aluminum foil,所述热封层的制备原料含碳酸钙，且所述碳酸钙含量占所述热封层总质量的5％-15％；The raw material for preparing the heat sealing layer contains calcium carbonate, and the content of calcium carbonate accounts for 5%-15% of the total mass of the heat sealing layer;所述中间层的制备原料含碳酸钙，且所述碳酸钙含量占所述中间层总质量的5％-15％。The raw material for preparing 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.
- 如权利要求1所述的热法铝塑复合膜，其特征在于，所述碳酸钙经偶联剂进行预处理。The thermally processed aluminum-plastic composite film according to claim 1, characterized in that the calcium carbonate is pretreated with a coupling agent.
- 如权利要求2所述的热法铝塑复合膜，其特征在于，所述偶联剂为钛酸酯偶联剂。The thermally processed aluminum-plastic composite film according to claim 2, characterized in that the coupling agent is a titanate coupling agent.
- 如权利要求1所述的热法铝塑复合膜，其特征在于，所述热封层的制备原料包括质量比为5-15：82-94.5：0.5-3的所述碳酸钙、无规共聚聚丙烯和抗粘连母料。The thermally-processed aluminum-plastic composite film according to claim 1 is characterized in that the raw materials for preparing the heat sealing layer include the calcium carbonate, random copolymer polypropylene and anti-blocking masterbatch in a mass ratio of 5-15:82-94.5:0.5-3.
- 如权利要求1所述的热法铝塑复合膜，其特征在于，所述中间层的制备原料包括质量比为5-15：82-94.5：0.5-3的所述碳酸钙、均聚聚丙烯和聚烯烃弹性体。The thermally processed aluminum-plastic composite film according to claim 1 is characterized in that the raw materials for preparing the intermediate layer include calcium carbonate, homopolymer polypropylene and polyolefin elastomer in a mass ratio of 5-15:82-94.5:0.5-3.
- 如权利要求1所述的热法铝塑复合膜，其特征在于，所述粘接层的制备原料包括质量比为95-99：1-5的马来酸酐接枝改性聚丙烯和成核剂。 The thermally processed aluminum-plastic composite film according to claim 1 is characterized in that the raw materials for preparing the adhesive layer include maleic anhydride grafted modified polypropylene and a nucleating agent in a mass ratio of 95-99:1-5.
- 如权利要求1所述的热法铝塑复合膜，其特征在于，所述碳酸钙为1000目以上的轻质碳酸钙。The thermally processed aluminum-plastic composite film according to claim 1 is characterized in that the calcium carbonate is light calcium carbonate with a mesh size of 1000 or more.
- 一种如权利要求1-7任一项所述的热法铝塑复合膜的制备方法，其特征在于，包括步骤：A method for preparing a thermal aluminum-plastic composite film according to any one of claims 1 to 7, characterized in that it comprises the steps of:(1)制备聚丙烯膜(1) Preparation of polypropylene film1.1热封层造粒1.1 Heat seal layer granulation将碳酸钙与热封层其它制备原料造粒得到物料A；Granulate calcium carbonate and other raw materials for preparing the heat seal layer to obtain material A;1.2中间层造粒1.2 Intermediate layer granulation将碳酸钙与中间层其它制备原料造粒得到物料B；Granulate calcium carbonate and other raw materials for the intermediate layer to obtain material B;物料A、物料B和粘接层的制备原料分别混合后吸入到对应的料斗中，通过三螺杆定量输送、挤出机挤出及过滤、从T形模头流延经冷却辊冷却、切边、收卷、再分切，制得聚丙烯膜；The material A, the material B and the raw materials for preparing the bonding layer are mixed and sucked into the corresponding hoppers, quantitatively conveyed by three screws, extruded and filtered by an extruder, cast from a T-shaped die head, cooled by a cooling roller, trimmed, rolled, and then slit to obtain a polypropylene film;(2)提供铝箔，在铝箔的哑面复合尼龙层；(2) providing an aluminum foil, and compounding a nylon layer on the matte surface of the aluminum foil;(3)在铝箔的亮面热法复合聚丙烯膜，制得铝塑复合膜。(3) The bright side of the aluminum foil is thermally laminated with a polypropylene film to obtain an aluminum-plastic composite film.
- 如权利要求8所述的热法铝塑复合膜的制备方法，其特征在于，步骤(3)中，热法复合温度至少为160℃。The method for preparing a thermal aluminum-plastic composite film as described in claim 8, characterized in that in step (3), the thermal composite temperature is at least 160°C.
