CN117801711A - Hot melt adhesive film for water boiling resistant ASA/metal composite, and preparation method and application thereof - Google Patents
Hot melt adhesive film for water boiling resistant ASA/metal composite, and preparation method and application thereof Download PDFInfo
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- CN117801711A CN117801711A CN202311817033.0A CN202311817033A CN117801711A CN 117801711 A CN117801711 A CN 117801711A CN 202311817033 A CN202311817033 A CN 202311817033A CN 117801711 A CN117801711 A CN 117801711A
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
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- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 238000013329 compounding Methods 0.000 claims abstract description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005977 Ethylene Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 31
- 238000001125 extrusion Methods 0.000 claims description 19
- 239000000155 melt Substances 0.000 claims description 18
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- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 7
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- 229920006318 anionic polymer Polymers 0.000 claims description 3
- 238000003475 lamination Methods 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
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- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
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- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- VSVVZZQIUJXYQA-UHFFFAOYSA-N [3-(3-dodecylsulfanylpropanoyloxy)-2,2-bis(3-dodecylsulfanylpropanoyloxymethyl)propyl] 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OCC(COC(=O)CCSCCCCCCCCCCCC)(COC(=O)CCSCCCCCCCCCCCC)COC(=O)CCSCCCCCCCCCCCC VSVVZZQIUJXYQA-UHFFFAOYSA-N 0.000 description 1
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- 229920001567 vinyl ester resin Polymers 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of hot melt adhesive films, in particular to a hot melt adhesive film for boiling-resistant ASA/metal compounding, and a preparation method and application thereof. The hot melt adhesive film for ASA/metal compounding comprises a first adhesive layer, a core layer and a second adhesive layer which are arranged in a laminated manner; the first adhesive layer is mainly prepared from the following components in parts by weight: 10-50 parts of acrylic block copolymer, 50-90 parts of thermoplastic polyurethane elastomer and 0.1-0.5 part of antioxidant; the core layer is a maleic anhydride grafted ethylene-vinyl acetate copolymer, and the grafting rate of maleic anhydride in the maleic anhydride grafted ethylene-vinyl acetate copolymer is more than 0.1%; the second adhesive layer comprises maleic anhydride grafted ethylene; the mass ratio of the first adhesive layer, the core layer and the second adhesive layer is (3-6)/(2-3)/(1-3). The ASA/metal composite hot melt adhesive film has excellent water resistance and heat resistance, and widens the application of the ASA/metal composite hot melt adhesive film in outdoor products.
Description
Technical Field
The invention relates to the technical field of hot melt adhesive films, in particular to a hot melt adhesive film for boiling-resistant ASA/metal compounding, and a preparation method and application thereof.
Background
The acrylonitrile-styrene-acrylic ester ternary graft copolymer (ASA) is formed by copolymerizing styrene, acrylonitrile and acrylic ester rubber, integrates the impact resistance, weather resistance, chemical resistance and the like of acrylic ester and the excellent processability of styrene, and not only maintains the main characteristics of ABS, but also uses acrylic ester rubber without unsaturated double bonds to replace butadiene rubber with unsaturated double bonds in ABS, so that the ASA can resist degradation, aging and fading caused by ultraviolet irradiation, and can also strongly guarantee the degradation or discoloration caused by high temperature in the oxidation processing process in the atmosphere, thereby greatly improving the ageing resistance and weather resistance of the material and enabling the product to be applied to be extended to outdoor use.
The ASA film/metal clad plate can be used for building decorative materials, and compared with the PET film/metal clad plate which is mostly used at present, the PET material is inferior to the ASA material in weather resistance, acid and alkali resistance and the like. At present, in the ASA film/metal coating multi-production polyurethane hot melt adhesive and polyurethane liquid adhesive method, the water resistance and heat resistance of the polyurethane adhesive are relatively insufficient, the stripping force is greatly reduced after water boiling, the viscosity is insufficient, the quality safety hidden trouble exists for outdoor application, and the polyurethane liquid adhesive method has limited application due to the defects of environmental protection and product quality control.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a hot melt adhesive film for water boiling resistant ASA/metal composite, which solves the technical problems of poor water boiling resistance and the like of ASA/metal composite adhesive in the prior art.
