CN117487472A - Fireproof adhesive film and preparation method and application thereof - Google Patents

Fireproof adhesive film and preparation method and application thereof Download PDF

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Publication number
CN117487472A
CN117487472A CN202311655645.4A CN202311655645A CN117487472A CN 117487472 A CN117487472 A CN 117487472A CN 202311655645 A CN202311655645 A CN 202311655645A CN 117487472 A CN117487472 A CN 117487472A
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CN
China
Prior art keywords
parts
fireproof
raw materials
polyacrylate
acrylate
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Pending
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CN202311655645.4A
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Chinese (zh)
Inventor
尹朝辉
黄立志
郭俊
龚鑫
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Zhuzhou Feilu High Tech Materials Co ltd
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Zhuzhou Feilu High Tech Materials Co ltd
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Priority to CN202311655645.4A priority Critical patent/CN117487472A/en
Publication of CN117487472A publication Critical patent/CN117487472A/en
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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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C09D5/185—Intumescent paints
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • 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
    • C09J2467/006—Presence of polyester in the substrate

Abstract

The invention discloses a fireproof adhesive film, a preparation method and application thereof, and relates to the technical field of fireproof, wherein the fireproof adhesive film comprises a fireproof surface and a self-adhesive surface; the fireproof surface comprises the following preparation raw materials: a first polyacrylate, a first curative, p-toluene sulfonic acid, ammonium polyphosphate, an organic filler, pentaerythritol, melamine, and ethyl acetate; the self-adhesive surface comprises the following preparation raw materials: a second polyacrylate, a second curative, a polyepoxide, and ethyl acetate; the organic filler comprises the following preparation raw materials: titanium dioxide modified silica sol, styrene, propyl trichlorosilane methacrylate, hexafluorobutyl acrylate, butyl acrylate, acrylic acid and an initiator. The fireproof surface of the fireproof adhesive film has excellent high temperature resistance, good heat insulation effect and excellent waterproof effect.

Description

Fireproof adhesive film and preparation method and application thereof
Technical Field
The invention relates to the technical field of fireproof adhesive films, in particular to a fireproof adhesive film and a preparation method and application thereof.
Background
The fireproof adhesive film is prepared from the following raw materials of fireproof paint and self-adhesive paint; fire-retardant coatings are generally classified into two categories, intumescent and non-intumescent, in terms of the fire-retardant mechanism. The non-expansion fireproof paint achieves the purposes of flame retardance and fire prevention by virtue of high flame retardance or incombustibility. The expansion type fireproof paint is characterized in that a honeycomb charring layer is formed by the heated expansion of a coating film, flame heat is isolated to reduce or slow down the transmission of flame heat to a substrate, meanwhile, the paint decomposes out non-combustible gas at high temperature to isolate and dilute air, and a series of physical and chemical reactions of the coating layer during fireproof absorb a large amount of heat to realize flame retardance and delay of flame expansion and spread. After the expansion type fireproof coating is heated and expanded, the generated porous foam defense layer is tens or even hundreds times thicker than the original coating, and the heat conductivity coefficient of the expanded foam layer is at least one order of magnitude lower than that of the coating before final expansion, so that the coating is very thin, and a very good fireproof effect can be achieved.
The related art improves the flame retardant property of the fireproof coating by adding an inorganic flame retardant, but the inorganic flame retardant and an organic system have poor compatibility and are separated out, so that the fireproof coating has poor flame retardant property.
Disclosure of Invention
The present invention is directed to a fireproof adhesive film, which solves at least one of the problems and disadvantages set forth in the background art.
The invention also provides a preparation method of the fireproof adhesive film.
The invention also provides application of the fireproof adhesive film.
The first aspect of the invention provides a fireproof adhesive film, which comprises a fireproof surface and a self-adhesive surface;
the fireproof surface comprises the following preparation raw materials:
a first polyacrylate, a first curative, p-toluene sulfonic acid, ammonium polyphosphate, an organic filler, pentaerythritol, melamine, and ethyl acetate;
the self-adhesive surface comprises the following preparation raw materials:
a second polyacrylate, a second curative, a polyepoxide, and ethyl acetate;
the organic filler comprises the following preparation raw materials:
titanium dioxide modified silica sol, styrene, propyl trichlorosilane methacrylate, hexafluorobutyl acrylate, butyl acrylate, acrylic acid and a first initiator.
According to one of the technical schemes of the invention, the invention has at least the following excellent effects:
in the invention, first polyacrylate is selected as main resin, and the first polyacrylate forms a cross-linked network structure under the action of a curing agent;
ammonium polyphosphate, pentaerythritol and melamine form intumescent flame retardants; when the combination is heated, a layer of uniform foam carbon layer can be formed on the surface, so that the heat insulation, oxygen insulation and smoke suppression can be realized, molten drops can be prevented, and good flame retardant performance is realized.
When the system is heated or burnt, the ammonium polyphosphate generates a strong dehydrating agent of polymetaphosphate to dehydrate and carbonize pentaerythritol, and the sticky carbonized substance releases NH in melamine 3 、H 2 The gas such as O expands to form a microporous carbon blocking layer, and heat transfer and diffusion of combustible volatile products and oxygen are prevented, so that the aim of flame retardance is fulfilled.
