CN114672257B - Anti-grid-scratching poached hot-melt adhesive film, preparation method thereof and film laminated plate - Google Patents

Anti-grid-scratching poached hot-melt adhesive film, preparation method thereof and film laminated plate Download PDF

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Publication number
CN114672257B
CN114672257B CN202210579553.1A CN202210579553A CN114672257B CN 114672257 B CN114672257 B CN 114672257B CN 202210579553 A CN202210579553 A CN 202210579553A CN 114672257 B CN114672257 B CN 114672257B
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melt adhesive
hot melt
parts
adhesive film
resin
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CN114672257A (en
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何敏
李忠人
谢洪德
朱庆玉
郑才
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Suzhou Kailun Polymer New Material Technology Co ltd
Jiangsu Canlon Building Materials Co Ltd
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Jiangsu Canlon Building 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • C09J11/06—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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0869—Acids or derivatives thereof
    • 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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
    • B32B2419/00—Buildings or parts thereof
    • B32B2419/06—Roofs, roof membranes
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/346—Applications of adhesives in processes or use of adhesives in the form of films or foils for building applications e.g. wrap foil
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C09J2301/1242—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape the opposite adhesive layers being different
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Abstract

The invention relates to a cross-cut-resistant boiled hot-melt adhesive film, a preparation method thereof and a film-coated plate, wherein the hot-melt adhesive film is used for bonding a metal layer and a nonmetal layer and comprises a first adhesive layer bonded with the metal layer, a second adhesive layer bonded with the nonmetal layer and a transition layer arranged between the first adhesive layer and the second adhesive layer, the raw materials of the first adhesive layer comprise EAA resin and a cross-linking agent, and the mass ratio of the cross-linking agent to the EAA resin is 0.1-1.5: 100, the cross-linking agent is metal organic carboxylate, organic carboxylic acid in the metal organic carboxylate comprises C6-C12 aliphatic organic acid, and metal in the metal organic carboxylate is one or a combination of more of zinc, cobalt, calcium, magnesium and tin. The invention can solve the problems that the laminated board prepared by the existing hot melt adhesive film has poor boiling performance after being subjected to lattice division, and the high polymer waterproof coiled material bulges or even falls off from the metal surface in the long-term outdoor exposure use process, thereby greatly prolonging the outdoor service life of the laminated board.

Description

Anti-grid-scratching post-poaching hot melt adhesive film, preparation method thereof and film-coated plate
Technical Field
The invention particularly relates to a grid-scratching-resistant poached hot-melt adhesive film, a preparation method thereof and a film-coated plate.
Background
The high-molecular waterproof coiled material is soft in texture and good in weldability, and can be widely applied to light steel single-layer roof waterproof systems, roof repair engineering and the like, and particularly the TPO waterproof coiled material can meet the severe requirements of long-term exposed use of metal roofs on water resistance, corrosion resistance, high weather resistance, high temperature resistance, high sunlight reflectivity and the like. By utilizing the characteristic of good weldability of TPO materials and adopting the full-welding process, the service life of a metal roof can be greatly prolonged, and the TPO material can be matched with a photovoltaic module for 25 years of service life when applied to a distributed photovoltaic roof. One way to do this is to bond the polymer waterproof roll to the metal plate to make a polymer waterproof roll/metal film coated plate.
However, when the polymer waterproof roll/metal film coated sheet is exposed for use in roof waterproofing works, the polymer waterproof roll/metal film coated sheet needs to be subjected to various use and environmental effects such as bending, high temperature, rain water and the like, and the phenomenon that the polymer waterproof roll bulges or even is separated from the metal sheet cannot occur, so that the polymer waterproof roll is required to have good adhesion property to the metal sheet, and the film coated sheet has good high temperature resistance and water resistance. The performance requirements of the product of the group label T/CBMCA 017. 2020 coating steel plate for buildings comprise the requirements of adhesive force (grid cutting method) and boiling water resistance. The size of the boiling water resistance test plate of the group standard is 20mm multiplied by 100mm, the adhesion test (divided into 3mm multiplied by 3mm small grids) is carried out at normal temperature, and the polymer waterproof coiled material/metal film-coated plate product meeting the two standards is found in the practical application process and can not keep the film-coated plate from bulging and separating in the outdoor long-term use process. Engineering application practices also find that if the macromolecular waterproof coiled material/metal film coating plate test piece is subjected to boiling water resistance performance test after being subjected to grid cutting at normal temperature, the film coating plate with 3mm multiplied by 3mm and no falling of small grids can be exposed for long-term use outdoors without the phenomena of bulging and falling off after being subjected to adhesive force test after being boiled for 48 hours. Obviously, due to the size effect, the boiling resistance test after the grid cutting puts higher requirements on the adhesive force of the high-molecular waterproof coiled material to the metal plate and the boiling water resistance of the film coating plate.
