CN109517538A - A kind of adhesive and preparation method thereof, Flexible copper-clad plate and preparation method thereof - Google Patents

A kind of adhesive and preparation method thereof, Flexible copper-clad plate and preparation method thereof Download PDF

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Publication number
CN109517538A
CN109517538A CN201811401832.9A CN201811401832A CN109517538A CN 109517538 A CN109517538 A CN 109517538A CN 201811401832 A CN201811401832 A CN 201811401832A CN 109517538 A CN109517538 A CN 109517538A
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Prior art keywords
adhesive
component
temperature
clad plate
parts
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CN201811401832.9A
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CN109517538B (en
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李政
盘冠华
何志球
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Guangdong Lyle New Materials Polytron Technologies Inc
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Guangdong Lyle New Materials Polytron Technologies Inc
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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
    • C09J127/00—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 a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/12—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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09J127/18—Homopolymers or copolymers of tetrafluoroethene
    • 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
    • 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
    • B32B15/04—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
    • B32B15/088—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 polyamides
    • 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
    • B32B15/09—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 polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/162—Cleaning
    • 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
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/02—Copolymers with acrylonitrile
    • 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
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J127/00—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 a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/12—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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C09J127/00—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 a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/12—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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09J127/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0016—Abrading
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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    • 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
    • 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
    • C08K3/38—Boron-containing compounds
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Thermal Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a kind of adhesives and preparation method thereof, adhesive is mixed by first component and second component, and first component includes the raw material of following mass parts: 0.5~1 part of 50~60 parts of fluorine-containing elastomer polymer, 20~40 parts of epoxy resin, 40~80 parts of organic solvent, 5~10 parts of environmental protection flame retardant filler, 1.5~5 parts of impact modifying agent and silane coupling agent and 0.1~1 part of reaction promoter；Second component includes the raw material of following mass parts: 2~4 parts and 2~10 parts of organic solvent of curing agent；Solid content ratio when first component and second component mix is 10:(0.2~0.4).The present invention also provides a kind of Flexible copper-clad plate and preparation method thereof, Flexible copper-clad plate includes substrate layer, adhesive layer and copper foil layer, and adhesive layer is coated with by above-mentioned adhesive, and adhesive layer bonds together substrate layer and copper foil layer.Products of the present invention has the characteristics that low-k, high-weatherability, high resistance to tortuosity, stability is higher, the service life is longer.

Description

A kind of adhesive and preparation method thereof, Flexible copper-clad plate and preparation method thereof
Technical field
The present invention relates to a kind of adhesives and preparation method thereof, Flexible copper-clad plate and preparation method thereof, belong to copper-clad plate skill Art field.
Background technique
Core industry of the IT industry as contemporary advanced IT application, the electronic equipment high frequency of IT industry must be that development becomes Gesture, especially wireless network, satellite communication it is increasingly developed, information products move towards high speed and high frequency and communication products move towards Voice, video and the data normalization of the big fireballing wireless transmission of capacity.Therefore the generation information product of development requires High frequency FPC (flexible circuit board) is necessarily rapidly developed again in the coming years, and high frequency FPC demand will jump up.
And core material one of of the Flexible copper-clad plate as FPC, Flexible copper-clad plate follow in the development of FPC high frequency, also become Development in terms of low dielectric.The development for considering novel high-frequency information equipment in recent years simultaneously, more wants the weather resistance of product It asks and more improves, such as using the communication products such as satellite system, high-frequency reception base station, open air transmission equipment in extreme circumstances Deng, to high frequency FPC weatherability require it is higher, and some novel device products its there are frequent dynamic sexual functions, certain The resistance to tortuous performance requirement of high frequency FPC is higher in degree.So under the development trend of novel information product, the property of Flexible copper-clad plate It can need it in the good bases performance such as low-k and low-dielectric loss in particular surroundings and functional application, have more High weatherability and resistance to tortuosity.And Flexible copper-clad plate made from existing adhesive is due to high dielectric constant, weatherability and resistance to Tortuosity is poor, so as to cause the problem that its dielectric loss is high, performance is unstable, service life is short, or even seriously affects high frequency FPC Service life and performance stability.
How a kind of adhesive is invented, and Flexible copper-clad plate obtained has low dielectric constant, high-weatherability, high resistance to complications Property, the characteristics of stability is higher, the service life is longer, are current those skilled in the art's urgent problems to be solved.
Summary of the invention
In view of the foregoing drawbacks, it is an object of the invention to propose a kind of adhesive and preparation method thereof, Flexible copper-clad plate and Preparation method, the adhesive and Flexible copper-clad plate of preparation have low-k, high-weatherability, high resistance to tortuosity, stability Higher, the characteristics of the service life is longer.
To achieve this purpose, the present invention adopts the following technical scheme:
A kind of adhesive, the adhesive are mixed by first component and second component, and the first component includes following quality The raw material of part: 50~60 parts of fluorine-containing elastomer polymer, 20~40 parts of epoxy resin, 40~80 parts of organic solvent, environmental protection flame retardant 5~10 parts of filler, 1.5~5 parts of impact modifying agent, 0.5~1 part of silane coupling agent and 0.1~1 part of reaction promoter；
The second component includes the raw material of following mass parts: 2~4 parts and 2~10 parts of organic solvent of curing agent；
Solid content ratio when the first component and the second component mix is 10:(0.2~0.4).
Preferably, the fluorine-containing elastomer polymer is epoxy resin modification vinylidene fluoride-hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) Copolymer, chlorotrifluoroethylene-vinylidene fluoride copolymers, polytetrafluoroethylmodified modified butylbenzene/nitrile rubber, vinylidene-tetrafluoro second One of alkene-perfluoro methyl vinyl ether-cure site monomer quadripolymer and the hydrocarbon propylene copolymer of tetrafluoroethene-are more Kind；
The epoxy resin is more phenolic tetraglycidel ether epoxy resins, heterocyclic type glycidyl epoxide resin, organic titanium One of modified bisphenol A type epoxy resin, glycidyl amine type epoxy resin and aliphatic epoxy olefin(e) compound are more Kind；
The environmental protection flame retardant filler is by phosphorus flame retardant and inorganic salts fire retardant with 1:(1~3) mass ratio mix, The phosphorus flame retardant is ammonium polyphosphate, hypophosphites, the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9,10- dihydro-9-oxy, triphenyl One of double two (2,6- 3,5-dimethylphenyl) phosphates of phosphorous oxide, diethyl hypo-aluminum orthophosphate and resorcinol are a variety of；It is described Inorganic salts fire retardant is one of aluminium hydroxide, magnesium hydroxide, zinc borate and silicate or a variety of；
The impact modifying agent is chliorinated polyvinyl chloride, ethylene-vinyl acetate copolymer and 4,5- epoxy tetrahydro neighbour benzene two One of formic acid dioctyl ester is a variety of；
The silane coupling agent is γ-glycidol ether propyl trimethoxy silicane, three second of 3- glycidyl ether oxygen propyl Oxysilane, 3- glycidyl ether oxygen propyl trimethoxy silicane, 3- glycidyl ether oxygen propyl trimethoxy silicane and 2- (3, 4- 7-oxa-bicyclo[4.1.0 base) one of ethyl trimethoxy silane or a variety of；
The reaction promoter is organic ureas, N, N '-diphenylguanidine, N, tri- (diformazan of N- diethylaniline and 2,4,6- Amino methyl) one of phenol or a variety of；
The curing agent is amino resin crosslinked polycondensation-acrylic polymer system curing agent, dicyandiamide latent curing It is one or more in agent and mixed type polyisocyanate curing agent；
The organic solvent is in butanone, acetone, hexamethylene, cyclohexanone, toluene, dimethylbenzene and N,N-dimethylformamide It is one or more.
