CN112877019A - AEP bonding adhesive film, preparation method thereof and AEP plate - Google Patents

AEP bonding adhesive film, preparation method thereof and AEP plate Download PDF

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Publication number
CN112877019A
CN112877019A CN202110163780.1A CN202110163780A CN112877019A CN 112877019 A CN112877019 A CN 112877019A CN 202110163780 A CN202110163780 A CN 202110163780A CN 112877019 A CN112877019 A CN 112877019A
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aep
ethylene
adhesive film
maleic anhydride
acrylate
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CN112877019B (en
Inventor
杜壮
唐舫成
汪加胜
朱庆柯
邓志业
龚力
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Guangzhou Lushan New Materials Co Ltd
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Guangzhou Lushan New Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/046—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0221—Vinyl resin
    • B32B2266/0235—Vinyl halide, e.g. PVC, PVDC, PVF, PVDF
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane

Abstract

The invention relates to the technical field of hot melt adhesives, in particular to an AEP adhesive film, a preparation method thereof and an AEP plate. The AEP bonding adhesive film is mainly prepared from the following components in percentage by mass: 50-70% of polyester material, 10-38% of ionic polymer, 1-5% of modified inorganic nano material and 10-30% of ethylene-acrylate-maleic anhydride compatilizer. Compared with the existing polyurethane glue, epoxy resin glue, acrylic acid glue and the like, the AEP bonding glue film disclosed by the invention has no VOC problem, can form good bonding on foamed PVC and aluminum materials in an AEP plate, has the peel strength of more than 150N/25mm, is resistant to boiling water boiling and cold and hot cycle impact at-40-80 ℃, and can be used in outdoor environments.

Description

AEP bonding adhesive film, preparation method thereof and AEP plate
Technical Field
The invention relates to the technical field of hot melt adhesives, in particular to an AEP adhesive film, a preparation method thereof and an AEP plate.
Background
AEP (Aluminum metal foam PVC Energy-saving Composite plate) building materials originate from Europe, have the performance advantages of sound and heat insulation, flame retardance, self-extinguishing, high strength, high impact resistance and the like, are widely applied to the field of Composite building materials at present, and are particularly mainly applied to the fields of building ceilings, office partitions, cabinet body plates and the like. The AEP is characterized in that a skinned and foamed PVC core material is used as a heat-insulating, sound-insulating and flame-retardant base material, aluminum plates are used as a reinforcing layer and a decorative layer on two sides of the PVC core material, and the PVC core material and the aluminum plates are connected into a whole by adopting an adhesive.
The adhesive for AEP compounding at present mainly comprises two categories of liquid adhesive and hot melt adhesive. The liquid glue for AEP compounding mainly comprises epoxy glue, polyurethane glue, acrylic acid glue and the like, but glue compounding mainly has the defects of VOC pollution, incapability of continuous production and the like. The AEP composite hot melt adhesive mainly comprises two categories of PUR and polyester hot melt adhesives, PUR glue can be continuously brushed for construction, but the bonding force to metal is low, the peel strength is below 150N/25mm, the composite structure is not resistant to boiling, the bonding reliability is insufficient, and the AEP composite hot melt adhesive is not suitable for outdoor occasions and indoor decoration occasions with strict requirements on service life; the polyester hot melt adhesive such as the hot melt adhesive modified by taking polyurethane TPU, copolyester PES and the like as matrix resin also has the defects of low bonding strength to metal and unsusceptibility to boiling, the bonding reliability is poorer than that of moisture-cured PUR, and the prepared AEP building material can not be applied to outdoor occasions.
In conclusion, no hot melt adhesive film is available in the market at present, which has the advantages of no VOC (volatile organic compounds) of the hot melt adhesive and continuous construction, has the advantages of high composite AEP bonding strength, boiling resistance, cold and heat shock resistance and can be used outdoors, and the prior art has technical defects in the aspects of environmental friendliness, continuous production, bonding reliability and outdoor application.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide an AEP bonding adhesive film which can form good bonding effect on PVC and metal aluminum materials in an AEP structure and has good cold and hot shock resistance reliability.