The invention further aims at providing a preparation method of the hot melt adhesive film for the boiling-resistant ASA/metal composite.
It is a further object of the present invention to provide the use of a hot melt adhesive film for a water boiling resistant ASA/metal composite.
In order to achieve the above object of the present invention, in one aspect, the present invention provides a hot melt adhesive film for a water boiling resistant ASA/metal composite, comprising a first adhesive layer, a core layer and a second adhesive layer which are laminated;
the first adhesive layer is mainly prepared from the following components in parts by weight:
10-50 parts of acrylic block copolymer, 50-90 parts of thermoplastic polyurethane elastomer and 0.1-0.5 part of antioxidant;
the core layer is a maleic anhydride grafted ethylene-vinyl acetate copolymer, and the grafting rate of maleic anhydride in the maleic anhydride grafted ethylene-vinyl acetate copolymer is more than 0.1%;
the second adhesive layer comprises maleic anhydride grafted ethylene;
the mass ratio of the first adhesive layer, the core layer and the second adhesive layer is (3-6)/(2-3)/(1-3).
In a specific embodiment of the invention, the acrylic block copolymer is a living anionic polymer elastomer.
In ase:Sub>A specific embodiment of the present invention, the acrylic block copolymer comprises an acrylic copolymer of the A-B-A and/or A-B type.
In ase:Sub>A specific embodiment of the invention, the acrylic block copolymer is an A-B-A type triblock copolymer, wherein block A is PMMA and block B is PBA or P (BA/2 EHA).
In a specific embodiment of the invention, the melt flow index of the acrylic block copolymer is 1-15 g/10min under the conditions of the temperature of 190 ℃ and the load of 2.16 kg.
In a specific embodiment of the present invention, the thermoplastic polyurethane elastomer comprises a polyester polyurethane and/or a polyether polyurethane.
In a specific embodiment of the present invention, the thermoplastic polyurethane elastomer has a melt flow index of 1 to 30g/10min at 190℃under a load of 2.16 kg.
In a specific embodiment of the invention, the grafting ratio of maleic anhydride in the maleic anhydride grafted ethylene-vinyl acetate copolymer is 0.12-0.2%.
In a specific embodiment of the present invention, the melt flow index of the maleic anhydride grafted ethylene-vinyl acetate copolymer is 1 to 24g/10min at 190℃under a load of 2.16 kg.
In a specific embodiment of the present invention, the maleic anhydride grafted polyethylene in the second adhesive layer has a melt flow index of 1 to 15g/10min at 190℃under a load of 2.16 kg.
In a specific embodiment of the present invention, the maleic anhydride grafted polyethylene in the second adhesive layer satisfies: the stripping force after heat sealing with the aluminum sheet is more than 70N/25mm; wherein, the heat lamination condition includes: the mixture was hot-pressed at 130℃and 0.6MPa for 5 seconds in the order of aluminum sheet, 10 μm thick maleic anhydride-grafted polyethylene film, and PE 7042.
In a specific embodiment of the present invention, the raw material of the second adhesive layer is at least one of VB550A, VB770 and VB 570A.
In another aspect, the present invention provides a method for preparing the hot melt adhesive film for boiling-resistant ASA/metal composite, comprising the steps of:
and carrying out multilayer coextrusion casting on the first adhesive layer raw material, the core layer raw material and the second adhesive layer raw material.
In a specific embodiment of the present invention, the temperature in the coextrusion casting is 150 to 200 ℃. The temperature of the extrusion section of the first adhesive layer is 150-180 ℃, the temperature of the extrusion section of the core layer is 150-180 ℃, the temperature of the extrusion section of the second adhesive layer is 160-180 ℃, and the temperature of the die head is 170-210 ℃.
In a specific embodiment of the present invention, the preparation of the first adhesive layer raw material includes: and (3) carrying out twin-screw extrusion granulation on the acrylic block copolymer, the thermoplastic polyurethane elastomer and the antioxidant.
In another aspect, the invention provides the use of any one of the above-described hot melt adhesive films for the combination of a water-boiling-resistant ASA/metal in the combination of an ASA film and a metal.