A kind of preparation method according to above-mentioned adhesive, includes the following steps:
(a) it is carried out after mixing the organic solvent of fluorine-containing elastomer polymer, epoxy resin and first component by formula ratio permanent The silane coupling agent of formula ratio is added in warm stir process, and reduction of speed stirs 40min~60min, and first component host agent is made；
(b) environmental protection flame retardant filler is prepared, impact modifying agent and environmental protection flame retardant filler is added by formula ratio to first component host agent, 60min~90min is stirred for 1000rpm~3000rpm with revolving speed, reaction promoter is added by formula ratio again after mixing evenly, And keeping revolving speed is that 1000rpm~3000rpm stirs 10min~15min, and first component is made；
(c) curing agent and the organic solvent of second component are mixed and is dissolved by formula ratio, second component is made；
(d) first component and second component are mixed in proportion, stirs 30min~40min, adhesive is made in sieving.
Preferably, in the step (a), the parameter of the constant temperature stir process are as follows: temperature is in 60 DEG C~80 DEG C One value, revolving speed be 1000rpm~1500rpm, time 4h, and the process that the silane coupling agent is added keeps the constant temperature to stir The temperature of processing is mixed, the revolving speed of the reduction of speed stirring is 500rpm~800rpm.
Preferably, the revolving speed of step (d) stirring is 800rpm~1500rpm, and crossing grit number is 300~400 mesh.
A kind of Flexible copper-clad plate using above-mentioned adhesive, including substrate layer, adhesive layer and copper foil layer, the adhesive layer by The adhesive is coated with, and the adhesive layer bonds together the substrate layer and the copper foil layer.
Preferably, the substrate layer is the molding base material film of biaxial tension, and the base material film is PI film, PEFT film, pen film One of with Aramid film；The copper foil layer is electrolytic copper foil or rolled copper foil；
The substrate layer with a thickness of 15 μm~110 μm；The adhesive layer with a thickness of 5 μm~70 μm；The copper foil layer With a thickness of 12 μm~150 μm.
A kind of preparation method according to the above-mentioned Flexible copper-clad plate using adhesive, includes the following steps:
(1) substrate layer surface is subjected to sided corona treatment；
(2) chemical cleaning is carried out to copper foil layer surface and mechanical lapping is handled, made copper foil layer surface with hair side, obtain pre- Handle copper foil layer；
(3) it is coated with adhesive on the sided corona treatment face of substrate layer, makes substrate layer with adhesive layer, and by drying Reason obtains bonding substrate layer；
(4) bonding plane for being bonded substrate layer is bonded with the hair side of pretreatment copper foil layer, it is pre- laminating carries out room temperature roller, then lead to Excessively high warm roller is laminating, and the laminating temperature of high temperature hot-rolling is set as 110 DEG C~150 DEG C, obtains Flexible copper-clad plate semi-finished product；
(5) stage maturation process after Flexible copper-clad plate semi-finished product loose winding, will be carried out, Flexible copper-clad plate finished product is obtained.
Preferably, the corona value set in the sided corona treatment of the step (1) is greater than 52dy；The step (3) is coated with glue The speed of glutinous agent is 2m/min~10m/min, and the temperature of drying and processing is 140 DEG C~220 DEG C.
Preferably, the stage maturation process of the step (5): first stage temperature in 100min is risen to by 30 DEG C 100℃；Second stage keeps 100 DEG C of temperature in 120min；Phase III temperature in 180min by 100 DEG C rises to 150 ℃；Fourth stage keeps 150 DEG C of temperature in 120min；5th stage temperature in 120min by 150 DEG C rises to 180 DEG C； 6th stage temperature in 60min by 180 DEG C drops to 30 DEG C.
The beneficial effects of the present invention are: the core component of (1) this adhesive is fluorine-containing elastomer polymer, have good The dielectric loss of Flexible copper-clad plate is effectively reduced in low Jie's property, resistance to medium and noninflammability；Fluorine-containing elastomer polymer has excellent Stability, by adhesive be bonded substrate layer and copper foil layer perfection be bonded, make Flexible copper-clad plate weatherability with higher Energy；Fluorine-containing elastomer polymer has favorable elasticity and restorability, assigns Flexible copper-clad plate resistance to tortuosity and good deformation by force Recovery capability；(2) epoxy resin plays the role of carrier in adhesive, has good dielectricity, high-low temperature resistant, water absorption resistance Deng the stability and weather resistance of adhesive needed for capable of improving, while there is good impact flexibility and adhesive property and fluorine-containing Elastomer polymer is used in mixed way the adhesive force and impact property that can improve it to metal substrate surface；(3) silicon in adhesive Alkane coupling agent can react with environmental protection flame retardant filler, improve the applicability and dispersibility of environmental protection flame retardant filler；It can make to contain Fluoro elastomer copolymer and epoxy resin crosslink reaction, play the role of molecular bridge；The work of tackifier can also be played With effectively increasing the adhesive strength of binder, also improve water-fast, weatherability；(4) copper is covered using soft made of this adhesive Plate has low-dielectric loss, high-weatherability and Gao Nai tortuosity, meets and covers copper to soft under the development of high frequency novel information product The specific demand of plate makes it keep good product stability and service life in a variety of extreme environments and application；(5) soft Stage maturation process in copper-clad plate preparation process can promote strand gradually to move, be conducive to first group by gradually heating up Epoxy resin and second component in point carry out curing reaction, keep product slaking reaction balanced and completion of cure, are effectively ensured soft Copper-clad plate finished product stability.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of Flexible copper-clad plate of the invention.
Wherein: substrate layer 1；Adhesive layer 2；Copper foil layer 3.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
The present invention provides a kind of adhesive, adhesive is mixed by first component and second component, and first component includes as follows The raw material of mass parts: 50~60 parts of fluorine-containing elastomer polymer, 20~40 parts of epoxy resin, 40~80 parts of organic solvent, environmental protection 5~10 parts of fire-retardant filler, 1.5~5 parts of impact modifying agent, 0.5~1 part of silane coupling agent and 0.1~1 part of reaction promoter；
Second component includes the raw material of following mass parts: 2~4 parts and 2~10 parts of organic solvent of curing agent；
Solid content ratio when first component and second component mix is 10:(0.2~0.4).
This adhesive is used for Flexible copper-clad plate, dexterously by fluorine-containing elastomer polymer, epoxy resin and silane coupled Agent is used in compounding, and the high adhesion property that adhesive treats adhesives is significantly improved, and reduces the dielectric of product after its bonding Constant reduces dielectric loss, improves the weatherability and resistance to tortuosity of product after bonding, to meet high frequency novel information product hair The specific demand of exhibition, the product after making bonding keep good product stability in a variety of extreme environments and application and use the longevity Life.
