CN108676475A - A kind of halogen-free resin composition, flexible printed-circuit board cover film, flexibility coat copper plate and preparation method thereof - Google Patents
A kind of halogen-free resin composition, flexible printed-circuit board cover film, flexibility coat copper plate and preparation method thereof Download PDFInfo
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- CN108676475A CN108676475A CN201810462519.XA CN201810462519A CN108676475A CN 108676475 A CN108676475 A CN 108676475A CN 201810462519 A CN201810462519 A CN 201810462519A CN 108676475 A CN108676475 A CN 108676475A
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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
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/04—Epoxynovolacs
-
- 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
- B32B15/20—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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- 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
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/04—Epoxynovolacs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention provides a kind of halogen-free resin composition, flexible printed-circuit board cover film, flexibility coat copper plate and preparation method thereof, the halogen-free resin composition includes the polyester being scattered in organic solvent and polyamide block copolymer, flexible-epoxy, phosphorous epoxy resin, polyfunctional epoxy resin, curing agent, curing accelerator, phosphonium flame retardant and antioxidant.The present invention can form interpenetrating polymer networks structure by the cooperation of the block copolymer of polyester and polyamide and flexible-epoxy, phosphorous epoxy resin, polyfunctional epoxy resin, with excellent flexibility, be not in dendrite when resistance to Ion transfer is tested, good insulating, there is excellent peel strength, heat resistance, dimensional stability, chemical resistance and processing performance simultaneously, anti-flammability is up to 0 grade of UL94 VTM.
Description
Technical field
The invention belongs to flexibility coat copper plate technical field, it is related to a kind of halogen-free resin composition, flexible printed-circuit board is used
Cover film, flexibility coat copper plate and preparation method thereof.
Background technology
In recent years, while electronic product is rapidly developed towards light, thin, short, small direction, flexible print has also effectively been pushed
The development of circuit board processed.The flexible printed-circuit board made of flexibility coat copper plate is very suitable for three dimensions installation, can make cloth
Line more rationally, more compact structure, save installation space, be widely used in mobile phone, digital camera, laptop etc. just
It takes in formula electronic equipment and the fields such as flat panel TV, automotive electronics, instrument and meter, medical instrument, aerospace, military project.
Flexibility coat copper plate can be divided into gluing dosage form flexibility coat copper plate and adhesion without adhesiver dosage form flexibility coat copper plate two major classes.Adhesive
Type flexibility coat copper plate has certain comparative advantages relative to adhesion without adhesiver dosage form flexibility coat copper plate, and over a period to come, the two will simultaneously
It deposits.Cover film is the film-shaped insulative material in Kapton or polyester film surface single spreading, primarily serves welding resistance
And protection circuit is not damaged by forms such as the pollutions of dust, moisture, chemicals, while there is certain flexibility and enhancing
Effect, can reduce the influence of conductor stress in bending process, improve the resistance to deflection of flexible printed-circuit board.
Either gluing dosage form flexibility coat copper plate or cover film, are required for using adhesive, and common adhesive master
It to be epoxy adhesive.However, common epoxy adhesive brittleness is big, the flexibility and flex endurant of flexible printed circuit cannot be satisfied
Property require.Generally use nbr carboxyl terminal is to epoxy adhesive toughening, and in general, nbr carboxyl terminal dosage is got over
More, flexibility is better, but dosage too conference directly results in the decline of the performances such as heat resistance, resistance to ion transport.Currently, end carboxyl
Application of the nitrile rubber toughening modifying epoxy adhesive in flexibility coat copper plate and cover film is primarily present resistance to ag(e)ing difference and resistance to
The problem of ion transport, first problem is due to containing a large amount of unsaturated double-bonds in nbr carboxyl terminal strand, in height
Oxidative cleavage occurs for Wen Shiyi；Second Problem is due to having used initiator, emulsifier when synthesizing nbr carboxyl terminal
Etc. a variety of auxiliary agents so that remain sodium ion, potassium ion and hydrolysis chlorion plasma impurity in product, cause to use end carboxyl fourth
The epoxy binder modified cover film of nitrile rubber generates dendrite when resistance to Ion transfer is tested.Two above problem be all by
It is determined in the chemical constitution and synthetic method of nbr carboxyl terminal, it is difficult to thoroughly be solved from the angle of formula adjustment.
Therefore, it is badly in need of a kind of technical strategies to solve the problems, such as this.
Invention content
In view of the problems of the existing technology, the purpose of the present invention is to provide a kind of halogen-free resin composition, flexible prints
Circuit board cover film processed, flexibility coat copper plate and preparation method thereof.
For this purpose, the present invention uses following technical scheme：
On the one hand, the present invention provides a kind of halogen-free resin composition, and the halogen-free resin composition is organic including being scattered in
Polyester in solvent and polyamide block copolymer, flexible-epoxy, phosphorous epoxy resin, polyfunctional epoxy resin, solidification
Agent, curing accelerator, phosphonium flame retardant and antioxidant.
In the present invention, by the block copolymer of polyester and polyamide and flexible-epoxy, phosphorous epoxy resin, more
The cooperation of functional epoxy resins can form interpenetrating polymer networks structure, have excellent flexibility, be tested in resistance to Ion transfer
When be not in dendrite, good insulating, while there is excellent peel strength, heat resistance, dimensional stability, chemical resistance
And processing performance, anti-flammability is up to UL94VTM-0 grades.
Preferably, the halogen-free resin composition includes the component of following parts by weight：10-30 parts (such as 10 parts, 13 parts,
15 parts, 18 parts, 20 parts, 23 parts, 25 parts, 28 parts or 30 parts) polyester and polyamide block copolymer, 10-20 parts (such as 10 parts,
12 parts, 14 parts, 16 parts, 18 parts or 20 parts) flexible-epoxy, 5-10 parts (such as 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts)
Phosphorous epoxy resin, 45-50 parts of (such as 45 parts, 46 parts, 47 parts, 48 parts, 49 parts or 50 parts) polyfunctional epoxy resins, 1-15 parts
(such as 1 part, 2 parts, 3 parts, 4 parts or 5 parts) curing agent, 0.1-0.3 parts (such as 0.1 part, 0.15 part, 0.2 part, 0.25 part or 0.3
Part) curing accelerator, 15-20 parts of (such as 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts) phosphonium flame retardants and 0.1-0.5
Part (such as 0.1 part, 0.2 part, 0.3 part, 0.4 part or 0.5 part) antioxidant.
Preferably, the solid content of the halogen-free resin composition be 30-50wt%, such as 30wt%, 32wt%,
34wt%, 36wt%, 38wt%, 40wt%, 43wt%, 45wt%, 48wt% or 50wt%.
Composition includes organic solvent in the present invention so that the solid content of the halogen-free resin composition is 30-
50wt% so that composition has suitable viscosity, to provide good processability, ensures do not occur apparent lack in coating procedure
It falls into.
Preferably, the organic solvent is acetone, butanone, toluene, ethyl alcohol, isopropanol, cyclohexanone, ethylene glycol monomethyl ether, third
In glycol methyl ether, propylene glycol methyl ether acetate or ethyl acetate any one or at least two combination.
Preferably, the crystallinity of the polyester and polyamide block copolymer be 5-15%, such as 5%, 6%, 7%,
8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%.Crystallinity is too high, then can not be dissolved with solvent；Crystallinity is too
Low, then heat resistance is insufficient, cannot be satisfied the heat resistant requirements of flexible printed-circuit board.