The organic filler adopts titanium dioxide modified silica sol as a main raw material, wherein the titanium dioxide modified silica sol is used as a core layer material, the shell layer material is a poly (styrene-propyl trichlorosilane-hexafluorobutyl acrylate-butyl acrylate-acrylic acid) hydrophobic copolymer, and the hydrophobic copolymer can enable the titanium dioxide modified silica sol to reach a stable state; meanwhile, the hydrophobic polymer is favorable for protecting the titanium dioxide modified silica sol particles, and the titanium dioxide modified silica sol particles can be uniformly dispersed in the fireproof surface; in the high temperature process, the titanium dioxide modified silica sol particles migrate to the surface of the fireproof surface at a slightly high temperature to form an effective protective layer, so that heat transfer is hindered, the combustion speed and the heat release speed are delayed, and the flame retardance is improved. Meanwhile, as the organic filler has excellent hydrophobic effect, the invasion of moisture from the waterproof surface can be further prevented, so that the waterproof effect of the self-adhesive surface is affected; meanwhile, the organic filler, ammonium polyphosphate, pentaerythritol and melamine play a role in synergistic flame retardance, so that the flame retardance of the fireproof surface is further improved, and finally the fireproof adhesive film with excellent flame retardance is prepared.
According to some embodiments of the invention, the fireproof surface comprises the following preparation raw materials in parts by weight:
100 parts of first polyacrylate, 3-5 parts of first curing agent, 0.01-1 part of p-toluenesulfonic acid, 30-50 parts of ammonium polyphosphate, 10-20 parts of organic filler, 10-20 parts of pentaerythritol, 10-20 parts of melamine and 30-50 parts of ethyl acetate.
According to some embodiments of the invention, the first curing agent comprises an isocyanate and an amino resin.
According to some embodiments of the invention, the isocyanate comprises at least one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), and Lysine Diisocyanate (LDI).
According to some embodiments of the invention, the self-adhesive surface comprises the following preparation raw materials in parts by weight:
100 parts of second polyacrylate, 3-5 parts of second curing agent, 0.01-1 part of polyepoxide polymer and 50-70 parts of ethyl acetate.
According to some embodiments of the invention, the second curative comprises an isocyanate and an amino resin.
According to some embodiments of the invention, the isocyanate comprises at least one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), and Lysine Diisocyanate (LDI).
According to some embodiments of the invention, the organic filler comprises the following preparation raw materials in parts by weight:
100 parts of titanium dioxide modified silica sol, 0.01 to 3 parts of styrene, 0.01 to 3 parts of propyl trichlorosilane, 0.01 to 3 parts of hexafluorobutyl acrylate, 0.01 to 3 parts of butyl acrylate, 0.01 to 3 parts of acrylic acid and 0.001 to 0.3 part of a first initiator.
According to some embodiments of the invention, the organic filler comprises the following preparation raw materials in parts by weight:
100 parts of titanium dioxide modified silica sol, 0.01 to 3 parts of styrene, 0.01 to 3 parts of propyl trichlorosilane, 0.01 to 3 parts of hexafluorobutyl acrylate, 0.01 to 3 parts of butyl acrylate, 0.01 to 3 parts of acrylic acid and 0.001 to 0.3 part of a first initiator.
According to some embodiments of the invention, the first initiator comprises at least one of Azobisisobutyronitrile (AIBN) and dibenzoyl peroxide (BPO).
According to some embodiments of the invention, the titanium dioxide modified silica sol comprises the following preparation raw materials:
titanium dioxide and silica sol.
According to some embodiments of the invention, the mass ratio of the titanium dioxide to the silica sol is 1:40-60.
According to some embodiments of the invention, the titanium dioxide has an average particle size of 1nm to 500nm.
According to some embodiments of the invention, the titanium dioxide has an average particle size of 30nm to 50nm.
According to some embodiments of the invention, the silica sol has an average particle size of 40nm to 150nm.
According to some embodiments of the invention, the silica sol has an average particle size of 40nm to 130nm.
According to some embodiments of the invention, the first polyacrylate comprises the following preparation raw materials:
butyl acrylate, methacrylic acid, hydroxypropyl methacrylate, isocyanate acrylate, difunctional acrylate, isooctyl acrylate, ethyl acetate, toluene and a second initiator.
According to some embodiments of the invention, the first polyacrylate comprises the following preparation raw materials in parts by weight:
100 parts of butyl acrylate, 10-15 parts of methacrylic acid, 10-15 parts of hydroxypropyl methacrylate, 0.1-1 part of isocyanate acrylate, 10-15 parts of difunctional acrylate, 150-200 parts of isooctyl acrylate, 100-300 parts of ethyl acetate, 100-150 parts of toluene and 0.1-1 part of a second initiator.
The difunctional methacrylate can adjust the curing rate of the fireproof surface preparation raw material, and realizes rapid curing.
According to some embodiments of the invention, the isocyanate acrylate includes isocyanate ethyl acrylate (CAS number 13641-96-8).
According to some embodiments of the invention, the difunctional acrylates include at least one of triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate.
According to some embodiments of the invention, the second initiator comprises at least one of Azobisisobutyronitrile (AIBN) and dibenzoyl peroxide (BPO).
According to some embodiments of the invention, the second polyacrylate comprises the following preparation raw materials in parts by weight:
butyl acrylate, methacrylic acid, hydroxypropyl acrylate, dipropylene glycol diacrylate, isooctyl acrylate, ethyl acetate, and a third initiator.