In the prior art, some techniques for bonding a non-metal sheet to a metal plate by using a hot melt adhesive or a liquid adhesive are available.
For example, chinese patent CN 112831308A discloses a single-component solvent-free hot melt adhesive, and a preparation method and a use method thereof, which is a polyurethane type hot melt adhesive, although the solvent-free hot melt adhesive is mentioned herein to have good boiling resistance, high temperature cooking resistance, etc., the solvent-free hot melt adhesive has a single high polymer structure, has a poor adhesion force to TPO polymer waterproof sheets with extremely low surface energy, is difficult to achieve high-strength effective adhesion to surfaces of non-polar substrates with low surface energy such as TPO and polar substrates such as metal plates, and is not suitable for adhesion between polymer waterproof rolls and metal plates. Meanwhile, the boiling resistance and high-temperature steaming resistance test method in the patent is not clear, and whether the hot melt adhesive meets the boiling performance after division or not can not be expected.
Chinese patent CN 107538864B discloses a method for preparing an aluminized film and a film-coated color steel plate with wire-drawing effect, wherein the composite adhesive layer mentioned herein is a high-temperature resistant polyester resin containing a blocked polyurethane curing agent, and is a solvent-based resin, although the resin selected by the composite adhesive layer has high-temperature resistance, boiling resistance and other properties, the resin is a solvent-based resin, and a large amount of solvent is generated during the compounding process of the aluminized film and the metal plate, which causes great pollution and high energy consumption. And whether the boiling performance after the grid cutting is met after the composite adhesive layer is applied to a high-molecular waterproof coiled material and a metal plate cannot be expected.
In addition, if the hot melt adhesive or the liquid adhesive is applied to the bonding between the polymer coiled material and the metal plate, the problems of complex construction process, high cost, poor construction quality and the like caused by the difficulty in maintaining stable composite strength exist.
The hot melt adhesive film is adopted to compound the high molecular waterproof coiled material and the metal plate together by hot pressing to prepare the high molecular waterproof coiled material/the metal film coated plate, so that the construction cost of a light steel single-layer roof waterproof system and roof repair engineering can be saved, the construction quality and the construction efficiency can be improved, and the hot melt adhesive film can be widely applied to the repair of metal roofs of new industrial plants and old plant metal roofs. However, at present, most of the hot melt adhesive films applied to the polymer waterproof roll/metal film coated sheet on the market can effectively bond the polymer waterproof roll such as TPO and the like and the metal sheet at normal temperature, and even can pass a boiling water resistance performance test of a relevant standard, but the adhesive force to the metal sheet at high temperature is still limited, so that the hot melt adhesive films are difficult to pass a severe test of boiling water adhesive force after lattice division, and the long-term exposed use of the polymer waterproof roll/metal film coated sheet outdoors, especially on a roof, is difficult to maintain.
Disclosure of Invention
The invention aims to solve the technical problem that the existing hot-melt adhesive film is difficult to pass a boiling adhesion test after grid cutting, and provides an improved hot-melt adhesive film and a preparation method thereof.
The second purpose of the invention is to provide a film coating plate which can meet the long-term outdoor exposed use.
In order to achieve the purpose, the invention adopts the technical scheme that:
the utility model provides a hot melt adhesive membrane for bonding between metal level and the non-metal layer, hot melt adhesive membrane including be used for with the first glue film that the metal level bonded, be used for with the second glue film that the non-metal layer bonded and setting are in transition layer between first glue film and the second glue film, the raw materials of first glue film include EAA resin and cross-linking agent, the mass ratio of cross-linking agent and EAA resin is 0.1~ 1.5: 100, wherein the cross-linking agent is metal organic carboxylate, the organic carboxylic acid in the metal organic carboxylate comprises C6-C12 aliphatic organic acid, and the metal in the metal organic carboxylate is one or more of zinc, cobalt, calcium, magnesium and tin.