Core component in this adhesive first component formula is fluorine-containing elastomer polymer, has good low Jie's property, resistance to Medium and noninflammability, are effectively reduced dielectric loss；Fluorine-containing elastomer polymer has excellent stability, viscous by adhesive It connects material and realizes perfect fitting, the product weather resistance with higher after making bonding；Fluorine-containing elastomer polymer has good Elasticity and restorability assign the product after being bonded resistance to tortuosity and good deformation recovery capability by force；But fluoroelastomer polymerize Object itself is poor to metal cohesive force and epoxy resin is used in mixed way can effectively improve and improve adhesive to the attached of metal material Put forth effort performance, to meet the needs of Flexible copper-clad plate product.
Epoxy resin plays the role of carrier in adhesive, has the energy such as good dielectricity, high-low temperature resistant, water absorption resistance The stability and weather resistance of adhesive needed for improving, while there is good impact flexibility and adhesive property and fluorine-containing elasticity Body mixed with polymers use can improve its adhesive force and impact property to metal material surface.But epoxy resin has certain crisp The property changed improves the durability of product after bonding, the additional amount of epoxy resin is not suitable for higher to keep high resiliency；Moreover, ring The dielectric constant of oxygen resin is higher, is unfavorable for the dielectric loss of product after reduction bonding, so the ratio of its additional amount is not suitable for It is excessive, and fluorine-containing elastomer polymer should be lower than, it can guarantee that the low-dielectric of fluorine-containing elastomer polymer can be sent out in this way It waves.
Silane coupling agent can react with environmental protection flame retardant filler, improve the applicability and dispersion of environmental protection flame retardant filler Property；Fluorine-containing elastomer polymer and epoxy resin can be made to crosslink reaction, play the role of molecular bridge；It can also play The effect of tackifier, effectively increases the adhesive strength of binder, also improves water-fast, weatherability.But silane coupling agent additional amount It is excessive excessively to will cause adhesive viscosity, and influences processing performance, adhesive viscosity and friendship has been effectively ensured by above-mentioned formula ratio Join effect.
Environmental protection flame retardant filler can be effectively controlled the water absorption resistance energy and viscosity of adhesive, but excessive be added will lead to gluing The viscosity of agent increases and process time extends, and therefore, is advisable by the addition of above-mentioned formula ratio.
Impact modifying agent is adjustable the brittleness after adhesive bonding, and control is added and can be effectively controlled in the range of formula ratio Brittleness after adhesive bonding, while also controlling cost.
Reaction promoter can be reacted with curing agent, can effectively be accelerated binder solidification, be reduced reaction temperature, adhesive layer is made to exist Faster reach stable solid state in thermo-curing stage.
Organic solvent adjusts the solid content of adhesive for dissolving the substance for being insoluble in water, reaches appropriate contain Gu amount, adjusts the quality of adhesive.
In conclusion fluorine-containing elastomer polymer itself is also poor to the adhesive ability of substrate, will affect to a certain extent Adhesive treats the adhesive property of adhesives, but silane is added in fluorine-containing elastomer polymer and epoxy resin composition After coupling agent is crosslinked, modifying function is played, increases substantially fluorine-containing elastomer polymer to the adhesive force of substrate.Silicon simultaneously The addition of alkane coupling agent can make fluorine-containing elastomer polymer and epoxy resin play cross-linking reaction, erect molecular bridge, make fluorine-containing bullet The mixing of elastomer polymer and epoxy resin is more stable, moreover it is possible to make the adhesive property of adhesive stronger and more longlasting.Therefore, contain Fluoro elastomer copolymer, epoxy resin, silane coupling agent are used in compounding, and are constituted the host agent of this adhesive first component, are effectively changed It has been apt to fluorine-containing elastomer polymer to the adhesion property of substrate and outer metallic surface, has had adhesive and significantly treat adhesives High adhesion property, while combining between component can be more stable, avoids the occurrence of the exception of component compatibility, at the same time, performance contains Low Jie's property of fluoro elastomer copolymer, high-weatherability, high resistance to tortuosity ability.On this basis, and environmental protection flame retardant filler, The first component constituted after impact modifying agent, reaction promoter and organic solvent enables water absorption resistance, the viscosity, brittleness of first component It is further adjusted with solid content.Finally, proposing the stability of adhesive with including that curing agent second component mixes Height, optimizes the curing performance of adhesive, and plays adhesive and treat the significant high adhesion force of adhesives, the production after promoting bonding Product have low Jie's property, weatherability, the ability of resistance to tortuosity, improve stability, prolong the service life.It solves and uses existing glue Product made from glutinous agent leads to the dielectric loss height of product, performance not since high dielectric constant, weatherability and resistance to tortuosity are poor Stablize, the problem that service life is short.
Further, fluorine-containing elastomer polymer is that epoxy resin modification vinylidene fluoride-hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) is total Polymers, chlorotrifluoroethylene-vinylidene fluoride copolymers, polytetrafluoroethylmodified modified butylbenzene/nitrile rubber, vinylidene-tetrafluoroethene- One of perfluoro methyl vinyl ether-cure site monomer quadripolymer and the hydrocarbon propylene copolymer of tetrafluoroethene-are a variety of；
Epoxy resin is more phenolic tetraglycidel ether epoxy resins, heterocyclic type glycidyl epoxide resin, organic titanium are modified One of bisphenol A type epoxy resin, glycidyl amine type epoxy resin and aliphatic epoxy olefin(e) compound are a variety of；
Environmental protection flame retardant filler is by phosphorus flame retardant and inorganic salts fire retardant with 1:(1~3) mass ratio mix, phosphorus system Fire retardant be ammonium polyphosphate, hypophosphites, the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9,10- dihydro-9-oxy, Triphenylphospine oxide, One of diethyl hypo-aluminum orthophosphate and double two (2,6- 3,5-dimethylphenyl) phosphates of resorcinol are a variety of；Inorganic salts fire retardant For one of aluminium hydroxide, magnesium hydroxide, zinc borate and silicate or a variety of；
Impact modifying agent is chliorinated polyvinyl chloride, ethylene-vinyl acetate copolymer and 4,5- epoxy tetrahydrophthalic acid One of dioctyl ester is a variety of；
Silane coupling agent is γ-glycidol ether propyl trimethoxy silicane, 3- glycidyl ether oxygen propyl triethoxy Silane, 3- glycidyl ether oxygen propyl trimethoxy silicane, 3- glycidyl ether oxygen propyl trimethoxy silicane and 2- (3,4- ring Oxygen cyclohexyl) one of ethyl trimethoxy silane or a variety of；
Reaction promoter is organic ureas, N, N '-diphenylguanidine, N, tri- (dimethylamino of N- diethylaniline and 2,4,6- Methyl) one of phenol or a variety of；
Curing agent be amino resin crosslinked polycondensation-acrylic polymer system curing agent, dicyandiamide latent curing agent and It is one or more in mixed type polyisocyanate curing agent；
Organic solvent is one in butanone, acetone, hexamethylene, cyclohexanone, toluene, dimethylbenzene and N,N-dimethylformamide Kind is a variety of.