The second purpose of the invention is to provide a preparation method of the AEP bonding adhesive film.
A third object of the present invention is to provide an AEP sheet using an AEP adhesive film.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the AEP bonding adhesive film is mainly prepared from the following components in percentage by mass:
50-70% of polyester material, 10-38% of ionic polymer, 1-5% of modified inorganic nano material and 10-30% of ethylene-acrylate-maleic anhydride compatilizer.
The AEP bonding adhesive film disclosed by the invention has the advantages that through the matching of the components, the AEP bonding adhesive film can have a good bonding effect with PVC and metal aluminum materials, is high in peeling strength and good in cold and heat shock resistance reliability, and can be used in the outdoor field. By adding the ionic polymer, the ionic polymer can be combined with the metal aluminum material in a physical crosslinking point mode, so that the peeling strength and the bonding reliability are improved; meanwhile, the addition of the modified inorganic nano material can improve the crystallization speed of the polyester material, improve the bonding speed and the mechanical property of the adhesive film system and further improve the bonding effect of the adhesive film.
In a specific embodiment of the present invention, the modified inorganic nanomaterial is at least one of a fatty acid-modified inorganic nanomaterial and an aminated modified inorganic nanomaterial.
In a particular embodiment of the invention, the inorganic nanomaterial comprises calcium carbonate and/or silica.
In a specific embodiment of the invention, the modified inorganic nano material is fatty acid modified nano calcium carbonate and/or aminated nano silica.
In a specific embodiment of the invention, the modified inorganic nano material is higher fatty acid modified nano calcium carbonate and/or aminosilane coupling agent modified nano silicon dioxide.
In a particular embodiment of the invention, the polyester material comprises at least one of copolyester PES, thermoplastic polyurethane TPU and polyester elastomer TPEE.
In a specific embodiment of the invention, the polyester material has a melt flow rate of 0.1g/10min to 20g/10min (190 ℃, 2.16kg) and a melting point of 100 ℃ to 180 ℃.
In a particular embodiment of the invention, the ionic polymer is selected from at least one of ethylene-acrylic acid type ionic polymers.
In a specific embodiment of the present invention, the ionic polymer includes at least one of an ethylene-acrylic acid-sodium salt polymer, an ethylene-methacrylic acid-sodium salt polymer, an ethylene-acrylic acid-zinc salt polymer, and an ethylene-methacrylic acid-zinc salt polymer.
In a specific embodiment of the invention, the melt flow rate of the ionomer is 0.3g/10min to 7g/10min (190 ℃, 2.16kg) and the melting point is 70 ℃ to 110 ℃.
In a specific embodiment of the present invention, the ethylene-acrylate-maleic anhydride compatibilizer comprises an ethylene-acrylate copolymer grafted maleic anhydride and/or an ethylene-acrylate-maleic anhydride terpolymer.
In a specific embodiment of the invention, the melt flow rate of the ethylene-acrylate-maleic anhydride compatilizer is 2g/10 min-40 g/10min (190 ℃, 2.16kg), and the melting point is 70-120 ℃.
In a specific embodiment of the present invention, an antioxidant is further included. Furthermore, the dosage of the antioxidant is 0.1-1% of the sum of the mass of the polyester material, the mass of the ionic polymer, the mass of the modified inorganic nano material and the mass of the ethylene-acrylate-maleic anhydride compatilizer.
In a specific embodiment of the present invention, the antioxidant includes at least one of aromatic amine-based antioxidants, hindered phenol-based antioxidants, phosphorus-containing or sulfur-containing antioxidants.
In a specific embodiment of the invention, the AEP adhesive film is mainly prepared from the following components in percentage by mass:
50-70% of polyester material, 10-38% of ionic polymer, 0.1-25% of ethylene copolymer, 1-5% of modified inorganic nano material and 10-30% of ethylene-acrylate-maleic anhydride compatilizer;
in a specific embodiment of the present invention, the ethylene-based copolymer includes at least one of an ethylene-acrylate copolymer, an ethylene-vinyl acetate copolymer, and an ethylene-vinyl acetate-maleic anhydride copolymer.