According to some preferred embodiments of the present invention, preferably, the organic carboxylic acid is a C6-C10 aliphatic organic acid, more preferably a C7-C9 aliphatic organic acid.
Further preferably, the metal organic carboxylate is selected from zinc octoate, calcium octoate, cobalt octoate, magnesium octoate. More preferably, the metal organic carboxylate is zinc octoate.
According to some preferred embodiments of the present invention, the raw material of the first glue layer further includes an auxiliary cross-linking agent, and the mass ratio of the auxiliary cross-linking agent to the EAA resin is 0.1 to 1.5: 100, wherein the auxiliary crosslinking agent is one or the combination of o-anisic acid and p-anisic acid.
Preferably, the auxiliary crosslinking agent is o-anisic acid.
Preferably, the mass ratio of the cross-linking agent to the auxiliary cross-linking agent to the EAA resin is 0.1-1: 0.1-1: 100.
according to some embodiments of the present invention, the metal layer is a galvanized steel sheet, and the non-metal layer is a polymer waterproof roll, such as a TPO polymer waterproof roll or a PVC polymer waterproof roll, with different surface polarities.
In the present invention, the TPO is a polyolefin thermoplastic elastomer.
Further, the first adhesive layer further comprises one or a combination of more of maleic anhydride grafted polyethylene modifier and POE, and the mass of the EAA resin accounts for more than 20% of the total mass of the raw materials of the first adhesive layer.
In some preferred and specific embodiments, the mass ratio of the EAA resin, the maleic anhydride grafted polyethylene modifier and the POE is 1: 0.3-4: 0.5 to 4.
Preferably, the mass ratio of the EAA resin to the maleic anhydride grafted polyethylene modifier to the POE is 1: 1-2: 1 to 2.
In some further preferred and specific embodiments, the raw material formula of the first adhesive layer comprises the following components in parts by weight: 10-30 parts of EAA resin, 10-40 parts of maleic anhydride grafted polyethylene modifier, 20-40 parts of POE, 0.01-0.45 part of cross-linking agent, 0.01-0.45 part of auxiliary cross-linking agent and 0.1-2 parts of first auxiliary agent, wherein the first auxiliary agent comprises one or a combination of several of antioxidant and ultraviolet absorbent.
In the present invention, the EAA resin is an ethylene and acrylic acid copolymer resin, and in some embodiments, the EAA resin is, for example, 3990 from DuPont.
The SEBS is styrene-ethylene-butylene-styrene block copolymer, such as SEBS of Keteng of America, specifically Kraton G1657 and Kraton G1726.
In the present invention, the POE refers to a random copolymer elastomer in which ethylene and high-carbon α -olefin (1-butene, 1-hexene, 1-octene, etc.) are polymerized in situ using a metallocene catalyst. Preferably, the POE is an ethylene-octene copolymer. Specifically, the POE may be gag series products of dow, such as gag 8440 and gag 6002.
The polyethylene in the maleic anhydride grafted polyethylene modifier is selected from any one or more of LDPE (low density polyethylene), LLDPE (linear low density polyethylene), HDPE (high density polyethylene), MDPE (medium density polyethylene), VLDPE (very low density polyethylene) and mLLDPE (metallocene linear low density polyethylene), and is specifically FB19E5 of Fine-Blend which is good and easy in Shanghai.
Further, the raw material of the second adhesive layer comprises a matrix resin, and the matrix resin is at least one of HDPE, LDPE, LLDPE, SEBS and POE.
Furthermore, the raw material of the second adhesive layer further comprises a tackifying resin and a second auxiliary agent, wherein the tackifying resin comprises one or more of hydrogenated petroleum resin, rosin resin, hydrogenated rosin resin, terpene phenolic resin and terpene resin, and the second auxiliary agent comprises one or more of an antioxidant and an ultraviolet absorbent.
Preferably, the tackifying resin is hydrogenated petroleum resin, such as 5600 of Ekson, USA.
Further, the raw material formula of the second adhesive layer comprises, by weight, 15-55 parts of matrix resin, 0-30 parts of tackifying resin and 0.1-2 parts of a second auxiliary agent. The selection of the matrix resin is selected according to different non-metal layers to be bonded.
Preferably, the raw material formula of the second adhesive layer comprises 15-55 parts of matrix resin, 5-20 parts of tackifying resin and 0.1-2 parts of second auxiliary agent.