Preferably, the number-average molecular weight of the polyester and polyester block in polyamide block copolymer is 500-3000, example
Such as 500,600,800,1000,1300,1500,1800,2000,2300,2500,2800 or 3000, the number of polyamide-block is equal
Molecular weight is 2000-12000, such as 2000,3000,5000,8000,10000,11000 or 12000.
In the present invention, polyamide-block content is more, and heat resistance is better, but flexibility is insufficient, polarity is big, water absorption rate
It is high, poor with the cementability of thin polymer film；Polyester block content is higher, and heat resistance is poorer, but flexibility is better and polymer
The cementability of film and metal is good.
Preferably, in the polyester and polyamide block copolymer polyamide segment account in block copolymer polyester segment with
Polyamide segment total mole number at least 50% (such as 50%, 53%, 55%, 58%, 60%, 65%, 68%, 70%,
75%, 80% etc.), polyester segment accounts for at least 10% (example of polyester segment and polyamide segment total mole number in block copolymer
Such as 10%, 15%, 18%, 20%, 25%, 28%, 30%).
Preferably, the polyester and polyamide block copolymer tool is there are two glass transition temperature, respectively -40~-
60 DEG C (such as -40 DEG C, -43 DEG C, -45 DEG C, -48 DEG C, -50 DEG C, -53 DEG C, -55 DEG C, -58 DEG C or -60 DEG C) and -80~-130 DEG C
(such as -80 DEG C, -83 DEG C, -85 DEG C, -90 DEG C, -100 DEG C, -110 DEG C, -120 DEG C or -130 DEG C).
Preferably, the amine value of the polyester and polyamide block copolymer be 3-10mgKOH/g, such as 3mgKOH/g,
4mgKOH/g, 4.5mgKOH/g, 5mgKOH/g, 5.5mgKOH/g, 6mgKOH/g, 7mgKOH/g, 8mgKOH/g, 9mgKOH/g or
10mgKOH/g in the present invention, can not be anti-with epoxy resin if the amine value of polyester and polyamide block copolymer is too low
It answers, poor compatibility, toughening effect is limited；Amine value is too high, and reactivity is too high, easily leads to glue system (the i.e. described Halogen resin
Composition system) it is unstable.
Preferably, the flexible-epoxy is the epoxy resin having the following structure：
Wherein, m represents 1-3 (such as 1,2 or 3).
Preferably, the phosphorous epoxy resin is DOPO types phosphorous epoxy resin and/or the phosphorous asphalt mixtures modified by epoxy resin of DOPO-HQ types
Fat.Commercially available commodity include the XZ925309 of Dow Chemical Company manufactures, phosphorus content 3.0wt%, rivers and mountains
The G24, phosphorus content 2.4wt% of Jiang Huanhua Industrial Co., Ltd manufacture；Dainippon ink and Chemicals,
The Epiclon EXA9710, phosphorus content 3.0wt% of Incorporated manufactures.
Preferably, the polyfunctional epoxy resin be phenol type novolac epoxy resin, it is o-cresol type novolac epoxy resin, double
Phenol A types novolac epoxy resin, dicyclopentadiene phenol epoxy resin, biphenyl type novolac epoxy resin or four phenol ethane four shrink
One kind in glycerin ether or at least two mixture.The crosslinking of resin curing system can be improved in the polyfunctional epoxy resin
Density increases the cohesive strength of adhesive, improves peel strength, while the heat resistance and chemical resistance of resin also can be improved；It is excellent
Select biphenyl type novolac epoxy resin.
Preferably, the epoxide equivalent of the biphenyl type novolac epoxy resin be 310-350g/eq (such as 310g/eq,
315g/eq, 318g/eq, 320g/eq, 325g/eq, 328g/eq, 330g/eq, 335g/eq, 340g/eq, 345g/eq or
350g/eq), the biphenyl type epoxy novolac carbon yield is high, not only has excellent heat resistance, but also can improve resin system
Anti-flammability.
Preferably, the curing agent is amine curing agent and/or phenolic curing agent.
Preferably, the amine curing agent can be selected from dicyandiamide, 4,4'- diaminodiphenylsulfones, 3,3'- diaminodiphenylsulfones
In diaminodiphenylmethane any one or at least two mixture.
Preferably, the phenolic curing agent is phosphorus containing phenolic resin.The phosphorus containing phenolic resin can improve resin
The anti-flammability of composition, commercially available commodity have the XZ92741 etc. that Dow Chemical Company are manufactured.
Preferably, the curing accelerator be imidazoles accelerating agent, preferably 2-methylimidazole, 2-ethyl-4-methylimidazole,
In 2- phenylimidazoles or 1- 1-cyanoethyl-2-methylimidazoles any one or at least two mixture.
Preferably, the preferred SPB-100 of the phosphonium flame retardant (manufacture of Ben Otsuka Chemical Co., Ltd), OP-935
(German Clariant Corporation manufacture), OP-930 (German Clariant Corporation manufacture), SP-703H (four countries are melted into Co., Ltd.'s manufacture)
Deng.
Preferably, the antioxidant is Hinered phenols antioxidant, the preferred antioxidant 1010 of the Hinered phenols antioxidant, anti-
In oxygen agent 168, antioxidant 1222 or antioxidant 1076 any one or at least two mixture.Antioxidant can slow down or
The progress for preventing ageing process in cover film hot pressing, is necessary in resin combination.
The preparation method of halogen-free resin composition of the present invention is by polyester and polyamide block copolymer, flexible epoxy
Resin, phosphorous epoxy resin, polyfunctional epoxy resin, curing agent, curing accelerator, phosphonium flame retardant, antioxidant and organic molten
Agent is mixed into liquid dispersion, using similar devices such as ball mill, jar mill, sand mills, and with the use of high shear stirring point
It is casually arranged with standby, the inorganic solid components of organic solid component and addition in the present composition and organic solvent is blended in one
It rises, obtains the halogen-free resin composition.
On the other hand, the present invention provides a kind of flexible printed-circuit board cover film, and the cover film includes polyimides
Film, halogen-free resin composition as described above coated in Kapton surface coating and be pressed on Halogen resin group
Close the release paper on object coating.
Preferably, the thickness of the polyimide insulative film is 10-50 μm, such as 10 μm, 15 μm, 20 μm, 25 μm, 30 μ
M, 35 μm, 40 μm, 45 μm or 50 μm.
Preferably, the thickness of the halogen-free resin composition coating is 5-45 μm, such as 5 μm, 8 μm, 10 μm, 13 μm, 15 μ
M, 18 μm, 20 μm, 23 μm, 25 μm, 28 μm, 30 μm, 33 μm, 35 μm, 40 μm, 45 μm, 48 μm or 50 μm.If coating thickness is too
It is thin, then it is bad to cover type；If coating thickness is too thick, excessive glue is serious, pollutes circuit.
On the other hand, described the present invention provides the preparation method of flexible printed-circuit board cover film as described above
Preparation method is：Halogen-free resin composition as described above is coated on polyimide insulative film, it is dry, organic solvent is removed,
The cured halogen-free resin composition coating in part is formed on polyimide insulative film, then presses itself and release paper,
Obtain the flexible printed-circuit board cover film.
Preferably, the drying is realized by online dry baking oven.
Preferably, the drying be 80~160 DEG C (such as 80 DEG C, 85 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130
DEG C, 140 DEG C, 150 DEG C or 160 DEG C) heating (such as 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes or 8 2~8 minutes
Minute).
Preferably, the temperature of the pressing is 70-90 DEG C, such as 70 DEG C, 75 DEG C, 78 DEG C, 80 DEG C, 83 DEG C, 85 DEG C, 88 DEG C
Or 90 DEG C.