In a specific embodiment of the present invention, the ethylene copolymer has a melt flow rate of 0.1g/10min to 40g/10min (190 ℃ C., 2.16kg) and a melting point of 75 ℃ to 120 ℃.
The invention also provides a preparation method of the AEP bonding adhesive film, which comprises the following steps:
the components are mixed and granulated and then cast to form a film.
In a specific embodiment of the present invention, the method for mixing and granulating comprises:
(a) mixing and granulating a mixture of the ionic polymer, the modified inorganic nano material and the ethylene-acrylate-maleic anhydride compatilizer by using a double-screw extruder to obtain a granular semi-finished product;
(b) and mixing and granulating the mixture of the semi-finished particle and the polyester material by a double-screw extruder to obtain a finished particle.
Further, carrying out tape casting film formation on the obtained finished particle product.
In actual operation, if the raw materials contain an antioxidant, the raw materials are mixed with the ionic polymer, the modified inorganic nano material and the ethylene-acrylate-maleic anhydride compatilizer to obtain a mixture in the step (a), and the mixture is subjected to mixing and granulation.
In practice, if the raw material contains an ethylene copolymer, the mixture is obtained in step (a) together with the ionic polymer, the modified inorganic nanomaterial, and the ethylene-acrylic ester-maleic anhydride compatibilizer, and the mixture is kneaded and granulated.
In a specific embodiment of the invention, in the step (a), the temperature of the mixing granulation is 185-195 ℃; in the step (b), the temperature for mixing and granulating is 145-155 ℃.
In a specific embodiment of the invention, in the step (a) and the step (b), the screw rotation speed of the twin-screw extruder is 200-350 rpm, the feeding frequency is 5-7 Hz, and the length-diameter ratio L/D of the twin-screw is 40: 1.
In the specific embodiment of the invention, the temperature of the casting film forming is 130-160 ℃.
In a specific embodiment of the invention, the thickness of the AEP adhesive film is 0.05-0.1 mm.
The invention also provides an AEP plate which comprises any one of the AEP adhesive films.
In a specific embodiment of the invention, the AEP board further comprises a PVC board, a first aluminum board and a second aluminum board, and the first aluminum board and the second aluminum board are respectively attached to two sides of the PVC board through the AEP adhesive film.
In a specific embodiment of the invention, the PVC plate is a skinned foamed PVC plate.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with the existing polyurethane glue, epoxy resin glue, acrylic acid glue and the like, the AEP adhesive film disclosed by the invention has no VOC (volatile organic compound) problem, can be used for continuously constructing and manufacturing AEP building materials, saves the links of manual glue spraying, glue brushing and the like, and solves the problems of physical damage to constructors and environmental protection in the later AEP application process;
(2) compared with the conventional PUR hot melt adhesive and polyester hot melt adhesive, the AEP adhesive film provided by the invention has the following advantages: the problems that the bonding strength of the PUR hot melt adhesive and the polyester hot melt adhesive to the metal aluminum plate is insufficient, the PUR hot melt adhesive is not boiling resistant, and the PUR hot melt adhesive cannot be applied outdoors can be solved;
(3) the AEP bonding adhesive film disclosed by the invention can form good bonding on foamed PVC and aluminum materials in an AEP plate, has the peel strength of more than 150N/25mm, is resistant to boiling water boiling and cold and hot cycle impact at-40-80 ℃, and can be used in outdoor environments.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The AEP bonding adhesive film is mainly prepared from the following components in percentage by mass:
50-70% of polyester material, 10-38% of ionic polymer, 1-5% of modified inorganic nano material and 10-30% of ethylene-acrylate-maleic anhydride compatilizer.