Compared with the prior art, the invention has the beneficial effects that:
(1) The ASA/metal composite hot melt adhesive film has excellent water resistance and heat resistance, overcomes the defects of the existing ASA/metal composite polyurethane hot melt adhesive in terms of water resistance and heat resistance, and widens the application of the ASA/metal composite hot melt adhesive film in outdoor products;
(2) The hot melt adhesive for ASA/metal compounding has good environmental protection, overcomes the problem of poor environmental protection of the existing polyurethane adhesive for ASA/metal compounding, and further meets the increasingly developed application requirements;
(3) When used in the compounding of ASA film and metal, the hot melt adhesive film has good and stable adhesive strength to ASA film and metal.
Detailed Description
The technical solution of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a hot melt adhesive film for water boiling resistant ASA/metal composite, which comprises a first adhesive layer, a core layer and a second adhesive layer which are arranged in a laminated manner;
the first adhesive layer is mainly prepared from the following components in parts by weight: 10-50 parts of acrylic block copolymer, 50-90 parts of thermoplastic polyurethane elastomer and 0.1-0.5 part of antioxidant;
the core layer is a maleic anhydride grafted ethylene-vinyl acetate copolymer, and the grafting rate of maleic anhydride in the maleic anhydride grafted ethylene-vinyl acetate copolymer is more than 0.1%;
the second adhesive layer comprises maleic anhydride grafted ethylene;
the mass ratio of the first adhesive layer, the core layer and the second adhesive layer is (3-6)/(2-3)/(1-3).
In the hot melt adhesive film, the first adhesive layer is compounded by using the acrylic block copolymer and the thermoplastic polyurethane elastomer in a certain proportion, so that the adhesive strength of an ASA film can be ensured, and the viscosity is ensured not to be reduced after the ASA film is boiled for 3 hours; the core layer can be used as a bridge to stably combine the first adhesive layer and the second adhesive layer, so that a stable three-layer composite structure is realized; the second adhesive layer takes maleic anhydride grafted ethylene as a main body, and under the action of hot pressing, the bonding between the hot melt adhesive film and metal can be realized through the actions of physical adsorption, chemical reaction and the like. The ASA/metal composite hot melt adhesive film obtained by three-layer compounding has excellent water resistance and heat resistance, and simultaneously has environmental protection.
In the first adhesive layer, the following components are used in parts by weight:
the amount of the acrylic block copolymer may be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts or a range consisting of any two thereof;
the thermoplastic polyurethane elastomer may be used in an amount ranging from 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, or any two thereof;
the antioxidant may be used in an amount ranging from 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, or any two thereof.
According to the invention, the acrylic block copolymer and the thermoplastic polyurethane elastomer are mixed in proportion, so that the boiling resistance of the thermoplastic polyurethane elastomer can be improved, and the problem of reduced stripping force after boiling is solved.
In the different embodiments, the mass ratio of the first adhesive layer, the core layer, and the second adhesive layer may be 3:1, 1:2:1, 3:1, and 4:2:1, 4:2.5:1, 4:3:1, 5:2:1, 5:2.5:1, 5:3:1, 6:2:1, 6:2.5:1, 6:3:1, 3:2:2, 3:2.5:2, 3:3:2, 4:2:2, 4:2.5:3, 4:3:3, 5:2:3, 5:2, 5:2.5:3, or any of the two components may be used.
In a specific embodiment of the invention, the acrylic block copolymer is a living anionic polymer elastomer. Further, the acrylic block copolymer includes an acrylic ester copolymer of ase:Sub>A-B-ase:Sub>A and/or ase:Sub>A-B.
The acrylic block copolymer is a new series of acrylic ester block copolymers produced by colali unique anionic living polymerization technology, and consists of a methyl methacrylate hard block (PMMA-block) and an acrylic ester soft block (PnBA-block or P (nBA/2 EHA) -block). Due to the structure, the acrylic block copolymer has excellent transparency, weather resistance and good compatibility with polar materials.
In ase:Sub>A specific embodiment of the invention, the acrylic block copolymer is an A-B-A type triblock copolymer wherein block A is PMMA and block B is PBA or P (BA/2 EHA).