Fluorine-containing elastomer polymer has good low Jie's property, resistance to medium and noninflammability, thermoplastic mobility and thermostabilization Property is excellent and weather-resistant property with higher.Fluorine-containing elastomer polymer has favorable elasticity and restorability simultaneously, assigns Give the strong resistance to tortuosity and good deformation recovery capability of product after being bonded.
Epoxy resin have good dielectricity, high-low temperature resistant, water absorption resistance etc. can improve required adhesive stability and Weather resistance, while its good impact flexibility and adhesive property and fluorine-containing elastomer polymer are used in mixed way that improve its right The adhesive force and impact property of metal material surface.
The addition of environmental protection flame retardant filler effectively promotes the flame retardant property of product after bonding, and Halogen, without ROSH meets environmental protection It is required that.But flame retardant effect is bad when phosphorus flame retardant is used alone, and can produce with inorganic salts fire retardant compounding and cooperates with effect It answers, is more conducive to raising flame retarding efficiency and better smoke suppressing effect, improve dispersibility and improve anti-with polymer compatibility, raising Impact property and hot property, to obtain good flame retardant effect.
Impact modifying agent can improve the storage stability of adhesive, while play toughening, low-temperature stabilization, durable, mechanical The effect of property modification.Silane coupling agent plays the role of tackifier, effectively increases the adhesive strength of adhesive, moreover it is possible to mention The performances such as high water resistance, weatherability.Reaction promoter can be reacted with curing agent, can effectively accelerate binder solidification, reduce reaction temperature Degree.Curing agent can effectively increase the stability of adhesive, reduce solidification temperature, improve solid rate, and more preferably improve adhesive layer Adhesion strength, thermal stability and weatherability.Organic solvent adjusts consolidating for adhesive and contains for dissolving the substance for being insoluble in water Amount, reaches solid content appropriate, adjusts the quality of adhesive.
A kind of preparation method according to above-mentioned adhesive, includes the following steps:
(a) it is carried out after mixing the organic solvent of fluorine-containing elastomer polymer, epoxy resin and first component by formula ratio permanent The silane coupling agent of formula ratio is added in warm stir process, and reduction of speed stirs 40min~60min, and first component host agent is made；
(b) environmental protection flame retardant filler is prepared, impact modifying agent and environmental protection flame retardant filler is added by formula ratio to first component host agent, 60min~90min is stirred for 1000rpm~3000rpm with revolving speed, reaction promoter is added by formula ratio again after mixing evenly, And keeping revolving speed is that 1000rpm~3000rpm stirs 10min~15min, and first component is made；
(c) curing agent and the organic solvent of second component are mixed and is dissolved by formula ratio, second component is made；
(d) first component and second component are mixed in proportion, stirs 30min~40min, adhesive is made in sieving.
Fluorine-containing elastomer polymer, epoxy resin stir under the dissolution of organic solvent and the adjusting of solid content through constant temperature Processing, mixes the bulk composition of first component at the temperature of setting and revolving speed and sufficiently reacts, reach stable molten condition, Improve the stability of first component host agent.Early period, high-speed stirred was to allow fluorine-containing elastomer polymer and epoxy resin to be sufficiently stirred Uniformly, the stirring of subsequent reduction of speed be guarantee to be added in order to which silane coupling agent is added the stabilization of silane coupling agent post-crosslinking reaction into Row.When impact modifying agent and environmental protection flame retardant filler is added by formula ratio to first component host agent, due to environmental protection flame retardant filler The viscosity that first component can be significantly increased increases the resistance of stirring, so significantly improving speed of agitator, is conducive between raw material Mixing and reaction, improve the preparation efficiency and quality of first component.Using organic solvent, curing agent is dissolved in advance, is made Solution, then be mixed with first component, be conducive to improve the reaction efficiency between first component and second component, make adhesive obtained It achieves the desired results.In whole preparation process, the solid content that organic solvent adjusts adhesive is 25%~60%.First component and Second component mixes in proportion, mixes well after stirring, and the larger particles in adhesive are separated in sieving, makes obtained The fineness and viscosity of adhesive reach requirement, it is ensured that the performance of adhesive obtained is up to standard.
Further, in step (a), the parameter of constant temperature stir process are as follows: temperature be 60 DEG C~80 DEG C in one value, Revolving speed is 1000rpm~1500rpm, time 4h, and the process that silane coupling agent is added keeps the temperature of constant temperature stir process, drop The revolving speed of speed stirring is 500rpm~800rpm.
The constant temperature stir process of step (a) promotes fluorine-containing elastomer polymer, epoxy resin to be sufficiently mixed, and heats Temperature be 60 DEG C~80 DEG C, and the process that silane coupling agent is added also keeps the temperature, keeps the reaction of silane coupling agent living Property.Early period, high speed was to allow fluorine-containing elastomer polymer and epoxy resin to stir, and subsequent reduction of speed is to add Enter silane coupling agent, guarantees that stablizing for coupling agent post-crosslinking reaction, which is added, to carry out.
Further, the revolving speed of step (d) stirring is 800rpm~1500rpm, and crossing grit number is 300~400 mesh.Step (d) revolving speed stirred is high speed revolving speed, and significant plus first component and second component mixing speed improves the preparation efficiency of adhesive, The mixed effect for also promoting first component and second component simultaneously, improves the stability of the performance of adhesive.First component and second component are pressed After ratio is mixed, 300~400 meshes are crossed, the larger particles in adhesive are separated, makes adhesive obtained Fineness≤10 μm, viscosity are 2000mPas~3500mPas, it is ensured that the performance of adhesive obtained is up to standard.
A kind of Flexible copper-clad plate using above-mentioned adhesive, as shown in Figure 1, including substrate layer 1, adhesive layer 2 and copper foil layer 3, adhesive layer 2 is coated with by adhesive, and adhesive layer 2 bonds together substrate layer 1 and copper foil layer 3.
The present invention in adhesive layer 2 is coated with by above-mentioned adhesive, significantly improves adhesive to substrate layer 1 and copper foil layer 3 high adhesion property, reduces the low-dielectric loss of Flexible copper-clad plate, improves the weatherability and resistance to tortuosity of Flexible copper-clad plate, from And meet the specific demand under the development of high frequency novel information product to Flexible copper-clad plate, make it in a variety of extreme environments and application It is middle to keep good product stability and service life.
The structure of the improving performance of this Flexible copper-clad plate is adhesive layer 2, is coated with by adhesive, and adhesive first group Core component in distribution side is fluorine-containing elastomer polymer, and fluorine-containing elastomer polymer has good low Jie's property, media-resistant Property and noninflammability, are effectively reduced the dielectric loss of Flexible copper-clad plate；Fluorine-containing elastomer polymer has excellent stability, passes through The perfect fitting of substrate layer 1 and copper foil layer 3 of adhesive bonding, makes Flexible copper-clad plate weather resistance with higher；Fluorine-containing elasticity Body polymer has favorable elasticity and restorability, assigns Flexible copper-clad plate resistance to tortuosity and good deformation recovery capability by force；But Fluorine-containing elastomer polymer itself is poor to metal cohesive force and epoxy resin is used in mixed way can effectively improve and improve it to copper The adhesion performance of layers of foil 3.