According to some embodiments of the invention, the second polyacrylate comprises the following preparation raw materials in parts by weight:
100 parts of butyl acrylate, 5-10 parts of methacrylic acid, 10-15 parts of hydroxypropyl acrylate, 5-10 parts of dipropylene glycol diacrylate, 150-200 parts of isooctyl acrylate, 300-400 parts of ethyl acetate and 0.4-1 part of a third initiator.
According to some embodiments of the invention, the third initiator comprises at least one of Azobisisobutyronitrile (AIBN) and dibenzoyl peroxide (BPO).
The second aspect of the invention provides a preparation method of the fireproof adhesive film, which comprises the following steps:
coating a preparation raw material of a self-adhesive surface on one surface of a substrate to form the self-adhesive surface, and performing heat curing for the first time;
after the first heat curing is completed, the fireproof surface is formed by coating the preparation raw materials of the fireproof surface on the other side of the substrate, and the second heat curing is performed.
And (3) coating one side of the substrate (the side A of the substrate) with a self-adhesive surface, thermally curing, attaching a release film for protection, and rolling. And then coating the fireproof surface on the other surface (the surface B of the substrate) of the substrate with the self-adhesive surface, which is bonded with the release film, and performing heat curing coating and rolling to obtain the product. According to some embodiments of the invention, the substrate comprises one of a fiberglass textile, a high temperature film, or a PET film.
According to some embodiments of the invention, the first thermal cure is at a temperature of 100 ℃ to 140 ℃.
According to some embodiments of the invention, the first thermal cure is for a time of 2min to 5min.
According to some embodiments of the invention, the release film is attached to the surface of the self-adhesive surface after the first heat curing.
According to some embodiments of the invention, the second thermal cure is at a temperature of 100 ℃ to 140 ℃.
According to some embodiments of the invention, the second thermal cure is for a time of 2min to 5min.
According to some embodiments of the invention, the second heat curing is post curing.
According to some embodiments of the invention, the curing temperature is 20 ℃ to 30 ℃.
According to some embodiments of the invention, the curing time is from 6 days to 8 days.
According to some embodiments of the invention, the substrate has a thickness of 0.03mm to 0.1mm.
According to some embodiments of the invention, the fire-protecting surface has a thickness of 0.1mm to 0.3mm.
According to some embodiments of the invention, the thickness of the self-adhesive face is between 0.03mm and 0.05mm.
The third aspect of the invention provides application of the fireproof adhesive film in the field of rail transit.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
In the description of the present invention, the descriptions of the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Titanium dioxide is available from TiO, inc. of New Belgium materials, suzhou 2 -2 (average particle size 30 nm).
Silica sol was purchased from Hui Erte nanotechnology as HSD50 (average particle size 40nm to 60 nm) HSD80 (average particle size 70nm to 90 nm), HSD100 (average particle size 90nm to 110 nm), HSD120 (average particle size 110nm to 130 nm), and HS-830 (average particle size 8nm to 10 nm).
Ammonium polyphosphate (CAS number 68333-79-9) was purchased from Guangzhou Shangxi chemical technology Co., ltd.
The amino resin was purchased from the us Zhan new amino resin CYMEL 308.
The polyepoxide polymer was purchased from Shenzhen Jiadieda New Material technology Co., ltd., ga-240 (original U.S. CVC).
Example 1
The embodiment is a fireproof adhesive film, which comprises a fireproof surface and a self-adhesive surface;
the fireproof surface is prepared from the following raw materials in parts by weight:
100 parts of first polyacrylate, 4.5 parts of first curing agent (2.5 parts of toluene diisocyanate and 2 parts of amino resin), 0.05 part of p-toluenesulfonic acid, 40 parts of ammonium polyphosphate, 12 parts of organic filler, 16 parts of pentaerythritol, 16 parts of melamine and 40 parts of ethyl acetate.
The self-adhesive noodle is prepared from the following raw materials in parts by weight:
100 parts of second polyacrylate, 3 parts of second curing agent (isophorone diisocyanate 1.5 parts and amino resin 1.5 parts), 0.05 part of polyepoxide polymer and 60 parts of ethyl acetate.
The organic filler comprises the following preparation raw materials in parts by weight:
100 parts of titanium dioxide modified silica sol, 2 parts of styrene, 0.05 part of propyl methacrylate trichlorosilane, 3 parts of hexafluorobutyl acrylate, 0.08 part of butyl acrylate, 2 parts of acrylic acid and 0.02 part of a first initiator (azodiisobutyronitrile (AIBN) and 0.03 part of dibenzoyl peroxide (BPO)).
The titanium dioxide modified silica sol comprises the following preparation raw materials in parts by weight:
titanium dioxide 1 part and silica sol (HSD 80) 50 parts.
The titanium dioxide and the silica sol were stirred and mixed well (stirring speed was 100rpm, stirring time was 30 min), to obtain a titanium dioxide modified silica sol.
The first polyacrylate is prepared from the following raw materials in parts by weight:
100 parts of butyl acrylate, 11 parts of methacrylic acid, 12 parts of hydroxypropyl methacrylate, 0.2 part of isocyanate acrylate (isocyanate ethyl acrylate (CAS number: 13641-96-8)), 12 parts of difunctional acrylate (triethylene glycol dimethacrylate), 168 parts of isooctyl acrylate, 200 parts of ethyl acetate, 120 parts of toluene and 0.3 part of a second initiator (azobisisobutyronitrile (AIBN) and 0.6 part of dibenzoyl peroxide (BPO)).