On the other hand, the present invention provides a kind of flexibility coat copper plate, and the flexibility coat copper plate includes polyimide insulative film, applies
The coating for the halogen-free resin composition as described above being overlying on polyimide insulative film and it is pressed on halogen-free resin composition
Copper foil on coating.
Preferably, the thickness of the polyimide insulative film is 10-100 μm, such as 10 μm, 15 μm, 20 μm, 25 μm, 30 μ
M, 35 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm.
Preferably, the thickness of the halogen-free resin composition coating be 10-35 μm, such as 10 μm, 13 μm, 15 μm, 18 μm,
20 μm, 23 μm, 25 μm, 28 μm, 30 μm, 33 μm or 35 μm.
Preferably, the copper foil is rolled copper foil or electrolytic copper foil.
Preferably, the thickness of the copper foil be 9-50 μm, such as 9 μm, 12 μm, 15 μm, 18 μm, 20 μm, 25 μm, 28 μm,
30 μm, 35 μm, 38 μm, 40 μm, 45 μm, 48 μm or 50 μm.
On the other hand, the present invention provides the preparation method of flexibility coat copper plate as described above, the method includes following
Step：Halogen-free resin composition of the present invention is coated on polyimide insulative film, it is dry, organic solvent is removed, poly-
The cured halogen-free resin composition layer in part is formed on acid imide insulating film, and then itself and copper foil are pressed, then cured,
Obtain the flexibility coat copper plate.
Preferably, described halogen-free resin composition of the present invention is coated on polyimide insulative film can be single side
Coating or dual coating.
Preferably, the drying is realized by online dry baking oven.
Preferably, the drying be 80~160 DEG C (such as 80 DEG C, 85 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130
DEG C, 140 DEG C, 150 DEG C or 160 DEG C) heating (such as 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes or 8 2~8 minutes
Minute).
Preferably, the temperature of the pressing be 80-100 DEG C, such as 80 DEG C, 85 DEG C, 88 DEG C, 90 DEG C, 93 DEG C, 95 DEG C, 98
DEG C or 100 DEG C.
Preferably, the cured temperature be 120-170 DEG C, such as 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C,
145 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 165 DEG C or 170 DEG C.
Compared with the existing technology, the invention has the advantages that：
The present invention passes through the block copolymer of polyester and polyamide and flexible-epoxy, phosphorous epoxy resin, multifunctional
The cooperation of epoxy resin can form interpenetrating polymer networks structure, have excellent flexibility, not when resistance to Ion transfer is tested
It will appear dendrite, good insulating, while there is excellent peel strength, heat resistance, dimensional stability, chemical resistance and add
Work performance, anti-flammability is up to UL94VTM-0 grades.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.Those skilled in the art should be bright
, the embodiment, which is only to aid in, understands the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of halogen-free resin composition, by weight, including polyester and 10 parts of polyamide block copolymer, flexible epoxy
10 parts of resin, 5 parts of phosphorous epoxy resin (G24), 45 parts of phenol type novolac epoxy resin, 0.8 part of dicyandiamide, 4,4'- diamino
0.5 part of diphenyl sulphone (DPS), 0.1 part of 2-methylimidazole, 15 parts of phosphonium flame retardant (SPB-100), 0.1 part of antioxidant 1010.
The crystallinity of the polyester and polyamide block copolymer be 5%, glass transition temperature be -40 DEG C, -80
DEG C, amine value 3mgKOH/g, polyester segment number-average molecular weight 500, polyamide segment number-average molecular weight 2000, polyester segment accounts for copolymerization
Polyester segment and polyamide segment total mole number 10%, polyamide segment account for polyester segment and polyamide segment in copolymer in object
Total mole number 90%.
The polyester is adjusted with ethyl acetate with polyamide block copolymer, epoxy resin, curing agent, solidification to promote
The glue (solid content 30wt%) that agent, fire retardant and antioxidant form, is blended into halogen-free resin composition.
The halogen-free resin composition is applied to flexible printed-circuit board cover film.
Halogen-free resin composition as described above is coated in coating machine on the Kapton that thickness is 12.5 μm, resin
Composition coating thickness is 5 μm；Then it is handled 3 minutes at 160 DEG C, to form cured group of part on Kapton
Close nitride layer；Finally the covering of the halogen-free fire-retardant epoxy resin composition is obtained with the compound winding of release paper at 70 DEG C
Film.
Embodiment 2
A kind of halogen-free resin composition, by weight, including polyester and 20 parts of polyamide block copolymer, flexible epoxy
15 parts of resin, 8 parts of phosphorous epoxy resin (XZ925309), 48 parts of dicyclopentadiene phenol epoxy resin, diaminodiphenylmethane
1.2 parts, 0.2 part of 2-ethyl-4-methylimidazole, 18 parts of phosphonium flame retardant (OP-935), 0.2 part of irgasfos 168.
The crystallinity of the polyester and polyamide block copolymer be 8%, glass transition temperature be -50 DEG C, -90
DEG C, amine value 5mgKOH/g, polyester segment number-average molecular weight 800, polyamide segment number-average molecular weight 4000, polyester segment accounts for copolymerization
Polyester segment and polyamide segment total mole number 20%, polyamide segment account for polyester segment and polyamide segment in copolymer in object
Total mole number 80%.
The polyester is adjusted with toluene and ethyl alcohol with polyamide block copolymer, epoxy resin, curing agent, solidification to promote
The glue (solid content 40wt%) that agent, fire retardant and antioxidant form, is blended into halogen-free resin composition.
The halogen-free resin composition is applied to flexible printed-circuit board cover film.
Halogen-free resin composition as described above is coated in coating machine on the Kapton that thickness is 25 μm, resin group
It is 20 μm to close object coating thickness；Then it is handled 5 minutes at 140 DEG C, to form cured group of part on Kapton
Close nitride layer；Finally the covering of the halogen-free fire-retardant epoxy resin composition is obtained with the compound winding of release paper at 80 DEG C
Film.
Embodiment 3
A kind of halogen-free resin composition, by weight, including polyester and 25 parts of polyamide block copolymer, flexible epoxy
20 parts of resin, 10 parts of phosphorous epoxy resin (EXA9710), 50 parts of biphenyl type novolac epoxy resin, 2 parts of dicyandiamide, 2- phenyl miaows
0.3 part of azoles, 20 parts of phosphonium flame retardant (SP-703H), 0.5 part of antioxidant 1076.
The crystallinity of the polyester and polyamide block copolymer be 12%, glass transition temperature be -55 DEG C, -120
DEG C, amine value 8mgKOH/g, polyester segment number-average molecular weight 2000, polyamide segment number-average molecular weight 9000, polyester segment accounts for total
Polyester segment and polyamide segment total mole number 40%, polyamide segment account for polyester segment and polyamide chains in copolymer in polymers
Section total mole number 60%.
The polyester and polyamide block copolymer, epoxy resin, curing agent, curing accelerator, resistance are adjusted with acetone
The glue (solid content 50wt%) for firing agent and antioxidant composition, is blended into halogen-free resin composition.
The halogen-free resin composition is applied to flexible printed-circuit board cover film.
Halogen-free resin composition as described above is coated in coating machine on the Kapton that thickness is 40 μm, resin group
It is 35 μm to close object coating thickness；Then it is handled 6 minutes at 120 DEG C, to form cured group of part on Kapton
Close nitride layer；Finally the covering of the halogen-free fire-retardant epoxy resin composition is obtained with the compound winding of release paper at 90 DEG C
Film.