The matrix resin in the second adhesive layer can be properly selected according to the non-metal layer to be bonded, for example, when the non-metal layer is a TPO-like polymer waterproof roll, the matrix resin is at least one selected from LDPE, LLDPE and POE; when the non-metal layer is a PVC polymer waterproof coiled material, the matrix resin is at least one selected from LLDPE, SEBS and POE.
In some preferred and specific embodiments, the raw material formula of the second adhesive layer comprises, by weight, 15-25 parts of LLDPE, 20-30 parts of POE, 25-35 parts of SEBS, 10-20 parts of hydrogenated petroleum resin and 0.1-2 parts of a second auxiliary agent. The second auxiliary agent comprises 0.1-1 part of antioxidant and 0.1-1 part of ultraviolet absorbent.
Further, the raw materials of the transition layer comprise a combination of at least one of HDPE, LDPE, LLDPE, SEBS and POE and a maleic anhydride grafted polyethylene modifier, and the mass ratio of the at least one of HDPE, LDPE, LLDPE, SEBS and POE to the maleic anhydride grafted polyethylene modifier is 0.2-8: 1.
in some preferred and specific embodiments, the raw material formula of the transition layer comprises, by weight, 10-40 parts of maleic anhydride grafted polyethylene modifier, 35-85 parts of at least one of HDPE, LDPE, LLDPE, SEBS and POE, and 0.1-2 parts of third auxiliary agent; the third auxiliary agent comprises one or a combination of several of an antioxidant and an ultraviolet absorbent.
Preferably, the raw material formula of the transition layer comprises 10-40 parts of maleic anhydride grafted polyethylene modifier, 15-25 parts of SEBS, 10-30 parts of LDPE or LLDPE, 0.1-1.0 part of antioxidant and 0.1-1.0 part of ultraviolet absorber. In the transition layer, the polarities of the maleic anhydride grafted polyethylene modifier, SEBS, LDPE or LLDPE are sequentially reduced, the transition layer with moderate polarity is obtained by matching the resin proportions of the components, and the first adhesive layer and the second adhesive layer can be firmly bonded together to form a complete three-layer composite hot melt adhesive film. Meanwhile, the transition layer also contributes to reducing the cost of the whole hot melt adhesive film.
According to some embodiments of the present invention, the maleic anhydride grafted polyethylene modifier in the first glue layer and the maleic anhydride grafted polyethylene modifier in the transition layer may be maleic anhydride grafted polyethylene modifiers of the same type. Preferably, the maleic anhydride grafted polyethylene modifier in the first glue layer and the maleic anhydride grafted polyethylene modifier in the transition layer are selected from the same maleic anhydride grafted polyethylene modifier.
Further, the antioxidant is one or any combination of antioxidant 1010, antioxidant 1076, antioxidant 168 and antioxidant 264.
Further, the ultraviolet absorbent is one or any combination of UV327, UV531, UV770 and UV 944.
According to some embodiments of the present invention, the thickness of the first adhesive layer, the thickness of the second adhesive layer, and the thickness of the transition layer are respectively selected from 0.01 to 0.05 mm.
The second technical scheme adopted by the invention is as follows: the hot melt adhesive film is prepared by respectively extruding and granulating the raw materials of the first adhesive layer, the second adhesive layer and the transition layer by using a double-screw extruder and then co-extruding the raw materials by using a film blowing machine.
The third technical scheme adopted by the invention is as follows: the preparation method of the hot melt adhesive film comprises the steps of respectively extruding and granulating the raw materials of the first adhesive layer, the second adhesive layer and the transition layer, and then carrying out co-extrusion to prepare the hot melt adhesive film.
In some preferred and specific embodiments, in the preparation method of the hot melt adhesive film, the raw material of the first adhesive layer is added into a double-screw extruder for granulation, wherein the extrusion temperature is 140-200 ℃, and the preferred temperature is 170-190 ℃; adding the raw materials of the second adhesive layer into a double-screw extruder for granulation, wherein the extrusion temperature is 130-200 ℃, and the preferred temperature is 150-190 ℃; adding the raw materials of the transition layer into a double-screw extruder for granulation, wherein the extrusion temperature is 130-180 ℃, and the preferred temperature is 150-170 ℃; the co-extrusion adopts a three-layer film blowing machine for co-extrusion, and the temperature of a co-extrusion die head of the film blowing machine is 160-200 ℃, and the preferred temperature is 170-185 ℃.