The preparation method of the first polyacrylate in the embodiment comprises the following steps:
s1, mixing 1/2 of butyl acrylate, 1/4 of methacrylic acid, 1/2 of hydroxypropyl methacrylate, isocyanate acrylic ester, 1/4 of difunctional acrylic ester, 2/3 of azobisisobutyronitrile and ethyl acetate, and reacting for 30min at 85 ℃ to prepare a first mixture;
s2, mixing isooctyl acrylate, the rest of methacrylic acid, the rest of butyl acrylate, the rest of hydroxypropyl methacrylate, the rest of bifunctional acrylate and dibenzoyl peroxide, and then dropwise adding the mixture into the first mixture (dropwise adding time is 4h, and the temperature is 85 ℃); preparing a second mixture;
s3, adding toluene and the rest of azodiisobutyronitrile into the second mixture, reacting for 2 hours at 85 ℃, and cooling (the time is 30 min).
The second polyacrylate is prepared from the following raw materials in parts by weight:
100 parts of butyl acrylate, 7.5 parts of methacrylic acid, 12.5 parts of hydroxypropyl acrylate, 5.3 parts of dipropylene glycol diacrylate, 190 parts of isooctyl acrylate, 380 parts of ethyl acetate and 0.85 part of a third initiator (azodiisobutyronitrile (AIBN) 0.45 parts and dibenzoyl peroxide (BPO) 0.4 parts).
The preparation method of the second polyacrylate in the embodiment comprises the following steps:
s1, mixing isooctyl acrylate, butyl acrylate, methacrylic acid, hydroxypropyl acrylate, dipropylene glycol diacrylate, 2/3 azodiisobutyronitrile, 2/3 dibenzoyl peroxide and 3/5 ethyl acetate for reaction (the reaction temperature is 90 ℃ C., the time is 4 hours) to prepare a first mixture;
s2, adding the rest of azodiisobutyronitrile, the rest of dibenzoyl peroxide and the rest of ethyl acetate into the first mixture for reaction (the reaction temperature is 85 ℃ C., the reaction time is 2 h), and cooling for 30min.
The preparation method of the fireproof adhesive film of the embodiment comprises the following steps:
coating a self-adhesive surface (thickness of 0.04 mm) on one surface of a substrate (PET film, 0.1 mm) to form a self-adhesive surface (thickness of 0.04 mm), and performing heat curing for the first time (temperature of 120 ℃ C., time of 2 min);
after the first heat curing is finished, attaching a release film on the self-adhesive surface;
coating the fireproof surface on the other side of the substrate to form a fireproof surface (thickness is 0.2 mm), and performing heat curing for the second time (temperature is 120 ℃ C., time is 2 min); curing after heat curing (temperature 25 ℃ C., time 7 days).
Example 2
The embodiment is a fireproof adhesive film, which comprises a fireproof surface and a self-adhesive surface;
the fireproof surface consists of the following preparation raw materials in parts by weight:
100 parts of first polyacrylate, 4.5 parts of first curing agent (isophorone diisocyanate 2.5 parts and amino resin 2 parts), 0.01 part of p-toluenesulfonic acid, 40 parts of ammonium polyphosphate, 10 parts of organic filler, 10 parts of pentaerythritol, 16 parts of melamine and 40 parts of ethyl acetate.
The self-adhesive surface is prepared from the following raw materials in parts by weight:
100 parts of second polyacrylate, 3 parts of second curing agent (1.5 parts of diphenylmethane diisocyanate and 1.5 parts of amino resin), 0.01 part of polyepoxide polymer and 60 parts of ethyl acetate.
The organic filler comprises the following preparation raw materials in parts by weight:
100 parts of titanium dioxide modified silica sol, 0.01 part of styrene, 0.07 part of propyl methacrylate trichlorosilane, 3 parts of hexafluorobutyl acrylate, 2 parts of butyl acrylate, 0.5 part of acrylic acid and 0.05 part of a first initiator (azodiisobutyronitrile (AIBN) 0.02 part and dibenzoyl peroxide (BPO) 0.03 part).
The titanium dioxide modified silica sol comprises the following preparation raw materials in parts by weight:
titanium dioxide 1 part and silica sol (HSD 100) 40 parts.
The titanium dioxide and the silica sol were stirred and mixed well (stirring speed was 100rpm, stirring time was 30 min), to obtain a titanium dioxide modified silica sol.
The first polyacrylate is prepared from the following raw materials in parts by weight:
100 parts of butyl acrylate, 10 parts of methacrylic acid, 15 parts of hydroxypropyl methacrylate, 0.1 part of isocyanate acrylate (isocyanate ethyl acrylate (CAS number: 13641-96-8)), 15 parts of difunctional acrylate (tripropylene glycol dimethacrylate), 150 parts of isooctyl acrylate, 200 parts of ethyl acetate, 150 parts of toluene and (azobisisobutyronitrile (AIBN) 0.3 parts and dibenzoyl peroxide (BPO) 0.6 parts) 0.9 parts.
The second polyacrylate is prepared from the following raw materials in parts by weight:
100 parts of butyl acrylate, 5 parts of methacrylic acid, 15 parts of hydroxypropyl acrylate, 5 parts of dipropylene glycol diacrylate, 200 parts of isooctyl acrylate, 380 parts of ethyl acetate and 0.85 part of a third initiator (azodiisobutyronitrile (AIBN) 0.45 parts and dibenzoyl peroxide (BPO) 0.4 parts).
The preparation methods of the fire-retardant adhesive film, the first polyacrylate and the second polyacrylate of the present example were carried out with reference to example 1.