Embodiment 4
A kind of halogen-free resin composition, by weight, including polyester and 30 parts of polyamide block copolymer, flexible epoxy
18 parts of resin, 10 parts of phosphorous epoxy resin (G24), 50 parts of four phenol ethane, four glycidol ether, 3,3'- diaminodiphenylsulfones 2
Part, 0.3 part of 1- 1-cyanoethyl-2-methylimidazoles, 20 parts of phosphonium flame retardant (SP-703H), 1,222 0.5 parts of antioxidant.
The crystallinity of the polyester and polyamide block copolymer be 15%, glass transition temperature be -60 DEG C, -130
DEG C, amine value 10mgKOH/g, polyester segment number-average molecular weight 3000, polyamide segment number-average molecular weight 12000, polyester segment accounts for
Polyester segment and polyamide segment total mole number 50%, polyamide segment account for polyester segment and polyamide in copolymer in copolymer
Segment total mole number 50%.
The polyester and polyamide block copolymer, epoxy resin, curing agent, curing accelerator, resistance are adjusted with butanone
The glue (solid content 45wt%) for firing agent and antioxidant composition, is blended into halogen-free resin composition.
The halogen-free resin composition is applied to flexible printed-circuit board cover film.
Halogen-free resin composition as described above is coated in coating machine on the Kapton that thickness is 50 μm, resin group
It is 45 μm to close object coating thickness；Then it is handled 8 minutes at 90 DEG C, to form the cured combination in part on Kapton
Nitride layer；Finally the cover film of the halogen-free fire-retardant epoxy resin composition is obtained with the compound winding of release paper at 90 DEG C.
Embodiment 5
A kind of halogen-free resin composition, by weight, including polyester and 25 parts of polyamide block copolymer, flexible epoxy
20 parts of resin, 8 parts of phosphorous epoxy resin (EXA9710), 45 parts of o-cresol type novolac epoxy resin, phosphorus containing phenolic resin
(XZ92741) 2 parts, 10 parts of diaminodiphenylmethane, 0.2 part of 2- phenylimidazoles, 15 parts of phosphonium flame retardant (SP703H), antioxidant
168 0.1 parts.
The crystallinity of the polyester and polyamide block copolymer be 12%, glass transition temperature be -55 DEG C, -120
DEG C, amine value 8mgKOH/g, polyester segment number-average molecular weight 2000, polyamide segment number-average molecular weight 9000, polyester segment accounts for total
Polyester segment and polyamide segment total mole number 40%, polyamide segment account for polyester segment and polyamide chains in copolymer in polymers
Section total mole number 60%.
The polyester and polyamide block copolymer, epoxy resin, curing agent, curing accelerator, resistance are adjusted with butanone
The glue (solid content 45wt%) for firing agent and antioxidant composition, is blended into halogen-free resin composition.
The halogen-free resin composition is applied to flexible printed-circuit board cover film.
Halogen-free resin composition as described above is coated in coating machine on the Kapton that thickness is 40 μm, resin group
It is 35 μm to close object coating thickness；Then it is handled 6 minutes at 120 DEG C, to form cured group of part on Kapton
Close nitride layer；Finally the covering of the halogen-free fire-retardant epoxy resin composition is obtained with the compound winding of release paper at 90 DEG C
Film.
Embodiment 6
A kind of halogen-free resin composition, by weight, including polyester and 30 parts of polyamide block copolymer, flexible epoxy
20 parts of resin, 10 parts of phosphorous epoxy resin (XZ925309), 50 parts of bisphenol A-type novolac epoxy resin, phosphorus containing phenolic resin
(XZ92741) 3 parts, 12 parts of 3,3 '=diaminodiphenylsulfone, 0.3 part of 1- 1-cyanoethyl-2-methylimidazoles, phosphonium flame retardant (OP-
935) 20 parts, 0.5 part of antioxidant 1076.
The crystallinity of the polyester and polyamide block copolymer be 15%, glass transition temperature be -60 DEG C, -130
DEG C, amine value 10mgKOH/g, polyester segment number-average molecular weight 3000, polyamide segment number-average molecular weight 12000, polyester segment accounts for
Polyester segment and polyamide segment total mole number 50%, polyamide segment account for polyester segment and polyamide in copolymer in copolymer
Segment total mole number 50%.
The polyester and polyamide block copolymer, epoxy resin, curing agent, accelerating agent, resistance are adjusted with ethyl acetate
The glue (solid content 35wt%) for firing agent and antioxidant composition, is blended into halogen-free resin composition.
Halogen-free resin composition as described above is coated in coating machine on the Kapton that thickness is 40 μm, resin group
It is 35 μm to close object coating thickness；Then it is handled 6 minutes at 120 DEG C, to form cured group of part on Kapton
Close nitride layer；Finally the covering of the halogen-free fire-retardant epoxy resin composition is obtained with the compound winding of release paper at 90 DEG C
Film.
Embodiment 7
Halogen-free resin composition described in embodiment 1 is applied to flexibility coat copper plate.
Halogen-free resin composition as described above is coated in the Kapton surface that thickness is 10 μm, resin with coating machine
Composition coating thickness is 10 μm；Then it is handled 5 minutes in 130 DEG C, with cured in Kapton surface forming part
Composition layer；Then the rolled copper foil for being 12 μm with thickness at 90 DEG C is compound, finally cures at 160 DEG C, obtained flexibility is covered
Copper coin.
Embodiment 8
Halogen-free resin composition described in embodiment 2 is applied to flexibility coat copper plate.
The halogen-free resin composition is coated in the Kapton surface that thickness is 50 μm, resin combination with coating machine
Object coating thickness is 20 μm；Then it is handled 5 minutes in 130 DEG C, in the cured combination of Kapton surface forming part
Nitride layer；Then the rolled copper foil for being 35 μm with thickness at 90 DEG C is compound, finally cures at 140 DEG C, and flexibility coat copper plate is made.
Embodiment 9
Halogen-free resin composition described in embodiment 3 is applied to flexibility coat copper plate.
Halogen-free resin composition as described above is coated in the Kapton surface that thickness is 100 μm, tree with coating machine
Oil/fat composition coating thickness is 35 μm；Then it is handled 5 minutes in 130 DEG C, to cure in Kapton surface forming part
Composition layer；Then the electrolytic copper foil for being 50 μm with thickness at 90 DEG C is compound, finally cures at 120 DEG C, and flexibility is made
Copper-clad plate.
Embodiment 10
Halogen-free resin composition described in embodiment 4 is applied to flexibility coat copper plate.
Resin combination as described above is coated in the Kapton surface that thickness is 70 μm, resin combination with coating machine
Object coating thickness is 20 μm；Then it is handled 5 minutes in 130 DEG C, in the cured combination of Kapton surface forming part
Nitride layer；Then the electrolytic copper foil for being 35 μm with thickness at 90 DEG C is compound, finally cures at 170 DEG C, and flexibility coat copper plate is made.
Embodiment 11
Halogen-free resin composition described in embodiment 5 is applied to flexibility coat copper plate.
Resin combination as described above is coated in the Kapton surface that thickness is 30 μm, resin combination with coating machine
Object coating thickness is 20 μm；Then it is handled 5 minutes in 130 DEG C, in the cured combination of Kapton surface forming part
Nitride layer；Then the electrolytic copper foil for being 35 μm with thickness at 90 DEG C is compound, finally cures at 170 DEG C, and flexibility coat copper plate is made.
Embodiment 12
Halogen-free resin composition described in embodiment 6 is applied to flexibility coat copper plate.
Halogen-free resin composition as described above is coated in the Kapton surface that thickness is 40 μm, resin with coating machine
Composition coating thickness is 35 μm；Then it is handled 6 minutes at 120 DEG C, it is cured to form part on Kapton
Composition layer；The rolled copper foil for being finally 9 μm with thickness at 90 DEG C is compound, finally cures at 140 DEG C, and flexible copper-clad is made
Plate.