The preparation of the hot melt adhesive film of the invention does not use solvent at all, thereby avoiding the problem of environmental pollution caused by the solvent.
The fourth technical scheme adopted by the invention is as follows: a film-coated plate comprises a metal plate and a high-molecular waterproof coiled material which is bonded with the metal plate through a hot-melt adhesive film in a hot-pressing mode, wherein the hot-melt adhesive film is the hot-melt adhesive film or the hot-melt adhesive film prepared by the preparation method of the hot-melt adhesive film.
Preferably, the metal sheet is a galvanized steel sheet, and the polymer waterproof roll is a TPO polymer waterproof roll.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the inventor of the invention unexpectedly finds that the EAA resin and the zinc octoate cross-linking agent are introduced into the first adhesive layer bonded with the metal layer, and the carboxylic acid functional group on the EAA resin and the zinc octoate are subjected to ion cross-linking reversible reaction, so that in a boiling water resistance performance test, part of ion groups subjected to cross-linking decomposition at high temperature can form chelation with oxidized metal ions on the surface of the metal layer, the adhesive force and the bonding strength of the hot-melt adhesive film on the surface of the metal layer are greatly improved, and the boiling water boiling performance of the film-coated plate after grid division is also obviously improved, so that the high-temperature aging resistance and the outdoor service life of the film-coated plate are improved. Based on this finding, the present invention has been made and proposed through further studies.
The hot melt adhesive film can solve the problems that a film-covered plate prepared by the existing hot melt adhesive film is poor in boiling water boiling performance after being subjected to lattice division, and a high-molecular waterproof coiled material bulges or even falls off from the metal surface in the long-term outdoor exposure use process, so that the outdoor service life of the film-covered plate is greatly prolonged.
Detailed Description
As described in the background art, although the conventional hot melt adhesive film can effectively bond a polymer waterproofing membrane such as TPO and the like and a metal plate at normal temperature, even the conventional hot melt adhesive film can pass the boiling water resistance of the relevant standard, the conventional hot melt adhesive film still cannot pass the harsh test of water boiling after lattice breaking, the conventional hot melt adhesive film cannot keep the long-term exposed use of the polymer waterproofing membrane/metal film coated plate outdoors, particularly on a roof, and therefore, the peeling strength of the hot melt adhesive film to the metal plate is high, and the hot melt adhesive film cannot pass the test of the harsh water boiling resistance after lattice breaking.
The invention mainly aims to introduce an ionic crosslinking reversible reaction into a first adhesive layer of a hot melt adhesive film, which is bonded with a metal layer, introduce EAA resin and a specific crosslinking agent into the first adhesive layer, wherein carboxylic acid functional groups on the EAA resin can perform the ionic crosslinking reversible reaction with the crosslinking agent, and partial ionic groups which are subjected to crosslinking release at high temperature can form chelation with oxidized metal ions on the surface of the metal layer in a boiling water performance test, so that the adhesive force and the bonding strength of the hot melt adhesive film to the surface of the metal layer are greatly improved, and the boiling performance of a boiling water film-coated plate after grid cutting is also obviously improved.
The invention further discloses that a specific auxiliary crosslinking agent is also introduced into the first adhesive layer, so that the water boiling performance after grid cutting can be further improved.
In addition, the inventor of the invention finds that when the metal layer is made of galvanized steel sheets, the cross-linking agent is made of zinc octoate, and the auxiliary cross-linking agent is made of o-anisic acid, the hot melt adhesive film can obtain more excellent boiling resistance after grid cutting and excellent normal-temperature and high-temperature peel strength for the metal layer.
The main principle is seen in the following reaction formula:
Figure 788326DEST_PATH_IMAGE001
(formula I);
Figure 377571DEST_PATH_IMAGE002
(formula II);
in the formula I and the formula II,
Figure 954046DEST_PATH_IMAGE003
for an EAA resin, R refers to a structure other than a carboxylate group in the molecular structure of the EAA resin.