Fluorine-containing elastomer polymer itself is also poor to the adhesive ability of substrate layer 1, will affect adhesive to a certain extent To the adhesive property of substrate layer 1, but in fluorine-containing elastomer polymer and epoxy resin composition be added silane coupling agent into After row crosslinking, modifying function is played, increases substantially fluorine-containing elastomer polymer to the adhesive force of substrate.Silane coupling agent simultaneously Addition fluorine-containing elastomer polymer and epoxy resin can be made to play cross-linking reaction, erect molecular bridge, polymerize fluoroelastomer The mixing of object and epoxy resin is more stable, moreover it is possible to make the adhesive property of adhesive stronger and more longlasting.Therefore, fluoroelastomer Polymer, epoxy resin, silane coupling agent are used in compounding, and constitute the host agent of this adhesive first component, are effectively improved fluorine-containing Elastomer polymer makes adhesive have the height significantly to substrate layer 1 and copper foil layer 3 adhesion property of substrate and outer metallic surface Adhesion property, while combining between component can be more stable, avoids the occurrence of the exception of component compatibility, at the same time, plays fluorine-containing Low Jie's property of elastomer polymer, high-weatherability, high resistance to tortuosity ability.On this basis, in addition environmental protection flame retardant filler, punching Hit the first component constituted after modifying agent, reaction promoter and organic solvent, enable the water absorption resistance of first component, viscosity, brittleness and Solid content is further adjusted.Finally, mixing with the second component for including curing agent, propose the stability of adhesive Height, optimizes the curing performance of adhesive, and plays adhesive to substrate layer 1 and the significant high adhesion force of copper foil layer 3, promotes this soft Property copper-clad plate have low Jie's property, weatherability, the ability of resistance to tortuosity, improve stability, prolong the service life.It solves existing Flexible copper-clad plate leads to that its dielectric loss is high, performance is unstable, makes since high dielectric constant, weatherability and resistance to tortuosity are poor With the problem that the service life is short.
Further, substrate layer 1 be the molding base material film of biaxial tension, base material film be PI film, PEFT film, pen film and One of Aramid film；Copper foil layer 3 is electrolytic copper foil or rolled copper foil；
Substrate layer 1 with a thickness of 15 μm~110 μm；Adhesive layer 2 with a thickness of 5 μm~70 μm；Copper foil layer 3 with a thickness of 12 μm~150 μm.
Base material film be PI (polyimides) film, PEFT (polytetrafluoroethylene (PTFE)) film, PEN (polyethylene naphthalate) film and One of Aramid (asymmetric aromatic polyamides) film is insulating film material composition, guarantor while playing its insulation function Flexible copper-clad plate is protected not by the invasion of external substance, keeps Flexible copper-clad plate more durable, performance is more stable；Copper foil layer 3, which provides, leads Body material is the material that Flexible copper-clad plate realizes conductor function.
According to actual use demand, the thickness of each layer of Flexible copper-clad plate is adjusted.Adhesive layer 2 is as crucial institute of the invention Low Jie's property, high-weatherability, the high resistance to complications of Flexible copper-clad plate entirety can be realized in the range of 5 μm~70 μm in, thickness Property, function and effect are obvious, thinner thickness, can effectively reduce the thickness of Flexible copper-clad plate, save cost.
A kind of preparation method according to the above-mentioned Flexible copper-clad plate using adhesive, includes the following steps:
(1) 1 surface of substrate layer is subjected to sided corona treatment；
(2) chemical cleaning is carried out to 3 surface of copper foil layer and mechanical lapping is handled, made 3 surface of copper foil layer with hair side, obtain Pre-process copper foil layer 3；
(3) it is coated with adhesive on the sided corona treatment face of substrate layer 1, makes substrate layer 1 with adhesive layer 2, and by drying Processing obtains bonding substrate layer 1；
(4) bonding plane for being bonded substrate layer 1 being bonded with the hair side of pretreatment copper foil layer 3, progress room temperature roller is pre- laminating, then Laminating by high temperature hot-rolling, the laminating temperature of high temperature hot-rolling is set as 110 DEG C~150 DEG C, obtains Flexible copper-clad plate semi-finished product；
(5) stage maturation process after Flexible copper-clad plate semi-finished product loose winding, will be carried out, Flexible copper-clad plate finished product is obtained.
1 surface of substrate layer carries out sided corona treatment, and the surface for improving substrate layer 1 has higher adhesion, avoids adhesive layer 2 There is adhesive force deficiency with substrate layer 1 and various abnormal problems occurs.3 surface of copper foil layer carries out at chemical cleaning and mechanical lapping Reason makes 3 surface of copper foil layer with hair side, improves adhesive layer 2 to the adhesive force of copper foil layer 3.On the sided corona treatment face of substrate layer 1 Drying and processing is carried out after coating adhesive, effective dry out solvent removes adhesive and completes remaining organic solvent after preparation.It will glue It connects after the bonding plane of substrate layer 1 be bonded with the hair side of pretreatment copper foil layer 3, it is pre- laminating to carry out room temperature roller, makes substrate layer 1, is bonded Layer 2 and copper foil layer 3 improve the degree of being flat and fit of three in nipping process；High temperature hot-rolling is laminating, utilizes 110 DEG C~150 DEG C High temperature roll-in, the fitting effect being remarkably improved between substrate layer 1, adhesive layer 2 and copper foil layer 3 improve adhesive layer 2 respectively to base The adhesion effect of material layer 1, copper foil layer 3.Finally, the stage maturation process carried out, can promote strand gradually to move, be conducive to Epoxy resin and second component in first component carry out curing reaction, keep product slaking reaction balanced and completion of cure, are effectively ensured Flexible copper-clad plate finished product stability.
Further, the corona value set in the sided corona treatment of step (1) is greater than 52dy；Step (3) is coated with adhesive Speed is 2m/min~10m/min, and the temperature of drying and processing is 140 DEG C~220 DEG C.
The corona value set in sided corona treatment, which is greater than the surface that substrate layer 1 is effectively ensured in 52dy, has higher adhesion, It avoids adhesive layer 2 and substrate layer 1 from adhesive force deficiency occur and various abnormal problems occurs.High temperature drying and processing, efficiently removes glue Remaining organic solvent after preparation is completed in glutinous agent, is promoted the production efficiency of this Flexible copper-clad plate, is improved the stability of adhesive.And Used organic solvent is related during the preparation process with adhesive for the speed of the coating adhesive of setting, while referring also to rear The temperature set and the drying equipment used in continuous drying and processing, it is ensured that the speed for being coated with adhesive is arranged in a suitable model In enclosing, organic solvent can be effectively dried as far as possible during subsequent drying and processing.