Comparative example 1
A kind of halogen-free resin composition, by weight, including polyester and 5 parts of polyamide block copolymer, flexible epoxy
10 parts of resin, 5 parts of phosphorous epoxy resin (G24), 45 parts of phenol type novolac epoxy resin, 0.8 part of dicyandiamide, 4,4'- diamino
0.5 part of diphenyl sulphone (DPS), 0.1 part of 2-methylimidazole, 15 parts of phosphonium flame retardant (SPB-100), 0.1 part of antioxidant 1010.
The crystallinity of the polyester and polyamide block copolymer be 5%, glass transition temperature be -40 DEG C, -80
DEG C, amine value 3mgKOH/g, polyester segment number-average molecular weight 500, polyamide segment number-average molecular weight 2000, polyester segment accounts for copolymerization
Polyester segment and polyamide segment total mole number 10%, polyamide segment account for polyester segment and polyamide segment in copolymer in object
Total mole number 90%.
The polyester is adjusted with ethyl acetate with polyamide block copolymer, epoxy resin, curing agent, solidification to promote
The glue (solid content 30wt%) that agent, fire retardant and antioxidant form, is blended into halogen-free resin composition.
The halogen-free resin composition is applied to flexible printed-circuit board cover film.
Halogen-free resin composition as described above is coated in coating machine on the Kapton that thickness is 12.5 μm, resin
Composition coating thickness is 5 μm；Then it is handled 3 minutes at 160 DEG C, to form cured group of part on Kapton
Close nitride layer；Finally the covering of the halogen-free fire-retardant epoxy resin composition is obtained with the compound winding of release paper at 70 DEG C
Film.
Comparative example 2
A kind of halogen-free resin composition, by weight, including polyester and 40 parts of polyamide block copolymer, flexible epoxy
15 parts of resin, 8 parts of phosphorous epoxy resin (XZ925309), 48 parts of dicyclopentadiene phenol epoxy resin, diaminodiphenylmethane
1.2 parts, 0.2 part of 2-ethyl-4-methylimidazole, 18 parts of phosphonium flame retardant (OP-935), 0.2 part of irgasfos 168.
The crystallinity of the polyester and polyamide block copolymer be 8%, glass transition temperature be -50 DEG C, -90
DEG C, amine value 5mgKOH/g, polyester segment number-average molecular weight 800, polyamide segment number-average molecular weight 4000, polyester segment accounts for copolymerization
Polyester segment and polyamide segment total mole number 20%, polyamide segment account for polyester segment and polyamide segment in copolymer in object
Total mole number 80%.
The polyester is adjusted with toluene and ethyl alcohol with polyamide block copolymer, epoxy resin, curing agent, solidification to promote
The glue (solid content 40wt%) that agent, fire retardant and antioxidant form, is blended into halogen-free resin composition.
The halogen-free resin composition is applied to flexible printed-circuit board cover film.
Halogen-free resin composition as described above is coated in coating machine on the Kapton that thickness is 25 μm, resin group
It is 20 μm to close object coating thickness；Then it is handled 5 minutes at 140 DEG C, to form cured group of part on Kapton
Close nitride layer；Finally the covering of the halogen-free fire-retardant epoxy resin composition is obtained with the compound winding of release paper at 80 DEG C
Film.
Comparative example 3
A kind of halogen-free resin composition, by weight, including 10 parts of polyester, 15 parts of polyamide, flexible-epoxy 20
Part, 10 parts of phosphorous epoxy resin (EXA9710), 50 parts of biphenyl type novolac epoxy resin, 2 parts of dicyandiamide, 2- phenylimidazoles 0.3
Part, 20 parts of phosphonium flame retardant (SP-703H), 0.5 part of antioxidant 1076.
The polyester fiberglass transition temperature is -120 DEG C；Polyamide crystallinity is 12%, amine value 8mgKOH/g, glass
It is -55 DEG C to change transition temperature.The polyester, polyamide, epoxy resin, curing agent, curing accelerator, fire-retardant is adjusted with acetone
The glue (solid content 50wt%) of agent and antioxidant composition, is blended into halogen-free resin composition.
The halogen-free resin composition is applied to flexible printed-circuit board cover film.
Halogen-free resin composition as described above is coated in coating machine on the Kapton that thickness is 40 μm, resin group
It is 35 μm to close object coating thickness；Then it is handled 6 minutes at 120 DEG C, to form cured group of part on Kapton
Close nitride layer；Finally the covering of the halogen-free fire-retardant epoxy resin composition is obtained with the compound winding of release paper at 90 DEG C
Film.
Comparative example 4
A kind of halogen-free resin composition, by weight, including 30 parts of polyester, 18 parts of flexible-epoxy, phosphorous epoxy
10 parts of resin (G24), 50 parts of four phenol ethane, four glycidol ether, 2 parts of 3,3'- diaminodiphenylsulfones, 1- cyanoethyl -2- first
0.3 part of base imidazoles, 20 parts of phosphonium flame retardant (SP-703H), 1,222 0.5 parts of antioxidant.
The glass transition temperature of the polyester is -130 DEG C.
The polyester, epoxy resin, curing agent, curing accelerator, fire retardant and antioxidant composition are adjusted with butanone
Glue (solid content 45wt%), is blended into halogen-free resin composition.
The halogen-free resin composition is applied to flexible printed-circuit board cover film.
Halogen-free resin composition as described above is coated in coating machine on the Kapton that thickness is 50 μm, resin group
It is 45 μm to close object coating thickness；Then it is handled 8 minutes at 90 DEG C, to form the cured combination in part on Kapton
Nitride layer；Finally the cover film of the halogen-free fire-retardant epoxy resin composition is obtained with the compound winding of release paper at 90 DEG C.
Comparative example 5
A kind of halogen-free resin composition, by weight, including 25 parts of polyamide, 20 parts of flexible-epoxy, phosphorous ring
8 parts of oxygen resin (EXA9710), 45 parts of o-cresol type novolac epoxy resin, 2 parts of phosphorus containing phenolic resin (XZ92741), diamino two
10 parts of phenylmethane, 0.2 part of 2- phenylimidazoles, 15 parts of phosphonium flame retardant (SP703H), 0.1 part of irgasfos 168.
The glass transition temperature of the polyamide is -55 DEG C, crystallinity 12%, amine value 8mgKOH/g.
The polyamide, epoxy resin, curing agent, curing accelerator, fire retardant and antioxidant composition are adjusted with butanone
Glue (solid content 45wt%), be blended into halogen-free resin composition.
The halogen-free resin composition is applied to flexible printed-circuit board cover film.
Halogen-free resin composition as described above is coated in coating machine on the Kapton that thickness is 40 μm, resin group
It is 35 μm to close object coating thickness；Then it is handled 6 minutes at 120 DEG C, to form cured group of part on Kapton
Close nitride layer；Finally the covering of the halogen-free fire-retardant epoxy resin composition is obtained with the compound winding of release paper at 90 DEG C
Film.
Comparative example 6
A kind of halogen-free resin composition, by weight, including polyester and 30 parts of polyamide block copolymer, flexible epoxy
20 parts of resin, 10 parts of phosphorous epoxy resin (XZ925309), 50 parts of bisphenol A-type novolac epoxy resin, phosphorus containing phenolic resin
(XZ92741) 3 parts, 12 parts of 3,3 '-diaminodiphenylsulfone, 0.3 part of 1- 1-cyanoethyl-2-methylimidazoles, phosphonium flame retardant (OP-
935) 20 parts, 0.5 part of antioxidant 1076.