Under normal temperature, carboxylic acid functional group of EAA resin in the first adhesive layer bonded to the metal layer in the hot melt adhesive film can form ionic compound with zinc ion in oxide on the surface of the galvanized steel sheet or zinc ion in zinc octoate, zinc ion cross-linking dissociation reaction can occur under high temperature, after dissociation, octoate, o-methoxy benzoate or p-methoxy benzoate can form new ionic compound with zinc ion, the bonding force of the first adhesive layer bonded to the metal in the hot melt adhesive film to the surface of the galvanized steel sheet under high temperature is greatly improved, in boiling water resistance test, ionic group partially cross-linked under high temperature can form chelation with oxidized zinc ion on the surface of the galvanized steel sheet, the adhesive force and bonding strength of the adhesive film to the surface of the galvanized steel sheet are greatly improved, and the boiling water resistance of the waterproof/metal coated sheet of the high molecular coiled material after grid cutting is also obviously improved, therefore, the high-temperature aging resistance and the outdoor service life of the high-molecular waterproof coiled material/metal film-coated plate are also improved.
The technical solutions of the present invention are described in detail below with reference to specific examples so that those skilled in the art can better understand and implement the technical solutions of the present invention, but the present invention is not limited to the scope of the examples.
The sources of the raw materials used in the following examples are as follows:
EAA resins are derived from DuPont 3990;
the hydrogenated petroleum resin is derived from 5600 from exxon, usa;
the maleic anhydride grafted polyethylene modifier is derived from FB19E5 of Fine-Blend which is good and easy in Shanghai;
POE is derived from Dow Engage 8440;
SEBS is derived from Kraton G1657, Kraton, U.S.A.;
LLDPE is sourced from gillin petrochemical 7042.
Example 1
The hot melt adhesive membrane that this embodiment provided for bonding between metal level and the non-metal layer, non-metal layer adopt TPO class polymer waterproofing membrane, and the metal level adopts galvanized steel sheet, and this hot melt adhesive membrane is including being used for the first glue film that bonds with the metal level, being used for with the second glue film that the non-metal layer bonds and setting up the transition layer between first glue film and second glue film.
In this example, the raw material formulation of the first adhesive layer is as follows: 20 parts of EAA resin, 25 parts of maleic anhydride grafted polyethylene modifier, 30 parts of POE, 0.1 part of zinc octoate, 0.1 part of o-anisic acid, 0.5 part of antioxidant 1010 and 0.5 part of ultraviolet absorber UV 327.
The raw material formula of the transition layer is as follows: 25 parts of maleic anhydride grafted polyethylene modifier, 20 parts of SEBS, 20 parts of LDPE, 0.5 part of antioxidant 1010 and 0.5 part of ultraviolet absorbent UV 327.
The raw material formula of the second adhesive layer is as follows: 20 parts of LLDPE, 25 parts of POE, 30 parts of SEBS, 15 parts of hydrogenated petroleum resin, 0.5 part of antioxidant 1010 and 0.5 part of ultraviolet absorber UV 327.
In this example, the hot melt adhesive film was prepared by the following method:
(1) all the raw materials of the first adhesive layer are added into a double-screw extruder to be extruded and granulated, and the extrusion temperature is 170-190 ℃;
(2) all the raw materials of the second adhesive layer are added into a double-screw extruder to be extruded and granulated, and the extrusion temperature is 150-190 ℃;
(3) adding all the raw materials of the transition layer into a double-screw extruder for extrusion granulation, wherein the extrusion temperature is 150-170 ℃;
(4) and co-extruding the three layers of granules through a three-layer film blowing machine to prepare a three-layer hot melt adhesive film, wherein the temperature of a co-extrusion die head is 170-185 ℃, the thickness of the first adhesive layer is 0.02mm, the thickness of the second adhesive layer is 0.02mm, and the thickness of the transition layer is 0.02 mm.
Example 2
The preparation method and the bonding object of the hot melt adhesive film provided in this embodiment are the same as those of embodiment 1, and the difference from embodiment 1 is that the formula of the first adhesive layer is different, in this embodiment, the formula of the raw materials of the first adhesive layer is as follows: 30 parts of EAA resin, 10 parts of maleic anhydride grafted polyethylene modifier, 20 parts of POE, 0.1 part of zinc octoate, 0.05 part of o-anisic acid, 0.5 part of antioxidant 1010 and 0.5 part of ultraviolet absorber UV 327.
Example 3
The preparation method and the bonding object of the hot melt adhesive film provided in this embodiment are the same as those of embodiment 1, and the difference from embodiment 1 is that the formula of the first adhesive layer is different, in this embodiment, the formula of the raw materials of the first adhesive layer is as follows: 20 parts of EAA resin, 25 parts of maleic anhydride grafted polyethylene modifier, 30 parts of POE, 0.3 part of zinc octoate, 0.3 part of o-anisic acid, 0.5 part of antioxidant 1010 and 0.5 part of ultraviolet absorber UV 327.