The AEP bonding adhesive film disclosed by the invention has the advantages that through the matching of the components, the AEP bonding adhesive film can have a good bonding effect with PVC and metal aluminum materials, is high in peeling strength and good in cold and heat shock resistance reliability, and can be used in the outdoor field. By adding the ionic polymer, the ionic polymer can be combined with the metal aluminum material in a physical crosslinking point mode, so that the peeling strength and the bonding reliability are improved; meanwhile, the addition of the modified inorganic nano material can improve the crystallization speed of the polyester material, improve the bonding speed and the mechanical property of the adhesive film system and further improve the bonding effect of the adhesive film.
In a specific embodiment of the present invention, the modified inorganic nanomaterial is at least one of a fatty acid-modified inorganic nanomaterial and an aminated modified inorganic nanomaterial.
In a particular embodiment of the invention, the inorganic nanomaterial comprises calcium carbonate and/or silica.
In a specific embodiment of the invention, the modified inorganic nano material is higher fatty acid modified nano calcium carbonate and/or aminosilane coupling agent modified nano silicon dioxide.
The invention can improve the crystallization speed and cohesive energy of the polyester material, improve the mechanical property of the system and simultaneously improve the bonding speed of the ionic polymer to the metal aluminum material by adding the modified inorganic nano material. The research of the invention finds that the nano material can be better dispersed in the polyester material and the ionic polymer matrix resin without agglomeration through specific modification such as fatty acidification or amination modification performance, the fully dispersed nano material can only play a role in enhancing and improving the bonding speed, otherwise, more nano materials can only play a role in inorganic filler.
As in various embodiments, the modified inorganic nanomaterial can be used in an amount of 1%, 2%, 3%, 4%, 5%, and so forth. When the use level of the modified inorganic nano material is too low, the effects of enhancing and improving the bonding speed cannot be achieved; when the dosage of the modified inorganic nano material is too high, the melt strength of the system is reduced, the film is not easy to form, and the bonding effect of the system is reduced on the contrary.
In a particular embodiment of the invention, the polyester material comprises at least one of copolyester PES, thermoplastic polyurethane TPU and polyester elastomer TPEE.
In a specific embodiment of the invention, the polyester material has a melt flow rate of 0.1g/10min to 20g/10min (190 ℃, 2.16kg) and a melting point of 100 ℃ to 180 ℃.
The polyester material of the invention mainly plays a role of matrix resin and has good bonding effect on PVC. As in various embodiments, the polyester material may be used in an amount of 50%, 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, and so forth. When the dosage of the polyester material is too low, the peel strength of the polyester material to PVC is insufficient; when the amount of the polyester material is too high, the boiling resistance effect and the cold-hot cycle impact effect of the system are affected.
In a particular embodiment of the invention, the ionic polymer is selected from at least one of ethylene-acrylic acid type ionic polymers.
In a specific embodiment of the present invention, the ionic polymer includes at least one of an ethylene-acrylic acid-sodium salt polymer, an ethylene-methacrylic acid-sodium salt polymer, an ethylene-acrylic acid-zinc salt polymer, and an ethylene-methacrylic acid-zinc salt polymer.
In a specific embodiment of the invention, the melt flow rate of the ionomer is 0.3g/10min to 7g/10min (190 ℃, 2.16kg) and the melting point is 70 ℃ to 110 ℃.
The ionic polymer provided by the invention mainly plays a role in increasing the bonding force on metal materials and providing physical cross-linking points, improves the bonding strength of a bonding adhesive film on aluminum, and improves the heat-resistant reliability of an AEP composite structure. As in various embodiments, the ionic polymer can be used in an amount of 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, and so forth. When the dosage of the ionic polymer is too low, the adhesive effect on the metal aluminum material is poor, and the heat resistance of the system is poor; when the amount of the ionomer is too high, poor adhesion to PVC may result.
In a specific embodiment of the present invention, the ethylene-acrylate-maleic anhydride compatibilizer comprises an ethylene-acrylate copolymer grafted maleic anhydride and/or an ethylene-acrylate-maleic anhydride terpolymer.
In a specific embodiment of the invention, the melt flow rate of the ethylene-acrylate-maleic anhydride compatilizer is 2g/10 min-40 g/10min (190 ℃, 2.16kg), and the melting point is 70-120 ℃.