Example 3
The embodiment is a fireproof adhesive film, which comprises a fireproof surface and a self-adhesive surface;
the fireproof surface consists of the following preparation raw materials in parts by weight:
100 parts of first polyacrylate, 4.5 parts of first curing agent (2.5 parts of dicyclohexylmethane diisocyanate and 2 parts of amino resin), 1 part of p-toluenesulfonic acid, 36 parts of ammonium polyphosphate, 20 parts of organic filler, 14 parts of pentaerythritol, 14 parts of melamine and 40 parts of ethyl acetate.
The self-adhesive surface is prepared from the following raw materials in parts by weight:
100 parts of a second polyacrylate, 3 parts of a second curing agent (1.5 parts of dicyclohexylmethane diisocyanate and 1.5 parts of amino resin), 1 part of a polyepoxide polymer and 60 parts of ethyl acetate.
The organic filler comprises the following preparation raw materials in parts by weight:
100 parts of titanium dioxide modified silica sol, 3 parts of styrene, 0.01 part of propyl methacrylate trichlorosilane, 3 parts of hexafluorobutyl acrylate, 0.01 part of butyl acrylate, 3 parts of acrylic acid and 0.02 part of (azobisisobutyronitrile (AIBN) and 0.03 part of dibenzoyl peroxide (BPO)).
The titanium dioxide modified silica sol comprises the following preparation raw materials in parts by weight:
titanium dioxide 1 part and silica sol (HSD 120) 60 parts.
The titanium dioxide and the silica sol were stirred and mixed well (stirring speed was 100rpm, stirring time was 30 min), to obtain a titanium dioxide modified silica sol.
The first polyacrylate is prepared from the following raw materials in parts by weight:
100 parts of butyl acrylate, 15 parts of methacrylic acid, 10 parts of hydroxypropyl methacrylate, 1 part of isocyanate acrylate (ethyl isocyanate acrylate (CAS number: 13641-96-8)), 10 parts of difunctional acrylate (1, 4-butanediol dimethacrylate), 200 parts of isooctyl acrylate, 200 parts of ethyl acetate, 150 parts of toluene and (azobisisobutyronitrile (AIBN) 0.3 parts and dibenzoyl peroxide (BPO) 0.6 parts) 0.9 parts.
The second polyacrylate is prepared from the following raw materials in parts by weight:
100 parts of butyl acrylate, 10 parts of methacrylic acid, 15 parts of hydroxypropyl acrylate, 10 parts of dipropylene glycol diacrylate, 150 parts of isooctyl acrylate, 380 parts of ethyl acetate and 0.85 part of a third initiator (azodiisobutyronitrile (AIBN) 0.45 parts and dibenzoyl peroxide (BPO) 0.4 parts).
The preparation methods of the fire-retardant adhesive film, the first polyacrylate and the second polyacrylate of the present example were carried out with reference to example 1.
Example 4
The embodiment is a fireproof adhesive film, which comprises a fireproof surface and a self-adhesive surface;
the fireproof surface consists of the following preparation raw materials in parts by weight:
100 parts of first polyacrylate, 4.5 parts of first curing agent (2.5 parts of hexamethylene diisocyanate and 2 parts of amino resin), 0.2 part of p-toluenesulfonic acid, 35 parts of ammonium polyphosphate, 14 parts of organic filler, 14 parts of pentaerythritol, 14 parts of melamine and 40 parts of ethyl acetate.
The self-adhesive surface is prepared from the following raw materials in parts by weight:
100 parts of a second polyacrylate, 3 parts of a second curing agent (1.5 parts of lysine diisocyanate and 1.5 parts of amino resin), 0.2 part of a polyepoxide polymer and 60 parts of ethyl acetate.
The organic filler comprises the following preparation raw materials in parts by weight:
100 parts of titanium dioxide modified silica sol, 0.5 part of styrene, 0.05 part of propyl methacrylate trichlorosilane, 0.03 part of hexafluorobutyl acrylate, 0.6 part of butyl acrylate, 1.3 parts of acrylic acid and 0.05 part of (azodiisobutyronitrile (AIBN) 0.02 part and dibenzoyl peroxide (BPO) 0.03 part).
The titanium dioxide modified silica sol comprises the following preparation raw materials in parts by weight:
titanium dioxide 1 part and silica sol (HSD 50) 45 parts.
The titanium dioxide and the silica sol were stirred and mixed well (stirring speed was 100rpm, stirring time was 30 min), to obtain a titanium dioxide modified silica sol.
The first polyacrylate is prepared from the following raw materials in parts by weight:
100 parts of butyl acrylate, 12 parts of methacrylic acid, 14 parts of hydroxypropyl methacrylate, 0.8 part of isocyanate acrylate (isocyanate ethyl acrylate (CAS number: 13641-96-8)), 14 parts of difunctional acrylate (1, 6-hexanediol dimethacrylate), 160 parts of isooctyl acrylate, 200 parts of ethyl acetate, 150 parts of toluene and (azobisisobutyronitrile (AIBN) 0.3 parts and dibenzoyl peroxide (BPO) 0.6 parts).
The second polyacrylate is prepared from the following raw materials in parts by weight:
100 parts of butyl acrylate, 6 parts of methacrylic acid, 12 parts of hydroxypropyl acrylate, 6 parts of dipropylene glycol diacrylate, 170 parts of isooctyl acrylate, 380 parts of ethyl acetate and 0.85 part of a third initiator (azodiisobutyronitrile (AIBN) 0.45 parts and dibenzoyl peroxide (BPO) 0.4 parts).