Example 4
The hot melt adhesive film provided in this embodiment, the preparation method and the adhered object thereof are the same as those of embodiment 1, and the differences from embodiment 1 are as follows: the first glue layer is not added with maleic anhydride grafted polyethylene modifier and POE.
Example 5
The preparation method of the hot melt adhesive film provided in this embodiment is the same as that of embodiment 1, and is different from embodiment 1 in that: the metal layer in the bonding object adopts a common steel plate.
Example 6
The hot melt adhesive film provided in this embodiment, the preparation method and the adhered object thereof are the same as those of embodiment 1, and the differences from embodiment 1 are as follows: and no auxiliary crosslinking agent is added into the first adhesive layer.
Comparative example 1
The preparation method and the bonding object of the hot melt adhesive film provided by the comparative example are the same as those of the hot melt adhesive film in the example 1, and the differences from the example 1 are that: and no crosslinking agent or auxiliary crosslinking agent is added into the first adhesive layer.
Comparative example 2
The preparation method and the bonding object of the hot melt adhesive film provided by the comparative example are the same as those of the hot melt adhesive film in the example 1, and the differences from the example 1 are that: and no crosslinking agent is added into the first glue layer.
Adopt the hot melt adhesive membrane of embodiment 1~6 and comparative example 1~2 to bond galvanized steel sheet and TPO waterproofing membrane and make the tectorial membrane board, the preparation condition is: hot pressing at 160 ℃, pressure of 0.6MPa, hot pressing time of 20s, thickness of TPO waterproof coiled material of 0.8mm, thickness of galvanized steel sheet of 0.6mm, then subjecting the coated sheet to the following performance tests, the results are shown in Table 1:
boiling water test after grid cutting: the prepared film coating plate is subjected to lattice cutting according to an adhesion force test method in the glob mark T/CBMCA 017-2020 constructional film coating steel plate, and is divided into 3mm multiplied by 3mm, then the film coating plate subjected to lattice cutting is boiled in boiling water for 48h according to the standard, and the phenomena of bulging and falling off are observed.
Meanwhile, the peeling strength of the laminated plate at normal temperature and the peeling strength of the laminated plate at high temperature (70 ℃) are tested according to the group standard T/CBMCA 017. one' 2020 laminating steel plate for buildings.
Table 1 shows the results of performance tests of coated sheets prepared using the hot melt adhesive films of examples 1 to 6 and comparative examples 1 to 2
Figure 5047DEST_PATH_IMAGE004
The experimental results in table 1 show that, on the basis of reasonably matching the main resin of the first adhesive layer, the hot melt adhesive film added with the crosslinking agent zinc octoate and the auxiliary crosslinking agent o-anisic acid in a proper proportion has excellent anti-scratching post-boiling performance, higher normal temperature peel strength and high temperature peel strength.
The above embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention by this means. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

Claims (17)

1. The utility model provides a hot melt adhesive membrane for bonding between metal level and the non-metal layer, hot melt adhesive membrane including be used for with the first glue film that the metal level bonded, be used for with the second glue film that the non-metal layer bonded and setting are in transition layer between first glue film and the second glue film, its characterized in that: the raw materials of the first adhesive layer comprise EAA resin, a cross-linking agent and an auxiliary cross-linking agent, wherein the mass ratio of the cross-linking agent to the EAA resin is (0.1-1.5): 100, wherein the cross-linking agent is zinc octoate, and the auxiliary cross-linking agent is o-methoxybenzoic acid.
2. The hot melt adhesive film according to claim 1, wherein: the mass ratio of the auxiliary crosslinking agent to the EAA resin is 0.1-1.5: 100.
3. the hot melt adhesive film according to claim 2, wherein: the mass ratio of the cross-linking agent to the auxiliary cross-linking agent to the EAA resin is (0.1-1): 0.1-1: 100.
4. the hot melt adhesive film according to claim 1, wherein: the first adhesive layer further comprises one or a combination of more of maleic anhydride grafted polyethylene modifier and POE, and the mass of the EAA resin accounts for more than 20% of the total mass of the raw materials of the first adhesive layer.
5. The hot melt adhesive film according to claim 4, wherein: the mass ratio of the EAA resin to the maleic anhydride grafted polyethylene modifier to the POE is 1: 0.3-4: 0.5 to 4.