The ethylene-acrylic ester-maleic anhydride compatilizer mainly plays a role in improving the compatibility of a polyester material, an ionic polymer and a modified inorganic nano material, so that the components are not separated after being mixed, and good phase state distribution is formed. As in various embodiments, the ethylene-acrylate-maleic anhydride compatibilizer may be used in an amount of 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, and so forth. When the dosage of the ethylene-acrylate-maleic anhydride compatilizer is too low, the compatibility among the components cannot be effectively improved; when the amount of the ethylene-acrylate-maleic anhydride compatibilizer is too high, the peel strength of the system to PVC and metals is reduced.
In a specific embodiment of the present invention, an antioxidant is further included. Furthermore, the dosage of the antioxidant is 0.1-1% of the sum of the mass of the polyester material, the mass of the ionic polymer, the mass of the modified inorganic nano material and the mass of the ethylene-acrylate-maleic anhydride compatilizer.
In a specific embodiment of the present invention, the antioxidant includes at least one of aromatic amine-based antioxidants, hindered phenol-based antioxidants, phosphorus-containing or sulfur-containing antioxidants.
The primary function of the antioxidant is to prevent the problem of aging of the several components during processing or use. As in various embodiments, the antioxidant may be added in an amount of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, and so forth. When the using amount of the antioxidant is too low, the anti-aging effect is not obvious; when the amount of the antioxidant is too high, not only the cost is increased but also the adhesive property is deteriorated.
In a specific embodiment of the invention, the AEP adhesive film is mainly prepared from the following components in percentage by mass:
50-70% of polyester material, 10-38% of ionic polymer, 0.1-25% of ethylene copolymer, 1-5% of modified inorganic nano material and 10-30% of ethylene-acrylate-maleic anhydride compatilizer;
in a specific embodiment of the present invention, the ethylene-based copolymer includes at least one of an ethylene-acrylate copolymer, an ethylene-vinyl acetate copolymer, and an ethylene-vinyl acetate-maleic anhydride copolymer.
In a specific embodiment of the invention, the ethylene copolymer has a melt flow rate of 0.1g/10min to 40g/10min and a melting point of 75 ℃ to 120 ℃.
In actual operation, a certain amount of ethylene copolymer can be added according to actual requirements, so that the cost of the AEP adhesive film can be properly reduced, the cost of the adhesive film can be reduced along with the increase of the addition amount, but the adhesive performance is influenced to a certain extent, the addition amount is not more than 25%, otherwise, the adhesive performance and the like are insufficient.
The invention also provides a preparation method of the AEP bonding adhesive film, which comprises the following steps:
the components are mixed and granulated and then cast to form a film.
In a specific embodiment of the present invention, the method for mixing and granulating comprises:
(a) mixing and granulating a mixture of the ionic polymer, the modified inorganic nano material and the ethylene-acrylate-maleic anhydride compatilizer by using a double-screw extruder to obtain a granular semi-finished product;
(b) and mixing and granulating the mixture of the semi-finished particle and the polyester material by a double-screw extruder to obtain a finished particle.
Through the two-time mixing mode, on one hand, the ionic polymer, the modified inorganic nano material and the ethylene-acrylate-maleic anhydride compatilizer can be thoroughly and uniformly dispersed through two-time mixing, on the other hand, the polyester material is easily decomposed, and is added during the second mixing, the decomposition of the polyester material can be reduced through low-temperature mixing, and the performance is further improved.
Further, carrying out tape casting film formation on the obtained finished particle product.
In actual operation, if the raw materials contain an antioxidant, the raw materials are mixed with the ionic polymer, the modified inorganic nano material and the ethylene-acrylate-maleic anhydride compatilizer to obtain a mixture in the step (a), and the mixture is subjected to mixing and granulation.
In practice, if the raw material contains an ethylene copolymer, the mixture is obtained in step (a) together with the ionic polymer, the modified inorganic nanomaterial, and the ethylene-acrylic ester-maleic anhydride compatibilizer, and the mixture is kneaded and granulated.
In a specific embodiment of the invention, in the step (a), the temperature of the mixing granulation is 185-195 ℃; in the step (b), the temperature for mixing and granulating is 145-155 ℃.