In a specific embodiment of the invention, the melt flow index of the acrylic block copolymer is 1-15 g/10min at 190 ℃ under a load of 2.16 kg. The Shore A hardness of the acrylic block copolymer is 10-35.
As in the various embodiments, the melt flow index of the acrylic block copolymer at 190 ℃ under a load of 2.16kg may be 1g/10min, 2g/10min, 5g/10min, 8g/10min, 10g/10min, 12g/10min, 15g/10min, or a range of any two of these; the shore a hardness may be 10, 12, 15, 20, 25, 30, 32, 35 or any two of these ranges.
In a specific embodiment of the present invention, the thermoplastic polyurethane elastomer comprises a polyester polyurethane and/or a polyether polyurethane.
In a specific embodiment of the present invention, the thermoplastic polyurethane elastomer has a melt flow index of 1 to 30g/10min at 190℃under a load of 2.16 kg.
As in the various embodiments, the melt flow index of the thermoplastic polyurethane elastomer at 190℃under a load of 2.16kg may be in the range of 1g/10min, 5g/10min, 10g/10min, 15g/10min, 20g/10min, 25g/10min, 30g/10min, or any two of these.
In a specific embodiment of the present invention, the maleic anhydride graft ethylene-vinyl acetate copolymer has a maleic anhydride grafting ratio of 0.12% to 0.2%, such as 0.15%.
As in the various embodiments, the maleic anhydride grafted ethylene vinyl acetate copolymer may have a grafting ratio of 0.12%, 0.15%, 0.18%, 0.2% or a range of any two of these.
In the maleic anhydride grafted ethylene-vinyl acetate copolymer adopted as the raw material of the core layer, the ethylene-vinyl acetate copolymer is a random copolymer of ethylene and vinyl acetate, and because a huge vinyl ester group is introduced into a polyethylene molecule, the crystallinity is reduced, the flexibility is increased, the surface tension is small when the polyethylene is melted, the polyethylene has thermal adhesion to a plurality of materials, the surface of a base material can be well infiltrated, and the adhesion is increased. As the middle core layer, the adhesive can play the roles of compatilizer and bridging, increase the compatibility of materials with different polarities and improve the peeling strength of the whole structure of the hot melt adhesive film.
In a specific embodiment of the present invention, the melt flow index of the maleic anhydride grafted ethylene-vinyl acetate copolymer is 1 to 24g/10min at 190℃under a load of 2.16 kg.
As in the various embodiments, the melt flow index of the maleic anhydride grafted ethylene vinyl acetate copolymer at 190℃under a load of 2.16kg may be in the range of 1g/10min, 5g/10min, 10g/10min, 15g/10min, 20g/10min, 24g/10min, or any two of these.
In a specific embodiment of the present invention, the maleic anhydride grafted polyethylene in the second adhesive layer has a melt flow index of 1 to 15g/10min at 190℃under a load of 2.16 kg.
As in the various embodiments, the maleic anhydride grafted polyethylene in the second adhesive layer may have a melt flow index at 190 ℃ under a load of 2.16kg in the range of 1g/10min, 5g/10min, 10g/10min, 15g/10min, or any two of these.
In a specific embodiment of the present invention, the maleic anhydride grafted polyethylene in the second adhesive layer satisfies: the stripping force after heat sealing with the aluminum sheet is more than 70N/25mm; wherein, the heat lamination condition includes: the mixture was hot-pressed at 130℃and 0.6MPa for 5 seconds in the order of aluminum sheet, 10 μm thick maleic anhydride-grafted polyethylene film, and PE 7042.
The maleic anhydride grafted polyethylene meeting the above conditions can ensure that the hot melt adhesive film has good adhesive strength to metal.
In a specific embodiment of the present invention, the second adhesive layer is made of at least one of VB550A, VB, 770 and VB 570A.
In a specific embodiment of the present invention, the antioxidant comprises at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], thioethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite and pentaerythritol tetrakis (3-laurylthiopropionate).
The invention also provides a preparation method of any one of the hot melt adhesive films for the boiling-resistant ASA/metal composite, which comprises the following steps:
and carrying out multilayer coextrusion casting on the first adhesive layer raw material, the core layer raw material and the second adhesive layer raw material.