The preparation methods of the fire-retardant adhesive film, the first polyacrylate and the second polyacrylate of the present example were carried out with reference to example 1.
Example 5
The embodiment is a fireproof adhesive film, which comprises a fireproof surface and a self-adhesive surface;
the fireproof surface consists of the following preparation raw materials in parts by weight:
100 parts of first polyacrylate, 4.5 parts of first curing agent (2.5 parts of lysine diisocyanate and 2 parts of amino resin), 0.01 part of p-toluenesulfonic acid, 30 parts of ammonium polyphosphate, 10 parts of organic filler, 10 parts of pentaerythritol, 10 parts of melamine and 40 parts of ethyl acetate.
The self-adhesive surface is prepared from the following raw materials in parts by weight:
100 parts of second polyacrylate, 3 parts of second curing agent (1.5 parts of hexamethylene diisocyanate and 1.5 parts of amino resin), 0.01 part of polyepoxide polymer and 60 parts of ethyl acetate.
The organic filler comprises the following preparation raw materials in parts by weight:
100 parts of titanium dioxide modified silica sol, 0.01 part of styrene, 0.01 part of propyl methacrylate trichlorosilane, 0.01 part of hexafluorobutyl acrylate, 0.01 part of butyl acrylate, 0.01 part of acrylic acid and 0.005 part of (azobisisobutyronitrile (AIBN) 0.002 part and dibenzoyl peroxide (BPO) 0.003 part).
The titanium dioxide modified silica sol comprises the following preparation raw materials in parts by weight:
titanium dioxide 1 part and silica sol (HSD 50) 40 parts.
The titanium dioxide and the silica sol were stirred and mixed well (stirring speed was 100rpm, stirring time was 30 min), to obtain a titanium dioxide modified silica sol.
The first polyacrylate is prepared from the following raw materials in parts by weight:
100 parts of butyl acrylate, 10 parts of methacrylic acid, 10 parts of hydroxypropyl methacrylate, 0.1 part of isocyanate acrylate (isocyanate ethyl acrylate (CAS number: 13641-96-8)), 10 parts of difunctional acrylate (trimethylolpropane trimethacrylate), 150 parts of isooctyl acrylate, 200 parts of ethyl acetate, 150 parts of toluene and 0.3 part of Azobisisobutyronitrile (AIBN) and 0.6 part of dibenzoyl peroxide (BPO) 0.9 part.
The second polyacrylate is prepared from the following raw materials in parts by weight:
100 parts of butyl acrylate, 5 parts of methacrylic acid, 10 parts of hydroxypropyl acrylate, 5 parts of dipropylene glycol diacrylate, 150 parts of isooctyl acrylate, 380 parts of ethyl acetate and 0.85 part of a third initiator (azodiisobutyronitrile (AIBN) 0.45 parts and dibenzoyl peroxide (BPO) 0.4 parts).
The preparation methods of the fire-retardant adhesive film, the first polyacrylate and the second polyacrylate of the present example were carried out with reference to example 1.
Comparative example 1
The comparative example is a fire-proof adhesive film comprising a fire-proof surface and a self-adhesive surface;
the fireproof surface consists of the following preparation raw materials in parts by weight:
100 parts of first polyacrylate, 4.5 parts of first curing agent (2.5 parts of lysine diisocyanate and 2 parts of amino resin), 0.01 part of p-toluenesulfonic acid, 30 parts of ammonium polyphosphate, 10 parts of organic filler, 10 parts of pentaerythritol, 10 parts of melamine and 40 parts of ethyl acetate.
The preparation raw materials and parts by weight of the self-adhesive face were the same as in example 5.
The organic filler comprises the following preparation raw materials in parts by weight:
100 parts of titanium dioxide modified silica sol, 0.01 part of styrene, 0.01 part of propyl methacrylate trichlorosilane, 0.01 part of hexafluorobutyl acrylate, 0.01 part of butyl acrylate, 0.01 part of acrylic acid and 0.005 part of (azobisisobutyronitrile (AIBN) 0.002 part and dibenzoyl peroxide (BPO) 0.003 part).
The titanium dioxide modified silica sol comprises the following preparation raw materials in parts by weight:
titanium dioxide 1 part and silica sol (HSD 50) 20 parts.
The titanium dioxide and the silica sol were stirred and mixed well (stirring speed was 100rpm, stirring time was 30 min), to obtain a titanium dioxide modified silica sol.
The raw materials for preparing the first polyacrylate and the second polyacrylate and the parts by weight are the same as in example 5.
The preparation methods of the comparative fire-retardant adhesive film, the first polyacrylate and the second polyacrylate were performed with reference to example 1.
Comparative example 2
The comparative example is a fire-proof adhesive film comprising a fire-proof surface and a self-adhesive surface;
the fireproof surface consists of the following preparation raw materials in parts by weight:
100 parts of first polyacrylate, 4.5 parts of first curing agent (2.5 parts of lysine diisocyanate and 2 parts of amino resin), 0.01 part of p-toluenesulfonic acid, 30 parts of ammonium polyphosphate, 10 parts of organic filler, 10 parts of pentaerythritol, 10 parts of melamine and 40 parts of ethyl acetate.
The preparation raw materials and parts by weight of the self-adhesive face were the same as in example 5.