In a specific embodiment of the invention, in the step (a) and the step (b), the screw rotation speed of the twin-screw extruder is 200-350 rpm, the feeding frequency is 5-7 Hz, and the length-diameter ratio L/D of the twin-screw is 40: 1.
In the specific embodiment of the invention, the temperature of the casting film forming is 130-160 ℃.
In a specific embodiment of the invention, the thickness of the AEP adhesive film is 0.05-0.1 mm.
The invention also provides an AEP plate which comprises any one of the AEP adhesive films.
In a specific embodiment of the invention, the AEP board further comprises a PVC board, a first aluminum board and a second aluminum board, and the first aluminum board and the second aluminum board are respectively attached to two sides of the PVC board through the AEP adhesive film.
In a specific embodiment of the invention, the PVC plate is a skinned foamed PVC plate.
Example 1
The embodiment provides an AEP bonding adhesive film and a preparation method thereof, wherein the AEP bonding adhesive film comprises the following raw materials:
68 parts of polyester material (Wenzhou Huate hot melt adhesive Co., Ltd., PES, mark HT-5120-C), 20 parts of ionic polymer (DuPont, Salin resin, mark 8940, USA), 2 parts of modified inorganic nano material (Kaiens nano material Co., Ltd., fatty acid modified nano calcium carbonate, mark KS-80T), 10 parts of ethylene-acrylate-maleic anhydride compatilizer (France Akema, Lotader, mark 4700) and 2150.15 parts of antioxidant B.
The preparation method of the AEP bonding adhesive film comprises the following steps:
(1) weighing the ionic polymer, the modified inorganic nano material, the ethylene-acrylate-maleic anhydride compatilizer and the antioxidant according to the proportion, then carrying out high mixing for 15min through a high mixing machine, and then carrying out mixing through a double-screw extruder at 190 ℃ to obtain a granular semi-finished product; and then premixing the semi-finished product and the polyester material in the proportion, and putting the mixture into a double-screw extruder to be mixed at the temperature of 150 ℃ to obtain a granular finished product.
(2) And (3) carrying out primary tape casting on the particle finished product obtained in the step (1) by using a tape casting machine to obtain an AEP adhesive film with the thickness of 0.08 mm. In actual operation, the thickness of the adhesive film can be adjusted according to actual requirements.
The length-diameter ratio L/D of the twin-screw extruder in the step (1) is 40: 1, the screw rotating speed is 300rpm, and the feeding frequency is 6 Hz;
the casting temperature of the casting machine in the step (2) was 145 ℃.
Example 2
The embodiment provides an AEP bonding adhesive film and a preparation method thereof, wherein the AEP bonding adhesive film comprises the following raw materials:
60 parts of polyester material (Luborun, USA, TPU, No. D112H), 27 parts of ionic polymer (Dupont, America, Shalin resin, No. 8940), 3 parts of modified inorganic nano material (Kanes nano material Co., Ltd., fatty acid modified nano calcium carbonate, No. KS-80T), 10 parts of ethylene-acrylate-maleic anhydride compatilizer (France Achima, Lotader, No. 4700) and B2150.15 parts of antioxidant.
The preparation method of the AEP adhesive film of this example is the same as that of example 1.
Example 3
The embodiment provides an AEP bonding adhesive film and a preparation method thereof, wherein the AEP bonding adhesive film comprises the following raw materials:
55 parts of polyester material (Korea SK company, TPEE, brand G140D), 25 parts of ionic polymer (DuPont company, Shalin resin, brand 9910), 3 parts of modified inorganic nano material (Beijing Anbiqi biotechnology limited, aminated nano silicon dioxide, brand DNG-F035), 17 parts of ethylene-acrylate-maleic anhydride compatilizer (Guangzhou deer mountain new material, EBA-G-MAH, brand OE-1), 10100.15 parts of antioxidant and 2450.15 parts of antioxidant.
The preparation method of the AEP adhesive film of this example is the same as that of example 1.