The crystallinity of the polyester and polyamide block copolymer be 3%, glass transition temperature be -60 DEG C, -130
DEG C, amine value 10mgKOH/g, polyester segment number-average molecular weight 3000, polyamide segment number-average molecular weight 12000, polyester segment accounts for
Polyester segment and polyamide segment total mole number 50%, polyamide segment account for polyester segment and polyamide in copolymer in copolymer
Segment total mole number 50%.
The polyester and polyamide block copolymer, epoxy resin, composite curing agent, fire retardant are adjusted with ethyl acetate
And the glue (solid content 35wt%) of antioxidant composition, it is blended into halogen-free resin composition.
Halogen-free resin composition as described above is coated in coating machine on the Kapton that thickness is 40 μm, resin group
It is 35 μm to close object coating thickness；Then it is handled 6 minutes at 120 DEG C, to form cured group of part on Kapton
Close nitride layer；Finally the covering of the halogen-free fire-retardant epoxy resin composition is obtained with the compound winding of release paper at 90 DEG C
Film.
Comparative example 7
A kind of halogen-free resin composition, by weight, including polyester and 30 parts of polyamide block copolymer, flexible epoxy
20 parts of resin, 10 parts of phosphorous epoxy resin (XZ925309), 50 parts of bisphenol A-type novolac epoxy resin, phosphorus containing phenolic resin
(XZ92741) 3 parts, 12 parts of 3,3 '-diaminodiphenylsulfone, 0.3 part of 1- 1-cyanoethyl-2-methylimidazoles, phosphonium flame retardant (OP-
935) 20 parts, 0.5 part of antioxidant 1076.
The crystallinity of the polyester and polyamide block copolymer be 18%, glass transition temperature be -60 DEG C, -130
DEG C, amine value 10mgKOH/g, polyester segment number-average molecular weight 3000, polyamide segment number-average molecular weight 12000, polyester segment accounts for
Polyester segment and polyamide segment total mole number 50%, polyamide segment account for polyester segment and polyamide in copolymer in copolymer
Segment total mole number 50%.
The polyester and polyamide block copolymer, epoxy resin, composite curing agent, fire retardant are adjusted with ethyl acetate
And the glue of antioxidant composition, however since used block copolymer crystallinity is excessively high, it can not be obtained with solvent dissolving
Halogen-free resin composition, so that being unable to get cover film.
Comparative example 8
A kind of halogen-free resin composition, by weight, including polyester and 20 parts of polyamide block copolymer, flexible epoxy
15 parts of resin, 8 parts of phosphorous epoxy resin (XZ925309), 48 parts of dicyclopentadiene phenol epoxy resin, diaminodiphenylmethane
1.2 parts, 0.2 part of 2-ethyl-4-methylimidazole, 18 parts of phosphonium flame retardant (OP-935), 0.2 part of irgasfos 168.
The crystallinity of the polyester and polyamide block copolymer be 8%, glass transition temperature be -50 DEG C, -90
DEG C, amine value 5mgKOH/g, polyester segment number-average molecular weight 800, polyamide segment number-average molecular weight 4000, polyester segment accounts for copolymerization
Polyester segment and polyamide segment total mole number 60%, polyamide segment account for polyester segment and polyamide segment in copolymer in object
Total mole number 40%.
The polyester is adjusted with toluene and ethyl alcohol with polyamide block copolymer, epoxy resin, curing agent, solidification to promote
The glue (solid content 40wt%) that agent, fire retardant and antioxidant form, is blended into halogen-free resin composition.
The halogen-free resin composition is applied to flexible printed-circuit board cover film.
Halogen-free resin composition as described above is coated in coating machine on the Kapton that thickness is 25 μm, resin group
It is 20 μm to close object coating thickness；Then it is handled 5 minutes at 140 DEG C, to form cured group of part on Kapton
Close nitride layer；Finally the covering of the halogen-free fire-retardant epoxy resin composition is obtained with the compound winding of release paper at 80 DEG C
Film.
Comparative example 9
A kind of halogen-free resin composition, by weight, including polyester and 20 parts of polyamide block copolymer, flexible epoxy
15 parts of resin, 8 parts of phosphorous epoxy resin (XZ925309), 48 parts of dicyclopentadiene phenol epoxy resin, diaminodiphenylmethane
1.2 parts, 0.2 part of 2-ethyl-4-methylimidazole, 18 parts of phosphonium flame retardant (OP-935), 0.2 part of irgasfos 168.
The crystallinity of the polyester and polyamide block copolymer be 8%, glass transition temperature be -50 DEG C, -90
DEG C, amine value 5mgKOH/g, polyester segment number-average molecular weight 800, polyamide segment number-average molecular weight 4000, polyester segment accounts for copolymerization
Polyester segment and polyamide segment total mole number 5%, polyamide segment account for polyester segment and polyamide segment in copolymer in object
Total mole number 95%.
The polyester is adjusted with toluene and ethyl alcohol with polyamide block copolymer, epoxy resin, curing agent, solidification to promote
The glue (solid content 40wt%) that agent, fire retardant and antioxidant form, is blended into halogen-free resin composition.
The halogen-free resin composition is applied to flexible printed-circuit board cover film.
Halogen-free resin composition as described above is coated in coating machine on the Kapton that thickness is 25 μm, resin group
It is 20 μm to close object coating thickness；Then it is handled 5 minutes at 140 DEG C, to form cured group of part on Kapton
Close nitride layer；Finally the covering of the halogen-free fire-retardant epoxy resin composition is obtained with the compound winding of release paper at 80 DEG C
Film.
Comparative example 10
A kind of halogen-free resin composition, by weight, including polyester and 25 parts of polyamide block copolymer, flexible epoxy
20 parts of resin, 10 parts of phosphorous epoxy resin (EXA9710), 50 parts of biphenyl type novolac epoxy resin, 2 parts of dicyandiamide, 2- phenyl miaows
0.3 part of azoles, 20 parts of phosphonium flame retardant (SP-703H), 0.5 part of antioxidant 1076.
The crystallinity of the polyester and polyamide block copolymer be 12%, glass transition temperature be -55 DEG C, -120
DEG C, amine value 2mgKOH/g, polyester segment number-average molecular weight 2000, polyamide segment number-average molecular weight 9000, polyester segment accounts for total
Polyester segment and polyamide segment total mole number 40%, polyamide segment account for polyester segment and polyamide chains in copolymer in polymers
Section total mole number 60%.
The polyester and polyamide block copolymer, epoxy resin, curing agent, curing accelerator, resistance are adjusted with acetone
The glue (solid content 50wt%) for firing agent and antioxidant composition, is blended into halogen-free resin composition.
The halogen-free resin composition is applied to flexible printed-circuit board cover film.
Halogen-free resin composition as described above is coated in coating machine on the Kapton that thickness is 40 μm, resin group
It is 35 μm to close object coating thickness；Then it is handled 6 minutes at 120 DEG C, to form cured group of part on Kapton
Close nitride layer；Finally the covering of the halogen-free fire-retardant epoxy resin composition is obtained with the compound winding of release paper at 90 DEG C
Film.
Comparative example 11
A kind of halogen-free resin composition, by weight, including polyester and 25 parts of polyamide block copolymer, flexible epoxy
20 parts of resin, 10 parts of phosphorous epoxy resin (EXA9710), 50 parts of biphenyl type novolac epoxy resin, 2 parts of dicyandiamide, 2- phenyl miaows
0.3 part of azoles, 20 parts of phosphonium flame retardant (SP-703H), 0.5 part of antioxidant 1076.