In a specific embodiment of the invention, the temperature in the coextrusion casting is 150 to 200 ℃. Further, the temperature of the extrusion section of the first adhesive layer is 150-180 ℃, the temperature of the extrusion section of the core layer is 150-180 ℃, the temperature of the extrusion section of the second adhesive layer is 160-180 ℃, and the temperature of the die head is 170-210 ℃.
As in the various embodiments, the extrusion stage temperature of the first adhesive layer may be 150 ℃, 160 ℃, 170 ℃, 180 ℃, or a range of any two of these; the extrusion section temperature of the core layer may be 150 ℃, 160 ℃, 170 ℃, 180 ℃ or a range consisting of any two of them; the extrusion stage temperature of the second adhesive layer may be 160 ℃, 170 ℃, 180 ℃ or a range consisting of any two thereof; the die temperature may be 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃ or a range of any two of these.
In a specific embodiment of the present invention, the preparation of the first adhesive layer raw material includes: and (3) carrying out twin-screw extrusion granulation on the acrylic block copolymer, the thermoplastic polyurethane elastomer and the antioxidant.
Wherein, the length-diameter ratio of the twin-screw extruder can be 40:1, and 11 temperature zones can be arranged, and the temperature of each temperature zone is set as follows: 10 ℃, 20 ℃, 150 ℃, 170 DEG C170 ℃, the die temperature is 170 ℃, and the screw rotating speed is 250-350 r/min, such as 300r/min.
In another aspect, the invention provides the use of any one of the above-described hot melt adhesive films for the combination of a water-boiling-resistant ASA/metal in the combination of ASA film and metal.
Wherein, first adhesive layer sets up with ASA membrane laminating, and the second adhesive layer sets up with the metal laminating.
Examples 1 to 5
The embodiment provides a preparation method of a hot melt adhesive film for compounding water-boiling-resistant ASA metal, which comprises the following steps:
(1) Uniformly mixing an acrylic strength copolymer, a thermoplastic polyurethane elastomer and an antioxidant according to a certain proportion, extruding and granulating by a double screw, and drying to obtain a raw material of a first adhesive layer; in the double-screw extrusion granulation, the length-diameter ratio of the double-screw extruder is 40:1, and the temperatures of the 11 temperature zones are respectively set as follows: 10 ℃, 20 ℃, 150 ℃, 170 DEG C170 ℃, the die temperature was 170℃and the screw speed was 300r/min.
(2) And (3) raw materials of the first adhesive layer, the maleic anhydride grafted ethylene-vinyl acetate copolymer and raw materials of the second adhesive layer (corresponding to the first adhesive layer, the middle core layer and the second adhesive layer respectively) in a certain proportion are subjected to multilayer coextrusion casting, cooling and rolling to obtain the ASA/metal composite hot melt adhesive film.
Wherein in the step (2), the melt flow index of the maleic anhydride grafted ethylene-vinyl acetate copolymer at 190 ℃/2.16kg is 11.2g/10min, and the grafting rate of the maleic anhydride is 0.15%; the raw material of the second adhesive layer is hot melt adhesive granule VB550A (Guangzhou deer mountain New Material Co., ltd.); the mass ratio of the raw materials of the first adhesive layer, the maleic anhydride grafted ethylene-vinyl acetate copolymer and the raw materials of the second adhesive layer was 5:3:2, and the total thickness of the hot melt adhesive film was 80. Mu.m.
In examples 1 to 5, the composition and information of the raw materials for the first adhesive layer are shown in tables 1 and 2, respectively.
Table 1 raw material composition (parts by weight) of the first adhesive layer of examples 1 to 5
| Numbering device | Acrylic block copolymers | Thermoplastic polyurethane elastomer | Antioxidant agent |
| Example 1 | 20 | 80 | 0.2 |
| Example 2 | 30 | 70 | 0.2 |
| Example 3 | 20 | 80 | 0.2 |
| Example 4 | 50 | 50 | 0.2 |
| Example 5 | 10 | 90 | 0.2 |
Table 2 raw material information of the first adhesive layers of examples 1 to 5
Comparative example 1
Comparative example 1 reference example 1 was prepared with the difference that: step (1) is different.