Further, the stage maturation process of step (5): first stage temperature in 100min is risen to by 30 DEG C 100℃；Second stage keeps 100 DEG C of temperature in 120min；Phase III temperature in 180min by 100 DEG C rises to 150 ℃；Fourth stage keeps 150 DEG C of temperature in 120min；5th stage temperature in 120min by 150 DEG C rises to 180 DEG C； 6th stage temperature in 60min by 180 DEG C drops to 30 DEG C.
Using stage maturation process in place according to primary heating, is solidified since adhesive is multicomponent mixture React excessively violent, will lead to the generation of by-product, the inside and outside solidification of adhesive is not uneven, cause product stress is big, under performance The unfavorable problems such as drop；In addition, wherein the boiling point of different solvents is different, adopts if using mixed organic solvents in adhesive preparation Effectively residual solvent can be allowed to volatilize with stage gradually heating curing, further avoid the influence of organic solvent residual.Stage By gradually heating up during formula maturation process, strand can be promoted gradually to move, be conducive to the epoxy resin in first component Curing reaction is carried out with second component, keeps product slaking reaction balanced and completion of cure, Flexible copper-clad plate finished product is effectively ensured and stablizes Property.
Embodiment group A
1. preparing adhesive
(a) polytetrafluoroethylmodified modified butylbenzene/nitrile rubber, more phenolic tetraglycidel ether epoxy resins and hexamethylene are pressed With 80 DEG C of stirring 4h of revolving speed 1500rpm constant temperature after the formula ratio mixing that table one is arranged, then keep constant temperature that formula ratio is added γ-glycidol ether propyl trimethoxy silicane, reduction of speed to 800rpm stir 60min, be made first component host agent；
(b) ammonium polyphosphate and aluminium hydroxide are mixed with the mass ratio of 1:1, prepares environmental protection flame retardant filler；To first Chliorinated polyvinyl chloride and environmental protection flame retardant filler is added in the formula ratio that component host agent according to the form below one is arranged, and is stirred with revolving speed for 3000rpm 90min is mixed, N, N '-diphenylguanidine is added by formula ratio again after mixing evenly, and keeping revolving speed is that 3000rpm stirs 15min, system Obtain first component；
(c) formula ratio that dicyandiamide latent curing agent, N, N '-diphenylguanidine and acetone according to the form below one are arranged is mixed simultaneously Second component is made in dissolution；
(d) first component and second component are mixed by the solid content ratio of 10:0.2, is 1500rpm stirring with revolving speed 40min crosses 400 meshes, and adhesive is made.
2. preparing Flexible copper-clad plate
(1) 1 surface of substrate layer is subjected to sided corona treatment, corona value is set as 55dy, substrate layer 1 with a thickness of 15 μm；
(2) chemical cleaning and mechanical lapping is carried out to 3 surface of copper foil layer to handle, copper foil layer 3 with a thickness of 12 μm, make copper foil 3 surface of layer have hair side, obtain pretreatment copper foil layer 3；
(3) adhesive is coated with the speed of 10m/min on the sided corona treatment face of substrate layer 1, adhesive layer 2 with a thickness of 20 μm, make substrate layer 1 with adhesive layer 2, and pass through 220 DEG C of drying and processings, obtains bonding substrate layer 1；
(4) bonding plane for being bonded substrate layer 1 being bonded with the hair side of pretreatment copper foil layer 3, progress room temperature roller is pre- laminating, then Laminating by high temperature hot-rolling, the laminating temperature of high temperature hot-rolling is set as 150 DEG C, obtains Flexible copper-clad plate semi-finished product；
(5) by after Flexible copper-clad plate semi-finished product loose winding, stage maturation process: first stage temperature in 100min is carried out 100 DEG C are risen to by 30 DEG C；Second stage keeps 100 DEG C of temperature in 120min；Phase III in 180min temperature by 100 DEG C rise to 150 DEG C；Fourth stage keeps 150 DEG C of temperature in 120min；5th stage in 120min temperature by 150 DEG C Rise to 180 DEG C；6th stage temperature in 60min by 180 DEG C drops to 30 DEG C, obtains Flexible copper-clad plate finished product.
Table is arranged in one embodiment group A adhesive component content of table
Embodiment A1-A5 is prepared according to the method described above, the various embodiments described above are tested for the property, and test result is such as Following table two:
Two embodiment group A performance test of table
As shown in Table 2, the appearance of Flexible copper-clad plate made from embodiment A1-A5 is few or without discoloration, bumps, folding line, wrinkle The flaws such as line, bubble, shrinkage cavity, to the performance test that Flexible copper-clad plate made from embodiment A1-A5 carries out, in the frequency of 10GHZ Upper its dielectric constant≤2.85, dielectric loss≤0.001, surface insulation resistance >=1.0 × 1014Ω, peel strength 1.45~ 1.52N/mm range, whole flame retardant property reach UL94VTM-0 grade, and soldering resistance can be good without exception.In conjunction with high temperature height Wet test, high/low-temperature impact test, high/low temperature peel test, circulating temperature test verification sample weather resistance are extremely stable, change Less, abnormal few, illustrate that the weatherability of Flexible copper-clad plate made from embodiment A1-A5 is high, and in various extreme environment factors Its lower stability is also high；And also there is the resistance to tortuous performance of the height that can reach 1000000 times or more, also have high Resistance to tortuous service life.Therefore, Flexible copper-clad plate made from embodiment A1-A5 can low-dielectric loss, improve weatherability and resistance to Tortuosity.
Embodiment group B
1. preparing adhesive
(a) with revolving speed 1000rpm after taking fluorine-containing elastomer polymer 50g, epoxy resin 20g and organic solvent 40g to mix Then 60 DEG C of stirring 4h of constant temperature keep constant temperature that the silane coupling agent of formula ratio is added, reduction of speed to 500rpm stirs 40min, First component host agent is made；The specific ingredient of fluoro elastomer copolymer, epoxy resin and organic solvent and silane coupling agent presses table three Setting；
(b) phosphorus flame retardant and inorganic salts fire retardant are mixed with the mass ratio of 1:3, prepares environmental protection flame retardant and fills out Material；Impact modifying agent 1.5g and environmental protection flame retardant filler 5g is added to first component host agent, is that 1000rpm stirs 60min with revolving speed, stirs Reaction promoter 0.1g is added after mixing uniformly, 1000rpm revolving speed is kept to stir 10min, and first component is made；Phosphorus flame retardant, The specific ingredient of inorganic salts fire retardant, impact modifying agent and reaction promoter is arranged by table three；
(c) curing agent 2g, organic solvent 2g are mixed and is dissolved, second component is made；Curing agent and organic solvent it is specific Ingredient is arranged by table three；
(d) first component and second component are mixed by the solid content ratio of 10:0.4, is 800rpm stirring with revolving speed 30min crosses 300 meshes, and adhesive is made.