The organic filler comprises the following preparation raw materials in parts by weight:
100 parts of silica sol (HSD 50), 0.01 part of styrene, 0.01 part of propyl trichlorosilane, 0.01 part of hexafluorobutyl acrylate, 0.01 part of butyl acrylate, 0.01 part of acrylic acid and 0.005 part of Azobisisobutyronitrile (AIBN) 0.002 part and dibenzoyl peroxide (BPO) 0.003 part.
The raw materials for preparing the first polyacrylate and the second polyacrylate and the parts by weight are the same as in example 5.
The preparation methods of the comparative fire-retardant adhesive film, the first polyacrylate and the second polyacrylate were performed with reference to example 1.
Comparative example 3
The comparative example is a fire-proof adhesive film comprising a fire-proof surface and a self-adhesive surface;
the fireproof surface consists of the following preparation raw materials in parts by weight:
100 parts of first polyacrylate, 4.5 parts of first curing agent (2.5 parts of lysine diisocyanate and 2 parts of amino resin), 0.01 part of p-toluenesulfonic acid, 30 parts of ammonium polyphosphate, 10 parts of organic filler, 10 parts of pentaerythritol, 10 parts of melamine and 40 parts of ethyl acetate.
The preparation raw materials and parts by weight of the self-adhesive face were the same as in example 5.
The organic filler comprises the following preparation raw materials in parts by weight:
100 parts of titanium dioxide modified silica sol, 0.01 part of styrene, 0.01 part of propyl methacrylate trichlorosilane, 0.01 part of hexafluorobutyl acrylate, 0.01 part of butyl acrylate, 0.01 part of acrylic acid and 0.005 part of (azobisisobutyronitrile (AIBN) 0.002 part and dibenzoyl peroxide (BPO) 0.003 part).
The titanium dioxide modified silica sol comprises the following preparation raw materials in parts by weight:
1 part of titanium dioxide and 40 parts of silica sol (HS-830).
The titanium dioxide and the silica sol were stirred and mixed well (stirring speed was 100rpm, stirring time was 30 min), to obtain a titanium dioxide modified silica sol.
The raw materials for preparing the first polyacrylate and the second polyacrylate and the parts by weight are the same as in example 5.
The preparation methods of the comparative fire-retardant adhesive film, the first polyacrylate and the second polyacrylate were performed with reference to example 1.
Comparative example 4
The comparative example is a fire-proof adhesive film comprising a fire-proof surface and a self-adhesive surface;
the fireproof surface consists of the following preparation raw materials in parts by weight:
100 parts of first polyacrylate, 4.5 parts of first curing agent (2.5 parts of lysine diisocyanate and 2 parts of amino resin), 0.01 part of p-toluenesulfonic acid, 30 parts of ammonium polyphosphate, 10 parts of organic filler, 10 parts of pentaerythritol, 10 parts of melamine and 40 parts of ethyl acetate.
The preparation raw materials and parts by weight of the self-adhesive face were the same as in example 5.
The organic filler comprises the following preparation raw materials in parts by weight:
100 parts of titanium dioxide, 0.01 part of styrene, 0.01 part of propyl trichlorosilane, 0.01 part of hexafluorobutyl acrylate, 0.01 part of butyl acrylate, 0.01 part of acrylic acid and 0.005 part of (azobisisobutyronitrile (AIBN) 0.002 part and dibenzoyl peroxide (BPO) 0.003 part).
The raw materials for preparing the first polyacrylate and the second polyacrylate and the parts by weight are the same as in example 5.
The preparation methods of the comparative fire-retardant adhesive film, the first polyacrylate and the second polyacrylate were performed with reference to example 1.
Comparative example 5
The comparative example is a fire-proof adhesive film comprising a fire-proof surface and a self-adhesive surface;
the fireproof surface consists of the following preparation raw materials in parts by weight:
100 parts of first polyacrylate, 4.5 parts of first curing agent (lysine diisocyanate 2.5 parts and amino resin 2 parts), 0.01 part of p-toluenesulfonic acid, 30 parts of ammonium polyphosphate, 10 parts of pentaerythritol, 10 parts of melamine and 40 parts of ethyl acetate.
The preparation raw materials and parts by weight of the self-adhesive face were the same as in example 5.
The raw materials for preparing the first polyacrylate and the second polyacrylate and the parts by weight are the same as in example 5.
The preparation methods of the comparative fire-retardant adhesive film, the first polyacrylate and the second polyacrylate were performed with reference to example 1.
The method for testing the fireproof expansion rate comprises the following steps: the thickness of the fireproof adhesive film layer is H0, the thickness of the expansion layer after fireproof test (15 min at about 1200 ℃) is H1, and the expansion rate of the fireproof adhesive film is calculated by H1/H0.
The fire-proof surface was sprayed with a flame gun for 15min (about 1200 c), and then the temperature of the self-adhesive surface on the opposite side of the substrate was detected with a temperature sensor and recorded.
Waterproof permeation resistance: and (3) completely pasting the self-adhesive layer of the fireproof adhesive film on the surface of the adhered material in the non-expansion initial state of the fireproof layer, soaking the self-adhesive layer in water, taking out the self-adhesive layer after a certain time, and ensuring that the fireproof adhesive film is free from damage, lifting, foaming and water penetration.