6. The hot melt adhesive film according to claim 5, wherein: the mass ratio of the EAA resin to the maleic anhydride grafted polyethylene modifier to the POE is 1: 1-2: 1 to 2.
7. The hot melt adhesive film according to claim 1, wherein: the raw material formula of the first adhesive layer comprises the following components in parts by weight: 10-30 parts of EAA resin, 10-40 parts of maleic anhydride grafted polyethylene modifier, 20-40 parts of POE, 0.01-0.45 part of cross-linking agent, 0.01-0.45 part of auxiliary cross-linking agent and 0.1-2 parts of first auxiliary agent, wherein the first auxiliary agent comprises one or a combination of several of antioxidant and ultraviolet absorbent.
8. The hot melt adhesive film according to claim 1, wherein: the raw material of the second adhesive layer comprises matrix resin, wherein the matrix resin is at least one of HDPE, LDPE, LLDPE, SEBS and POE; and/or the presence of a gas in the gas,
the transition layer is made of a combination of at least one of HDPE, LDPE, LLDPE, SEBS and POE and a maleic anhydride grafted polyethylene modifier, wherein the mass ratio of the at least one of HDPE, LDPE, LLDPE, SEBS and POE to the maleic anhydride grafted polyethylene modifier is (0.2-8): 1.
9. the hot melt adhesive film according to claim 8, wherein: the raw materials of the second adhesive layer also comprise tackifying resin and a second auxiliary agent, wherein the tackifying resin comprises one or more of hydrogenated petroleum resin, rosin resin, hydrogenated rosin resin, terpene phenolic resin and terpene resin, and the second auxiliary agent comprises one or more of an antioxidant and an ultraviolet absorbent; and/or the raw material formula of the second adhesive layer comprises 15-55 parts by weight of matrix resin, 0-30 parts by weight of tackifying resin and 0.1-2 parts by weight of second auxiliary agent.
10. The hot melt adhesive film according to claim 9, wherein: the raw material formula of the second adhesive layer comprises, by weight, 15-25 parts of LLDPE, 20-30 parts of POE, 25-35 parts of SEBS, 10-20 parts of hydrogenated petroleum resin and 0.1-2 parts of a second auxiliary agent.
11. The hot melt adhesive film according to claim 8, wherein: the transition layer comprises, by weight, 10-40 parts of maleic anhydride grafted polyethylene modifier, 35-85 parts of at least one of HDPE, LDPE, LLDPE, SEBS and POE and 0.1-2 parts of third aid; the third auxiliary agent comprises one or a combination of several of an antioxidant and an ultraviolet absorbent.
12. The hot melt adhesive film according to claim 11, wherein: the transition layer comprises, by weight, 10-40 parts of maleic anhydride grafted polyethylene modifier, 15-25 parts of SEBS, 10-30 parts of LDPE or LLDPE and 0.1-2 parts of third aid.
13. The hot melt adhesive film according to claim 1, wherein: the thickness of the first adhesive layer, the thickness of the second adhesive layer and the thickness of the transition layer are respectively selected from 0.01-0.05 mm; and/or the metal layer is a galvanized steel sheet, and the non-metal layer is a TPO polymer waterproof coiled material or a PVC polymer waterproof coiled material.
14. The hot melt adhesive film according to any one of claims 1 to 13, wherein: the hot melt adhesive film is prepared by adopting a double-screw extruder to extrude and granulate the raw materials of the first adhesive layer, the second adhesive layer and the transition layer respectively and then co-extruding the raw materials through a film blowing machine.
15. The method for preparing a hot melt adhesive film according to any one of claims 1 to 13, wherein the method comprises the following steps: the preparation method comprises the steps of respectively extruding and granulating the raw materials of the first adhesive layer, the second adhesive layer and the transition layer, and then obtaining the hot melt adhesive film through co-extrusion.
16. The utility model provides a tectorial membrane board, including the metal sheet and with the metal sheet passes through the polymer waterproofing membrane that hot melt adhesive membrane hot-pressing bonds together, its characterized in that: the hot melt adhesive film is prepared by the hot melt adhesive film of any one of claims 1 to 14 or the preparation method of the hot melt adhesive film of claim 15.
17. A membrane panel according to claim 16, wherein: the metal sheet is galvanized steel sheet, polymer waterproofing membrane is TPO class polymer waterproofing membrane.
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