2. preparing Flexible copper-clad plate
(1) 1 surface of substrate layer is subjected to sided corona treatment, table four is pressed in the thickness of substrate layer 1 and the setting of corona value；
(2) chemical cleaning is carried out to 3 surface of copper foil layer and mechanical lapping is handled, made 3 surface of copper foil layer with hair side, obtain Pre-process copper foil layer 3；
(3) adhesive is coated with the speed of 2m/min on the sided corona treatment face of substrate layer 1, makes substrate layer 1 with bonding The thickness of layer 2, adhesive layer 2 is arranged by table four, and passes through 140 DEG C of drying and processings, obtains bonding substrate layer 1；
(4) bonding plane for being bonded substrate layer 1 is bonded with the hair side of pretreatment copper foil layer 3, the thickness of copper foil layer 3 presses table four It is pre- laminating to carry out room temperature roller for setting, then laminating by high temperature hot-rolling, and the laminating temperature of high temperature hot-rolling is set as 110 DEG C, obtains soft Property copper-clad plate semi-finished product；
(5) by after Flexible copper-clad plate semi-finished product loose winding, stage maturation process: first stage temperature in 100min is carried out 100 DEG C are risen to by 30 DEG C；Second stage keeps 100 DEG C of temperature in 120min；Phase III in 180min temperature by 100 DEG C rise to 150 DEG C；Fourth stage keeps 150 DEG C of temperature in 120min；5th stage in 120min temperature by 150 DEG C Rise to 180 DEG C；6th stage temperature in 60min by 180 DEG C drops to 30 DEG C, obtains Flexible copper-clad plate finished product.
The specific ingredient setting of three embodiment group B of table
Table is arranged in four embodiment group B corona value of table and each thickness degree
Embodiment B1-B5 is prepared according to the method described above, the various embodiments described above are tested for the property, and test result is such as Following table five:
Five embodiment group B performance test of table
As shown in Table 5, the appearance of Flexible copper-clad plate finished product made from embodiment B1-B4 is few or without discoloration, bumps, folding The flaws such as trace, wrinkle, bubble, shrinkage cavity, the performance test to the progress of Flexible copper-clad plate finished product made from embodiment B1-B4, Its dielectric constant≤2.87, dielectric loss≤0.0012, surface insulation resistance >=1.0 × 10 in the frequency of 10GHZ14Ω, removing For intensity in 1.39~1.56N/mm range, whole flame retardant property reaches UL94VTM-0 grade, and soldering resistance can be well no different Often.Verification sample weatherability is tested in conjunction with high temperature and humidity test, high/low-temperature impact test, high/low temperature peel test, circulating temperature Can be extremely stable, with low uncertainty, abnormal few, illustrate that the weatherability of Flexible copper-clad plate finished product made from embodiment B1-B4 is high, and Its stability is also high under various extreme environment factors；And also there are the resistance to complications of height that can reach 1000000 times or more Performance also has high resistance to tortuous service life.Therefore, Flexible copper-clad plate finished product made from embodiment B1-B4 with it is existing Flexible copper-clad plate have low-dielectric loss, high-weatherability and Gao Nai tortuosity.
As shown in Table 5, Flexible copper-clad plate finished product made from embodiment B5 does not pass through in -65 DEG C of high/low-temperature impact tests, Do not pass through in -65 DEG C~160 DEG C circulating temperature tests, in 200000 resistance to tortuous tests and 1000000 resistance to tortuous tests Do not pass through, it follows that when being set as 52dy of corona value will affect the resistance to tortuous performance of manufactured Flexible copper-clad plate finished product, influence The adhesion on 1 surface of substrate layer, product quality decline.
The specific method is as follows for the test of Flexible copper-clad plate end properties made from above-described embodiment:
(1) appearance: whether visual Flexible copper-clad plate finished surface has the flaws such as discoloration, bumps, folding line, wrinkle, bubble, shrinkage cavity Defect.
(2) dielectric constant and dielectric loss: being tested using separate type dielectric resonance cell method, and test frequency 10GHZ can be with Verify the high-frequency dielectric performance of Flexible copper-clad plate finished product.
(3) it surface insulation resistance: using instrument specified in JISC1303, is surveyed according to standard preparation Flexible copper-clad plate finished product Test agent, and DC 500V voltage is applied on Flexible copper-clad plate finished product to be measured after holding 1min, measurement applies the table under voltage Face insulation resistance.
(4) peel strength: referring to IPC-TM650-2.4.9D, by Flexible copper-clad plate finished product be cut into 3.0 ± 1mm × The batten of 100mm carries out 90 degree of peel test forces using the speed of removing force tester setting 50mm/min, verifies to be measured soft The cohesive force of copper-clad plate finished product adhesive layer 2.
(5) resistance to scolding tin test: Flexible copper-clad plate finished product is cut into the sample of 30mm × 30mm, is set respectively using solder furnace It is 288 DEG C and 300 DEG C fixed, sample is immersed and carries out the test of 30s wicking in tin furnace, has seen whether bubble, layering, discoloration, disengaging Deng abnormal.
(6) flame retardant property: being tested using the test method of UL94VTM, verifying Flexible copper-clad plate finished product it is fire-retardant etc. Grade.
(7) weatherability is tested: being surveyed by high temperature and humidity test, high/low-temperature impact test, high/low temperature peel test, circulating temperature The synthesis such as examination is verified.It is equal to prepare test sample specification are as follows: 15 ± 1mm × 130 ± 5mm.
High temperature and humidity test: using 85 ± 5 DEG C of temperature, humidity 85% ± 5, and Flexible copper-clad plate finished product is placed in constant temperature perseverance Wet tank 96h, whether sample surfaces have oxidation after observation test, and blistering, removing, layering abnormal problem occur, and test peeling force, Its change rate≤10%.
High/low-temperature impact test: measurement obtains the sheet resistance of sample, and test sample is placed in the high and low temperature test machine, if Determine -65 DEG C of temperature, -20 DEG C, 100 DEG C, 160 DEG C and place 30min respectively, whether sample surfaces have oxidation after observation test, rise Bubble, removing, layering abnormal problem occur, and test front and rear surfaces resistance change rate≤10%.
High/low temperature peel test force: sample is placed in high/low temperature puller system, be set separately -50 DEG C, -10 DEG C, 100 DEG C, 150 DEG C, test the removing of sample and record under relevant temperature.
Circulating temperature test: sample is placed in accurate convection current high/low temperature baking oven, setting program has low high temperature circulation, low - 65 DEG C of temperature setting, high temperature set 160 DEG C, high/low temperature constant temperature time 15min, temperature transition time 10min, are continuously circulated 5 times. Whether the sample surfaces after whether sample is tested after observation test have oxidation, blistering, removing, layering abnormal problem to occur.
(8) resistance to tortuous test: reference standard IPC-TM650 prepares specification 15 ± 1mm × 130 ± 5mm test specimens, setting 4.9N (0.5kgf) load, crooked process radius 2mm, are tested with the speed of about 170 times/min by 135 ° ± 5 ° of bending angle, are seen Examine each stage sample and whether occur cracking, whiten, degumming etc. it is abnormal.
The technical principle of the invention is described above in combination with a specific embodiment.These descriptions are intended merely to explain of the invention Principle, and shall not be construed in any way as a limitation of the scope of protection of the invention.Based on the explanation herein, the technology of this field Personnel can associate with other specific embodiments of the invention without creative labor, these modes are fallen within Within protection scope of the present invention.