The crystallinity of the polyester and polyamide block copolymer be 12%, glass transition temperature be -55 DEG C, -120
DEG C, amine value 15mgKOH/g, polyester segment number-average molecular weight 2000, polyamide segment number-average molecular weight 9000, polyester segment accounts for total
Polyester segment and polyamide segment total mole number 40%, polyamide segment account for polyester segment and polyamide chains in copolymer in polymers
Section total mole number 60%.
The polyester and polyamide block copolymer, epoxy resin, curing agent, curing accelerator, resistance are adjusted with acetone
The glue (solid content 50wt%) for firing agent and antioxidant composition, is blended into halogen-free resin composition.
The halogen-free resin composition is applied to flexible printed-circuit board cover film.
Halogen-free resin composition as described above is coated in coating machine on the Kapton that thickness is 40 μm, however by
Excessively high in block copolymer amine value, glue system viscosity steeply rises, and can not be coated with and prepare cover film.
Comparative example 12
Halogen-free resin composition described in comparative example 1 is applied to flexibility coat copper plate.
The halogen-free resin composition is coated in the Kapton surface that thickness is 50 μm, resin combination with coating machine
Object coating thickness is 20 μm；Then it is handled 5 minutes in 130 DEG C, in the cured combination of Kapton surface forming part
Nitride layer；Then the rolled copper foil for being 35 μm with thickness at 90 DEG C is compound, finally cures at 140 DEG C, and flexibility coat copper plate is made.
Comparative example 13
Halogen-free resin composition described in comparative example 2 is applied to flexibility coat copper plate.
The halogen-free resin composition is coated in the Kapton surface that thickness is 10 μm, resin combination with coating machine
Object coating thickness is 10 μm；Then it is handled 5 minutes in 130 DEG C, in the cured combination of Kapton surface forming part
Nitride layer；Then the rolled copper foil for being 15 μm with thickness at 90 DEG C is compound, finally cures at 150 DEG C, and flexibility coat copper plate is made.
Comparative example 14
Halogen-free resin composition described in comparative example 3 is applied to flexibility coat copper plate.
The halogen-free resin composition is coated in the Kapton surface that thickness is 15 μm, resin combination with coating machine
Object coating thickness is 10 μm；Then it is handled 5 minutes in 140 DEG C, in the cured combination of Kapton surface forming part
Nitride layer；Then the rolled copper foil for being 9 μm with thickness at 90 DEG C is compound, finally cures at 150 DEG C, and flexibility coat copper plate is made.
Comparative example 15
Halogen-free resin composition described in comparative example 4 is applied to flexibility coat copper plate.
The halogen-free resin composition is coated in the Kapton surface that thickness is 25 μm, resin combination with coating machine
Object coating thickness is 18 μm；Then it is handled 5 minutes in 140 DEG C, in the cured combination of Kapton surface forming part
Nitride layer；Then the rolled copper foil for being 25 μm with thickness at 100 DEG C is compound, finally cures at 170 DEG C, and flexible copper-clad is made
Plate.
Comparative example 16
Halogen-free resin composition described in comparative example 5 is applied to flexibility coat copper plate.
The halogen-free resin composition is coated in the Kapton surface that thickness is 25 μm, resin combination with coating machine
Object coating thickness is 18 μm；Then it is handled 5 minutes in 140 DEG C, in the cured combination of Kapton surface forming part
Nitride layer；Then the rolled copper foil for being 25 μm with thickness at 100 DEG C is compound, finally cures at 170 DEG C, and flexible copper-clad is made
Plate.
Comparative example 17
Halogen-free resin composition described in comparative example 6 is applied to flexibility coat copper plate.
The halogen-free resin composition is coated in the Kapton surface that thickness is 50 μm, resin combination with coating machine
Object coating thickness is 30 μm；Then it is handled 5 minutes in 160 DEG C, in the cured combination of Kapton surface forming part
Nitride layer；Then the rolled copper foil for being 25 μm with thickness at 100 DEG C is compound, finally cures at 170 DEG C, and flexible copper-clad is made
Plate.
Comparative example 18
Halogen-free resin composition described in comparative example 8 is applied to flexibility coat copper plate.
The halogen-free resin composition is coated in the Kapton surface that thickness is 100 μm, resin group with coating machine
It is 30 μm to close object coating thickness；Then it is handled 5 minutes in 160 DEG C, in cured group of Kapton surface forming part
Close nitride layer；Then the rolled copper foil for being 50 μm with thickness at 100 DEG C is compound, finally cures at 170 DEG C, and flexible copper-clad is made
Plate.
Comparative example 19
Halogen-free resin composition described in comparative example 9 is applied to flexibility coat copper plate.
The halogen-free resin composition is coated in the Kapton surface that thickness is 25 μm, resin combination with coating machine
Object coating thickness is 20 μm；Then it is handled 5 minutes in 160 DEG C, in the cured combination of Kapton surface forming part
Nitride layer；Then the electrolytic copper foil for being 50 μm with thickness at 100 DEG C is compound, finally cures at 170 DEG C, and flexible copper-clad is made
Plate.
Comparative example 20
Halogen-free resin composition described in comparative example 10 is applied to flexibility coat copper plate.
The halogen-free resin composition is coated in the Kapton surface that thickness is 25 μm, resin combination with coating machine
Object coating thickness is 20 μm；Then it is handled 5 minutes in 120 DEG C, in the cured combination of Kapton surface forming part
Nitride layer；Then the electrolytic copper foil for being 50 μm with thickness at 100 DEG C is compound, finally cures at 170 DEG C, and flexible copper-clad is made
Plate.
Comparative example 21
Halogen-free resin composition described in comparative example 11 is applied to flexibility coat copper plate.
The halogen-free resin composition is coated in the Kapton surface that thickness is 75 μm, resin combination with coating machine
Object coating thickness is 35 μm；Then it is handled 5 minutes in 120 DEG C, in the cured combination of Kapton surface forming part
Nitride layer；Then the electrolytic copper foil for being 50 μm with thickness at 100 DEG C is compound, finally cures at 170 DEG C, however due to comparative example
Block copolymer amine value is excessively high in 11 halogen-free resin composition, and glue system viscosity steeply rises, and flexibility can not be prepared
Copper-clad plate.
Flexibility coat copper plate and cover film made from above-described embodiment and comparative example are tested for the property, performance data ratio
Relatively as shown in table 1-4.The wherein described existing product is polyamides prepared by CTBN (carboxyl-terminated polybutadiene acrylonitrile) modified epoxy
Imines cover film and flexibility coat copper plate.
Table 1
Table 2
Table 3
Table 4
The test method of the above covering membrane property is as follows：
(1) glue overflow amount：It is tested according to IPC-TM-650 2.3.17.1 methods, provides absolute value.
(2) type is covered：Covering filling capacity of the quantitative reaction cover film to circuit.Gained cover film is fitted in into p-wire
Road after pressing 80 seconds soon under the conditions of 180 DEG C/10MPa, whether there is bubble, filling not under 50 times of magnifying glasses between observation circuit
The defects of good.Measurement circuit includes the figure of 100 ± 10mm long straight lines, semicircle and right angle, and circuit copper is 25 μm thick, line width and line-spacing
It is 100 μm.
(3) peel strength：It is tested according to IPC-TM-650 2.4.9 methods, by cover film and 18 μm of rolled copper foil smooth surface pressures
It closes, is tested after solidification.
(4) the resistance to soldering dip temperature of the limit：Cover film is compound for the copper foil smooth surface of 5cm × 5cm with size, 180 DEG C/10MPa
Under the conditions of press soon 1 minute after in 170 DEG C cure 1 hour.By the sample after solidification immerse respectively 288 DEG C, 300 DEG C, 320 DEG C, 340
DEG C and 360 DEG C of tin liquors in 20 seconds, seen whether layering foaming phenomena, by maximum temperature be the resistance to soldering dip temperature of the limit.