Step (1) of comparative example 1 includes: uniformly mixing a thermoplastic polyurethane elastomer and an antioxidant according to the mass ratio of 100:0.2, extruding, granulating and drying by a double screw to obtain a raw material of a first adhesive layer; in the double-screw extrusion granulation, the length-diameter ratio of the double-screw extruder is 40:1, and the temperatures of the 11 temperature zones are respectively set as follows: 10 ℃, 20 ℃, 150 ℃, 170 DEG C170 ℃, the die temperature was 170℃and the screw speed was 300r/min.
Comparative example 2
Comparative example 2 the preparation of reference example 1 is distinguished in that: step (1) is different.
Step (1) of comparative example 2 includes: uniformly mixing an acrylic strength copolymer, a thermoplastic polyurethane elastomer and an antioxidant according to the mass ratio of 60:40:0.2, extruding and granulating by a double screw, and drying to obtain a raw material of a first adhesive layer; in the double-screw extrusion granulation, the length-diameter ratio of the double-screw extruder is 40:1, and the temperatures of the 11 temperature zones are respectively set as follows: 10 ℃, 20 ℃, 150 ℃, 170 DEG C170 ℃, the die temperature was 170℃and the screw speed was 300r/min.
Comparative example 3
Comparative example 3 the preparation of reference example 1 differs in that: step (1) is different.
Step (1) of comparative example 3 includes: uniformly mixing an acrylic strength copolymer, a thermoplastic polyurethane elastomer and an antioxidant according to the mass ratio of 70:30:0.2, extruding and granulating by a double screw, and drying to obtain a raw material of a first adhesive layer; in the double-screw extrusion granulation, the length-diameter ratio of the double-screw extruder is 40:1, and the temperatures of the 11 temperature zones are respectively set as follows: 10 ℃, 20 ℃, 150 ℃, 170 DEG C170 ℃, the die temperature was 170℃and the screw speed was 300r/min.
Comparative example 4
Comparative example 4 reference example 1 was prepared with the difference that: the maleic anhydride grafted ethylene-vinyl acetate copolymer in step (2) is different.
In comparative example 4, the melt flow index at 190℃C.2.16 kg of the maleic anhydride-grafted ethylene-vinyl acetate copolymer was 8.2g/10min, and the grafting ratio of maleic anhydride was 0.08%.
Comparative example 5
Comparative example 5 reference example 1 was prepared with the difference that: in the step (2), the mass ratio of the raw materials of the first adhesive layer, the maleic anhydride-grafted ethylene-vinyl acetate copolymer, and the raw materials of the second adhesive layer is different.
In comparative example 5, the mass ratio of the raw materials of the first adhesive layer, the maleic anhydride-grafted ethylene-vinyl acetate copolymer, and the raw materials of the second adhesive layer was 2:4:4.
Experimental example
The hot melt adhesive films prepared in examples 1 to 5 and comparative examples 1 to 5 were tested for their properties, and the hot melt adhesive films prepared in examples 1 to 5 and comparative examples 1 to 5 were subjected to hot pressing on a press vulcanizer at 150℃and 0.5MPa for 40 seconds in the order ASA film/hot melt adhesive film/aluminum sheet (the first adhesive layer in the hot melt adhesive film was laminated with a conventional commercially available ASA film and the second adhesive layer was laminated with a metallic aluminum sheet), and then cooled to obtain samples, and tested.
Peel strength: testing by referring to a 180-degree peel strength testing method in GB/T2792; the samples were tested for peel strength after being left at room temperature for 30min, and for type of interfacial failure after peeling after 3h cooling of the samples by boiling in water, respectively, and the test results are shown in table 3.
TABLE 3 test results of samples corresponding to different Hot melt adhesive films
Remarks: in the tables AF represents interfacial failure and CF represents cohesive failure.