Example 4
The embodiment provides an AEP bonding adhesive film and a preparation method thereof, wherein the AEP bonding adhesive film comprises the following raw materials:
50 parts of polyester material (Korea SK Co., Ltd., TPEE, brand G140D), 20 parts of ionic polymer (U.S. DuPont Co., Salin resin, brand 9910), 3 parts of modified inorganic nano material (Beijing Anbiqi Biotech Co., Ltd., aminated nano silicon dioxide, brand DNG-F035), 10 parts of ethylene-acrylate-maleic anhydride compatibilizer (Guangzhou deer mountain new material, EBA-G-MAH, brand OE-1), 10 parts of ethylene-vinyl acetate copolymer (Korea LG Co., EVA, brand 19150), EV 10100.15 parts of antioxidant and 2450.15 parts of antioxidant.
The preparation method of the AEP adhesive film of this example is the same as that of example 1.
Example 5
This example provides a method of making an AEP sheet comprising the steps of:
according to the aluminum material (thickness is 0.5mm), AEP adhesive film and skinning foaming PVC (thickness is 25mm, density is 0.7 g/cm)3) And sequentially stacking the AEP adhesive film and the aluminum material (with the thickness of 0.5mm), and laminating and compounding at 160 ℃ and 0.3MPa for 2min to obtain the AEP plate.
The AEP adhesive film is any one of embodiments 1 to 4.
Comparative example 1
Comparative example 1 a method for preparing an adhesive film is as in example 1, except that: the raw materials of the adhesive film have different compositions. The adhesive film of comparative example 1 had the same raw material composition as that of example 1 except that the modified inorganic nano-material was replaced with unmodified nano-calcium carbonate of the same weight.
Comparative example 2
The adhesive film of comparative example 2 is prepared by directly casting a film with a thickness of 0.08mm at 145 ℃ after Thermoplastic Polyurethane (TPU) and copolyester PES are blended according to a mass ratio of 1: 1.
Comparative example 3
Comparative example 3 is a PUR material, which was prepared by a method comprising:
(a) stirring 50 parts by weight of polyester polyol and 20 parts by weight of isocyanate for reaction to prepare an isocyanate group-terminated prepolymer;
(b) adding 20 parts by weight of thermoplastic acrylic resin, 10 parts by weight of tackifying resin, 0.1 part by weight of antioxidant, 0.2 part by weight of initiator and 2 parts by weight of filler into the prepolymer, and uniformly mixing to obtain the epoxy resin-modified epoxy resin prepolymer. Viscosity of 26000 mPas at 130 ℃ and curing time of 2 days.
Experimental example 1
In order to illustrate the properties of the materials of the different examples and comparative examples of the present invention by comparison, the following property tests were carried out, the test results of which are shown in Table 1.
The appearance corresponds to the color and state of the glue film or the PUR material.
Sample preparation: the adhesive films obtained in examples 1 to 4 and comparative examples 1 to 2 were respectively mixed with skinned foamed PVC (thickness 25mm, density 0.7 g/cm)3) Arranging an aluminum material (with the thickness of 0.5mm) according to the sequence of skinning foamed PVC, adhesive films and the aluminum material, laminating and compounding for 2min at 160 ℃ and 0.3MPa to obtain a sample to be tested, wherein the thickness of the adhesive films is 0.08 mm; for the PUR material of comparative example 3, the PUR material was brush-coated on the surface of skinned foamed PVC, and then an aluminum material was placed on the brush-coated PUR surface, laminated and compounded at 160 ℃ and 0.3MPa for 2min, and then left to cure at 25 ℃ and 50% humidity for 2 days to obtain a sample to be tested, wherein the thickness of the PUR layer was 0.08 mm.
The peel strength (test method reference GB/T2790-1995) refers to the bonding strength between the skinned foamed PVC/adhesive film or the PUR/aluminum material of the sample.
Cold and hot cycle impact test: keeping the sample at-40 ℃ for 2h and 80 ℃ for 2h as one cycle, and carrying out 50 cycles in total; the state of the sample after the cycle test was then observed and the peel strength of the sample after the test was tested.