- 如权利要求8所述的热法铝塑复合膜的制备方法，其特征在于，步骤(2)中，在铝箔的哑面涂覆胶黏层，再贴合尼龙层，在50-70℃条件下固化1-5天。 The method for preparing a thermal aluminum-plastic composite film as described in claim 8 is characterized in that in step (2), an adhesive layer is coated on the matte surface of the aluminum foil, and then a nylon layer is attached, and the mixture is cured at 50-70° C. for 1-5 days.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005104152A (en) * | 2003-09-12 | 2005-04-21 | Toyobo Co Ltd | Heat-sealable laminated polypropylene resin film and package |
| CN103030880A (en) * | 2012-04-16 | 2013-04-10 | 上海韬鸿化工科技有限公司 | Coupling agent modified calcium carbonate filled polypropylene plastic and preparation method thereof |
| CN206076292U (en) * | 2016-09-26 | 2017-04-05 | 东莞市卓越新材料科技有限公司 | A kind of impact resistance aluminum plastic film |
| CN109228590A (en) * | 2018-07-16 | 2019-01-18 | 天津市宝德包装有限公司 | A kind of ultralow temperature casting films |
| CN109866491A (en) * | 2018-12-28 | 2019-06-11 | 新纶复合材料科技（常州）有限公司 | A kind of aluminum-plastic composite membrane with agent of low hygroscopicity nylon outer layer |
| CN113978079A (en) * | 2021-09-27 | 2022-01-28 | 宁波瑞成包装材料有限公司 | Temperature-resistant anti-stripping film and production method thereof |
| CN115302883A (en) * | 2022-08-04 | 2022-11-08 | 江西省盛纬材料有限公司 | Aluminum-plastic composite film and preparation method thereof |
| CN115742489A (en) * | 2022-12-15 | 2023-03-07 | 江西省盛纬材料有限公司 | Thermal-process aluminum-plastic composite film and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100526691B1 (en) * | 1998-09-12 | 2005-12-29 | 삼성토탈 주식회사 | Polypropylene film with excellent heat resistance |
| US20030060547A1 (en) * | 2001-07-24 | 2003-03-27 | Chi-Ming Chan | Polypropylene/calcium carbonate nanocomposites |
| CN102532687A (en) * | 2010-12-21 | 2012-07-04 | 上海日之升新技术发展有限公司 | Composite material with low shrinkage rate and preparation method thereof |
| CN107283976B (en) * | 2017-06-30 | 2019-10-11 | 永新股份（黄山）包装有限公司 | A kind of microporous polyethylene breathable films and preparation method thereof |
| CN112123906A (en) * | 2020-08-12 | 2020-12-25 | 安徽国风塑业股份有限公司 | Curl-free BOPP (biaxially-oriented Polypropylene) matt film and preparation method thereof |
| CN112721354A (en) * | 2020-12-30 | 2021-04-30 | 苏州福斯特光伏材料有限公司 | Aluminum-plastic film and preparation method thereof |
| CN113594593B (en) * | 2021-07-12 | 2023-06-20 | 苏州福斯特光伏材料有限公司 | Design method of aluminum plastic film and aluminum plastic film |
-
2022
- 2022-12-15 CN CN202211629188.7A patent/CN115742489B/en active Active
-
2023
- 2023-05-31 WO PCT/CN2023/097290 patent/WO2024124817A1/en unknown
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005104152A (en) * | 2003-09-12 | 2005-04-21 | Toyobo Co Ltd | Heat-sealable laminated polypropylene resin film and package |
| CN103030880A (en) * | 2012-04-16 | 2013-04-10 | 上海韬鸿化工科技有限公司 | Coupling agent modified calcium carbonate filled polypropylene plastic and preparation method thereof |
| CN206076292U (en) * | 2016-09-26 | 2017-04-05 | 东莞市卓越新材料科技有限公司 | A kind of impact resistance aluminum plastic film |
| CN109228590A (en) * | 2018-07-16 | 2019-01-18 | 天津市宝德包装有限公司 | A kind of ultralow temperature casting films |
| CN109866491A (en) * | 2018-12-28 | 2019-06-11 | 新纶复合材料科技（常州）有限公司 | A kind of aluminum-plastic composite membrane with agent of low hygroscopicity nylon outer layer |
| CN113978079A (en) * | 2021-09-27 | 2022-01-28 | 宁波瑞成包装材料有限公司 | Temperature-resistant anti-stripping film and production method thereof |
| CN115302883A (en) * | 2022-08-04 | 2022-11-08 | 江西省盛纬材料有限公司 | Aluminum-plastic composite film and preparation method thereof |
| CN115742489A (en) * | 2022-12-15 | 2023-03-07 | 江西省盛纬材料有限公司 | Thermal-process aluminum-plastic composite film and preparation method thereof |
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