The ASA/metal composite hot melt adhesive film obtained by three-layer compounding has excellent water resistance and heat resistance, and can keep the viscosity from decreasing after being boiled for 3 hours.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The hot melt adhesive film for the water boiling resistant ASA/metal composite is characterized by comprising a first adhesive layer, a core layer and a second adhesive layer which are arranged in a laminated manner;
the first adhesive layer is mainly prepared from the following components in parts by weight:
10-50 parts of acrylic block copolymer, 50-90 parts of thermoplastic polyurethane elastomer and 0.1-0.5 part of antioxidant;
the core layer is a maleic anhydride grafted ethylene-vinyl acetate copolymer, and the grafting rate of maleic anhydride in the maleic anhydride grafted ethylene-vinyl acetate copolymer is more than 0.1%;
the second adhesive layer comprises maleic anhydride grafted ethylene;
the mass ratio of the first adhesive layer, the core layer and the second adhesive layer is (3-6)/(2-3)/(1-3).
2. The hot melt adhesive film for water boiling resistant ASA/metal composite of claim 1 wherein said acrylic block copolymer is a living anionic polymer elastomer;
preferably, the acrylic block copolymer comprises an acrylic copolymer of form ase:Sub>A-B-ase:Sub>A and/or ase:Sub>A-B.
3. The water resistant ASA/metal composite hot melt adhesive film according to claim 1, characterized in that the acrylic block copolymer is an A-B-A shaped triblock copolymer, wherein block A is PMMA and block B is PBA or P (BA/2EHA);
preferably, the melt flow index of the acrylic block copolymer is 1-15 g/10min under the conditions of the temperature of 190 ℃ and the load of 2.16 kg.
4. The hot melt adhesive film for water boiling resistant ASA/metal clad according to claim 1, wherein in the thermoplastic polyurethane elastomer, polyurethane comprises polyester polyurethane and/or polyether polyurethane;
preferably, the melt flow index of the thermoplastic polyurethane elastomer is 1-30 g/10min under the conditions of the temperature of 190 ℃ and the load of 2.16 kg.
5. The hot melt adhesive film for water boiling resistant ASA/metal composite according to claim 1, wherein in the maleic anhydride grafted ethylene-vinyl acetate copolymer, the grafting ratio of maleic anhydride is 0.12% to 0.2%;
preferably, the melt flow index of the maleic anhydride grafted ethylene-vinyl acetate copolymer is 1-24 g/10min under the conditions of the temperature of 190 ℃ and the load of 2.16 kg.
6. The hot melt adhesive film for water boiling resistant ASA/metal clad according to claim 1, wherein the maleic anhydride grafted polyethylene in the second adhesive layer has a melt flow index of 1 to 15g/10min at 190 ℃ under a load of 2.16 kg;
preferably, the maleic anhydride grafted polyethylene in the second adhesive layer satisfies: the stripping force after heat sealing with the aluminum sheet is more than 70N/25mm; wherein, the heat lamination condition includes: the mixture was hot-pressed at 130℃and 0.6MPa for 5 seconds in the order of aluminum sheet, 10 μm thick maleic anhydride-grafted polyethylene film, and PE 7042.
7. The hot melt adhesive film for water boiling resistant ASA/metal clad according to claim 1, wherein the raw material of the second adhesive layer is at least one of VB550A, VB770 and VB 570A.
8. The method for preparing the hot melt adhesive film for water boiling resistant ASA/metal composite according to any one of claims 1 to 7, which is characterized by comprising the following steps:
carrying out multilayer coextrusion casting on the first adhesive layer raw material, the core layer raw material and the second adhesive layer raw material;
preferably, in the coextrusion casting, the temperature is 150-200 ℃;
preferably, the first adhesive layer has an extrusion stage temperature of 150 to 180 ℃, the core layer has an extrusion stage temperature of 150 to 180 ℃, the second adhesive layer has an extrusion stage temperature of 160 to 180 ℃, and the die head has a temperature of 170 to 210 ℃.
9. The method of preparing according to claim 8, wherein the preparing of the first adhesive layer raw material comprises: and (3) carrying out twin-screw extrusion granulation on the acrylic block copolymer, the thermoplastic polyurethane elastomer and the antioxidant.
10. Use of the hot melt adhesive film for water-boiling resistant ASA/metal compounding according to any one of claims 1 to 7 in compounding ASA film with metal.
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| CN202311817033.0A CN117801711A (en) | 2023-12-27 | 2023-12-27 | Hot melt adhesive film for water boiling resistant ASA/metal composite, and preparation method and application thereof |
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