Boiling test: and (3) placing the sample in hot water of 98 +/-2 ℃ for boiling for 6 hours to carry out a boiling test, observing the state of the sample after the test, and testing the peel strength of the sample after the test.
TABLE 1 Performance index
Figure BDA0002936669570000151
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

  1. The AEP adhesive film is characterized by being mainly prepared from the following components in percentage by mass:
    50-70% of polyester material, 10-38% of ionic polymer, 1-5% of modified inorganic nano material and 10-30% of ethylene-acrylate-maleic anhydride compatilizer.
  2. 2. The AEP bonding adhesive film of claim 1, wherein the modified inorganic nanomaterial is at least one of a fatty acid modified inorganic nanomaterial and an aminated modified inorganic nanomaterial;
    preferably, the inorganic nanomaterial comprises calcium carbonate and/or silica;
    preferably, the modified inorganic nano material is higher fatty acid modified nano calcium carbonate and/or aminosilane coupling agent modified nano silicon dioxide.
  3. 3. The AEP adhesive film of claim 1, wherein the polyester material comprises at least one of copolyester PES, thermoplastic polyurethane TPU, and polyester elastomer TPEE.
  4. 4. The AEP bonding adhesive film of claim 1, wherein the ionomer is selected from at least one of ethylene-acrylic acid type ionomers;
    preferably, the ionic polymer includes at least one of an ethylene-acrylic acid-sodium salt polymer, an ethylene-methacrylic acid-sodium salt polymer, an ethylene-acrylic acid-zinc salt polymer, and an ethylene-methacrylic acid-zinc salt polymer.
  5. 5. The AEP adhesive film of claim 1, wherein the ethylene-acrylate-maleic anhydride compatibilizer comprises an ethylene-acrylate copolymer grafted maleic anhydride and/or an ethylene-acrylate-maleic anhydride terpolymer.
  6. 6. The AEP adhesive film of claim 1, further comprising an antioxidant;
    preferably, the amount of the antioxidant is 0.1-1% of the sum of the mass of the polyester material, the mass of the ionic polymer, the mass of the modified inorganic nano material and the mass of the ethylene-acrylate-maleic anhydride compatilizer;
    preferably, the antioxidant comprises at least one of aromatic amine antioxidant, hindered phenol antioxidant, phosphorus-containing or sulfur-containing antioxidant.
  7. 7. The AEP adhesive film according to claim 1, which is prepared from the following components in mass percent:
    50-70% of polyester material, 10-38% of ionic polymer, 0.1-25% of ethylene copolymer, 1-5% of modified inorganic nano material and 10-30% of ethylene-acrylate-maleic anhydride compatilizer;
    the ethylene copolymer includes at least one of an ethylene-acrylate copolymer, an ethylene-vinyl acetate copolymer, and an ethylene-vinyl acetate-maleic anhydride copolymer.
  8. 8. The method of preparing the AEP adhesive film of any one of claims 1 to 7, comprising the steps of:
    mixing and granulating the components, and then casting to form a film;
    preferably, the method for mixing and granulating comprises the following steps:
    (a) mixing and granulating a mixture of the ionic polymer, the modified inorganic nano material and the ethylene-acrylate-maleic anhydride compatilizer by using a double-screw extruder to obtain a granular semi-finished product;
    (b) and mixing and granulating the mixture of the semi-finished particle and the polyester material by a double-screw extruder to obtain a finished particle.
  9. 9. The preparation method of the AEP bonding adhesive film according to claim 8, wherein in the step (a), the temperature of the mixing granulation is 185-195 ℃; in the step (b), the temperature of mixing and granulating is 145-155 ℃;
    preferably, in the step (a) and the step (b), the screw rotating speed of the double-screw extruder is 200-350 rpm, and the feeding frequency is 5-7 Hz;
    preferably, the casting film forming temperature is 130-160 ℃.
  10. An AEP sheet comprising the AEP adhesive film of any one of claims 1 to 7.
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Denomination of invention: AEP adhesive film and its preparation method and AEP board

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