TABLE 1 Performance test results of the fireproof adhesive films prepared in examples 1 to 5 and comparative examples 1 to 5 of the present invention
In summary, the first polyacrylate is selected as the main resin, and forms a cross-linked network structure under the action of the curing agent; ammonium polyphosphate, pentaerythritol and melamine form intumescent flame retardants; when the combination is heated, a layer of uniform foam carbon layer can be formed on the surface, so that the heat insulation, oxygen insulation and smoke suppression can be realized, molten drops can be prevented, and good flame retardant performance is realized. When the system is heated or burnt, the ammonium polyphosphate generates a strong dehydrating agent of polymetaphosphate to dehydrate and carbonize pentaerythritol, and the sticky carbonized substance releases NH in melamine 3 、H 2 The gas such as O expands to form a microporous carbon blocking layer, and heat transfer and diffusion of combustible volatile products and oxygen are prevented, so that the aim of flame retardance is fulfilled. The organic filler adopts titanium dioxide modified silica sol as a main raw material, wherein the titanium dioxide modified silica sol is used as a core layer material, the shell layer material is a poly (styrene-propyl trichlorosilane-hexafluorobutyl acrylate-butyl acrylate-acrylic acid) hydrophobic copolymer, and the hydrophobic copolymer can enable the titanium dioxide modified silica sol to reach a stable state; meanwhile, the hydrophobic polymer is favorable for protecting the titanium dioxide modified silica sol particles, and the titanium dioxide modified silica sol particles can be uniformly dispersed in the fireproof surface; in the high temperature process, the titanium dioxide modified silica sol particles migrate to the surface of the fireproof surface at a slightly high temperature to form an effective protective layer, so that heat transfer is hindered, the combustion speed and the heat release speed are delayed, and the flame retardance is improved. Meanwhile, as the organic filler has excellent hydrophobic effect, the invasion of moisture from the waterproof surface can be further prevented, so that the waterproof effect of the self-adhesive surface is affected; namely, the organic filler, ammonium polyphosphate, pentaerythritol and melamine in the invention play a role in synergistic flame retardanceAnd the effect is further improved, so that the flame-retardant effect of the fireproof surface is further improved, and finally the fireproof adhesive film with excellent flame retardant property is prepared.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.

Claims (10)

1. The fireproof adhesive film is characterized by comprising a fireproof surface and a self-adhesive surface;
the fireproof surface comprises the following preparation raw materials:
a first polyacrylate, a first curative, p-toluene sulfonic acid, ammonium polyphosphate, an organic filler, pentaerythritol, melamine, and ethyl acetate;
the self-adhesive surface comprises the following preparation raw materials:
a second polyacrylate, a second curative, a polyepoxide, and ethyl acetate;
the organic filler comprises the following preparation raw materials:
titanium dioxide modified silica sol, styrene, propyl trichlorosilane methacrylate, hexafluorobutyl acrylate, butyl acrylate, acrylic acid and a first initiator.
2. The fireproof adhesive film according to claim 1, wherein the fireproof surface comprises the following preparation raw materials in parts by weight:
100 parts of first polyacrylate, 3-5 parts of first curing agent, 0.01-1 part of p-toluenesulfonic acid, 30-50 parts of ammonium polyphosphate, 10-20 parts of organic filler, 10-20 parts of pentaerythritol, 10-20 parts of melamine and 30-50 parts of ethyl acetate.
3. The fireproof adhesive film according to claim 1, wherein the self-adhesive surface comprises the following preparation raw materials in parts by weight:
100 parts of second polyacrylate, 3-5 parts of second curing agent, 0.01-1 part of polyepoxide polymer and 50-70 parts of ethyl acetate.
4. The fireproof adhesive film according to claim 1, wherein the organic filler comprises the following preparation raw materials in parts by weight:
100 parts of titanium dioxide modified silica sol, 0.01 to 3 parts of styrene, 0.01 to 3 parts of propyl trichlorosilane, 0.01 to 3 parts of hexafluorobutyl acrylate, 0.01 to 3 parts of butyl acrylate, 0.01 to 3 parts of acrylic acid and 0.001 to 0.3 part of a first initiator.
5. The fire-resistant adhesive film according to claim 1, wherein the titanium dioxide modified silica sol comprises the following preparation raw materials:
titanium dioxide and silica sol.
6. The fire-resistant adhesive film according to claim 1, wherein the first polyacrylate comprises the following preparation raw materials:
butyl acrylate, methacrylic acid, hydroxypropyl methacrylate, isocyanate acrylate, difunctional acrylate, isooctyl acrylate, ethyl acetate, toluene and a second initiator.
7. The fire-resistant adhesive film according to claim 1, wherein the second polyacrylate comprises the following preparation raw materials:
butyl acrylate, methacrylic acid, hydroxypropyl acrylate, dipropylene glycol diacrylate, isooctyl acrylate, ethyl acetate, and a third initiator.
8. A method of preparing the fire-retardant adhesive film according to any one of claims 1 to 7, comprising the steps of:
coating a preparation raw material of a self-adhesive surface on one surface of a substrate to form the self-adhesive surface, and performing heat curing for the first time;
after the first heat curing is completed, the fireproof surface is formed by coating the preparation raw materials of the fireproof surface on the other side of the substrate, and the second heat curing is performed.
9. The method of claim 8, wherein the second thermal cure is at a temperature of 100 ℃ to 140 ℃.
10. Use of the fire-retardant adhesive film according to any one of claims 1 to 7 in the field of rail transit.
CN202311655645.4A 2023-12-05 2023-12-05 Fireproof adhesive film and preparation method and application thereof Pending CN117487472A (en)

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