Claims (10)

1. a kind of adhesive, it is characterised in that: the adhesive is mixed by first component and second component, and the first component includes The raw material of following mass parts: 50~60 parts of fluorine-containing elastomer polymer, 20~40 parts of epoxy resin, 40~80 parts of organic solvent, 5~10 parts of environmental protection flame retardant filler, 1.5~5 parts of impact modifying agent, 0.5~1 part of silane coupling agent and reaction promoter 0.1~1 Part；
The second component includes the raw material of following mass parts: 2~4 parts and 2~10 parts of organic solvent of curing agent；
Solid content ratio when the first component and the second component mix is 10:(0.2~0.4).
2. adhesive according to claim 1, it is characterised in that: the fluorine-containing elastomer polymer is epoxy resin modification Vinylidene fluoride-tetrafluoraoethylene-hexafluoropropylene copolymer, chlorotrifluoroethylene-vinylidene fluoride copolymers, polytetrafluoroethylmodified modified fourth Benzene/nitrile rubber, vinylidene-tetrafluoroethylene-perfluoro methyl vinyl ether-cure site monomer quadripolymer and tetrafluoro second One of hydrocarbon propylene copolymer of alkene-is a variety of；
The epoxy resin is more phenolic tetraglycidel ether epoxy resins, heterocyclic type glycidyl epoxide resin, organic titanium are modified One of bisphenol A type epoxy resin, glycidyl amine type epoxy resin and aliphatic epoxy olefin(e) compound are a variety of；
The environmental protection flame retardant filler is by phosphorus flame retardant and inorganic salts fire retardant with 1:(1~3) mass ratio mix, it is described Phosphorus flame retardant is ammonium polyphosphate, hypophosphites, the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9,10- dihydro-9-oxy, triphenyl oxidation One of double two (2,6- 3,5-dimethylphenyl) phosphates of phosphorus, diethyl hypo-aluminum orthophosphate and resorcinol are a variety of；It is described inorganic Salt fire retardant is one of aluminium hydroxide, magnesium hydroxide, zinc borate and silicate or a variety of；
The impact modifying agent is chliorinated polyvinyl chloride, ethylene-vinyl acetate copolymer and 4,5- epoxy tetrahydrophthalic acid One of dioctyl ester is a variety of；
The silane coupling agent is γ-glycidol ether propyl trimethoxy silicane, 3- glycidyl ether oxygen propyl triethoxy Silane, 3- glycidyl ether oxygen propyl trimethoxy silicane, 3- glycidyl ether oxygen propyl trimethoxy silicane and 2- (3,4- ring Oxygen cyclohexyl) one of ethyl trimethoxy silane or a variety of；
The reaction promoter is organic ureas, N, N '-diphenylguanidine, N, tri- (dimethylamino of N- diethylaniline and 2,4,6- Methyl) one of phenol or a variety of；
The curing agent be amino resin crosslinked polycondensation-acrylic polymer system curing agent, dicyandiamide latent curing agent and It is one or more in mixed type polyisocyanate curing agent；
The organic solvent is one in butanone, acetone, hexamethylene, cyclohexanone, toluene, dimethylbenzene and N,N-dimethylformamide Kind is a variety of.
3. a kind of preparation method of adhesive according to claim 1 or 2, characterized by the following steps:
(a) constant temperature is carried out after mixing the organic solvent of fluorine-containing elastomer polymer, epoxy resin and first component by formula ratio to stir Processing is mixed, the silane coupling agent of formula ratio is added, reduction of speed stirs 40min~60min, and first component host agent is made；
(b) environmental protection flame retardant filler is prepared, impact modifying agent and environmental protection flame retardant filler is added by formula ratio to first component host agent, to turn Speed is that 1000rpm~3000rpm stirs 60min~90min, reaction promoter is added by formula ratio again after mixing evenly, and protect Holding revolving speed is that 1000rpm~3000rpm stirs 10min~15min, and first component is made；
(c) curing agent and the organic solvent of second component are mixed and is dissolved by formula ratio, second component is made；
(d) first component and second component are mixed in proportion, stirs 30min~40min, adhesive is made in sieving.
4. the preparation method of adhesive according to claim 3, it is characterised in that: in the step (a), the constant temperature The parameter of stir process are as follows: temperature is a value in 60 DEG C~80 DEG C, revolving speed is 1000rpm~1500rpm, time 4h, The process that the silane coupling agent is added keeps the temperature of the constant temperature stir process, and the revolving speed of the reduction of speed stirring is 500rpm ~800rpm.
5. the preparation method of adhesive according to claim 3, it is characterised in that: the revolving speed of the step (d) stirring is 800rpm~1500rpm, crossing grit number is 300~400 mesh.
6. a kind of Flexible copper-clad plate for having used adhesive as claimed in claim 1 or 2, it is characterised in that: including substrate layer, Adhesive layer and copper foil layer, the adhesive layer are coated with by the adhesive, and the adhesive layer is by the substrate layer and the copper Layers of foil bonds together.
7. the Flexible copper-clad plate according to claim 6 using adhesive, it is characterised in that: the substrate layer is two-way drawing Molding base material film is stretched, the base material film is one of PI film, PEFT film, pen film and Aramid film；The copper foil layer is electricity Solve copper foil or rolled copper foil；
The substrate layer with a thickness of 15 μm~110 μm；The adhesive layer with a thickness of 5 μm~70 μm；The thickness of the copper foil layer Degree is 12 μm~150 μm.
8. a kind of preparation method of the Flexible copper-clad plate according to claim 7 using adhesive, it is characterised in that: including Following steps:
(1) substrate layer surface is subjected to sided corona treatment；
(2) chemical cleaning is carried out to copper foil layer surface and mechanical lapping is handled, made copper foil layer surface with hair side, pre-processed Copper foil layer；
(3) it is coated with adhesive on the sided corona treatment face of substrate layer, makes substrate layer with adhesive layer, and pass through drying and processing, obtained Substrate layer must be bonded；
(4) bonding plane for being bonded substrate layer is bonded with the hair side of pretreatment copper foil layer, it is pre- laminating carries out room temperature roller, then pass through height It is laminating to warm roller, the laminating temperature of high temperature hot-rolling is set as 110 DEG C~150 DEG C, obtains Flexible copper-clad plate semi-finished product；
(5) stage maturation process after Flexible copper-clad plate semi-finished product loose winding, will be carried out, Flexible copper-clad plate finished product is obtained.
9. the preparation method of Flexible copper-clad plate according to claim 8, it is characterised in that: at the corona of the step (1) The corona value set in reason is greater than 52dy；The step (3) is coated with the speed of adhesive for 2m/min~10m/min, at drying The temperature of reason is 140 DEG C~220 DEG C.
10. the preparation method of Flexible copper-clad plate according to claim 8, it is characterised in that: the step (5) it is stage Maturation process: first stage temperature in 100min by 30 DEG C rises to 100 DEG C；Second stage keeps temperature in 120min 100℃；Phase III temperature in 180min by 100 DEG C rises to 150 DEG C；Fourth stage keeps temperature 150 in 120min ℃；5th stage temperature in 120min by 150 DEG C rises to 180 DEG C；6th stage temperature in 60min is declined by 180 DEG C To 30 DEG C.
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