(5) anti-flammability：It is tested according to UL94 vertical combustions.
(6) resistance to ion transport：SF201 0512SE (SHENGYI SCI.TECH's trade names) are taken to be lost without glue single-face flexibility copper-clad board
L/S=75/100 comb shape measurement circuits are carved, on the line by cover film pressing, is heating and curing, sample is made.Test processes item
Part is：85 DEG C of temperature, relative humidity 85% apply DC voltage 100V, sentence insulation when wire insulation resistance is less than 1M Ω
Failure；If the testing time reaches 1000h, wire insulation resistance passes through test still greater than 1M Ω.
(7) dendrite：Whether the sample after taking resistance to Ion transfer to test has under 40 power microscopes between observation circuit
" dendritic growth object ".
(8) resistance to ag(e)ing：Cover film and 18 μm of rolled copper foil smooth surfaces are pressed, solidification is placed on 150 DEG C of baking oven bakings 240
Hour, peel strength then is tested according to IPC-TM-650 2.4.9 methods, records peel strength conservation rate.
The test method of the above flexibility coat copper plate characteristic is as follows：
(1) peel strength：It is tested according to IPC-TM-650 2.4.9 methods.
(2) screen resilience can be with the flexibility of quantitative reaction flexibility coat copper plate, and screen resilience is smaller, and FCCL is more soft.Test side
Method is carried out by our company enterprise mark.
(3) resistance to dip solderability：It is tested by IPC-TM-650 2.4.13.
(4) anti-flammability：By UL94 standard testings.
(5) folding resistance：It is tested by JIS C-6471, test condition 0.5kg/0.8R, no cover film.Size of sample is
12.5 μm of PI/13 μm of composition coating/18 μm rolled copper foils.
By table 1-4 it is found that cover film and flexibility coat copper plate prepared by embodiment halogen-free resin composition using the present invention
With excellent resistance to ion transport, anti-flammability, heat resistance, flexibility, heat-resistant aging and folding resistance.But comparative example 7 by
It is excessively high in used block copolymer crystallinity, halogen-free resin composition, 11 He of comparative example can not be obtained with solvent dissolving
Block copolymer amine value used by comparative example 21 is excessively high, and glue system viscosity steeply rises, can not be coated with prepare cover film and
Flexibility coat copper plate, and used by remaining comparative example halogen-free resin composition prepare cover film and flexibility coat copper plate although it is resistance to from
Son migration test passes through, and wire insulation resistance is more than 1M Ω after test, and without dendrite, but comprehensive performance is poor,
Heat resistance, peel strength, folding resistance and flexibility etc. are not so good as embodiment.Therefore, resin combination of the invention requires tool
There is the block copolymer of appropriate proportioning and specific structure that could obtain the cover film and flexibility coat copper plate haveing excellent performance.
The present invention illustrates that the halogen-free resin composition of the present invention, flexible printed-circuit board cover by above-described embodiment
Film, flexibility coat copper plate and preparation method thereof, but the invention is not limited in above-described embodiments do not mean that the present invention must be according to
Bad above-described embodiment could be implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to this hair
The equivalence replacement of bright each raw material of product and the addition of auxiliary element, the selection etc. of concrete mode all fall within the protection model of the present invention
Enclose within the open scope.
Claims (10)
1. a kind of halogen-free resin composition, which is characterized in that the halogen-free resin composition includes being scattered in organic solvent
Polyester promotees with polyamide block copolymer, flexible-epoxy, phosphorous epoxy resin, polyfunctional epoxy resin, curing agent, solidification
Into agent, phosphonium flame retardant and antioxidant.
2. halogen-free resin composition according to claim 1, which is characterized in that the halogen-free resin composition includes as follows
The component of parts by weight：10-30 parts of polyester and polyamide block copolymer, 10-20 parts of flexible-epoxies, 5-10 parts of phosphorous epoxies
Resin, 45-50 part polyfunctional epoxy resin, 1-15 parts of curing agent, 0.1-0.3 parts of curing accelerators, 15-20 parts of phosphonium flame retardants
With 0.1-0.5 parts of antioxidant.
3. halogen-free resin composition according to claim 1 or 2, which is characterized in that the halogen-free resin composition is consolidated
Content is 30-50wt%；
Preferably, the organic solvent is acetone, butanone, toluene, ethyl alcohol, isopropanol, cyclohexanone, ethylene glycol monomethyl ether, propylene glycol
In methyl ether, propylene glycol methyl ether acetate or ethyl acetate any one or at least two combination.
4. halogen-free resin composition according to any one of claim 1-3, which is characterized in that the polyester and polyamide
The crystallinity of block copolymer is 5-15%；
Preferably, the number-average molecular weight of the polyester and polyester block in polyamide block copolymer is 500-3000, polyamide
The number-average molecular weight of block is 2000-12000；
Preferably, the polyester accounts for polyester segment and polyamides in block copolymer with polyamide segment in polyamide block copolymer
At least the 50% of amine segment total mole number, polyester segment account for polyester segment and polyamide segment total mole number in block copolymer
At least 10%；
Preferably, there are two glass transition temperatures, respectively -40~-60 DEG C with polyamide block copolymer tool for the polyester
With -80~-130 DEG C；
Preferably, the amine value of the polyester and polyamide block copolymer is 3-10mgKOH/g.
5. according to the halogen-free resin composition described in any one of claim 1-4, which is characterized in that the flexible-epoxy
For the epoxy resin having the following structure：
Wherein, m represents 1-3.
6. halogen-free resin composition according to any one of claims 1-5, which is characterized in that the phosphorous epoxy resin
For DOPO types phosphorous epoxy resin and/or DOPO-HQ type phosphorous epoxy resins；
Preferably, the polyfunctional epoxy resin is phenol type novolac epoxy resin, o-cresol type novolac epoxy resin, bisphenol-A
Type novolac epoxy resin, dicyclopentadiene phenol epoxy resin, biphenyl type novolac epoxy resin or four phenol ethane four shrink sweet
One kind in oily ether or at least two mixture, preferred biphenyl type novolac epoxy resin；
Preferably, the epoxide equivalent of the biphenyl type novolac epoxy resin is 310-350g/eq；
Preferably, the curing agent is amine curing agent and/or phenolic curing agent；
Preferably, the amine curing agent can be selected from dicyandiamide, 4,4'- diaminodiphenylsulfones, 3,3'- diaminodiphenylsulfones or two
In diaminodiphenylmethane any one or at least two mixture；
Preferably, the phenolic curing agent is phosphorus containing phenolic resin；
Preferably, the curing accelerator is imidazoles accelerating agent, preferably 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- benzene
In base imidazoles or 1- 1-cyanoethyl-2-methylimidazoles any one or at least two mixture；
Preferably, the phosphonium flame retardant is SPB-100, OP-935, OP-930 or SP-703H；
Preferably, the antioxidant is Hinered phenols antioxidant, the preferred antioxidant 1010 of the Hinered phenols antioxidant, antioxidant
168, any one in antioxidant 1222 or antioxidant 1076 or at least two mixture.
7. a kind of flexible printed-circuit board cover film, which is characterized in that the cover film includes Kapton, is coated in
The coating of the halogen-free resin composition as described in any one of claim 1-6 on Kapton surface and it is pressed on nothing
Release paper on halogen resin combination coating；
Preferably, the thickness of the polyimide insulative film is 10-50 μm；
Preferably, the thickness of the halogen-free resin composition coating is 5-45 μm.
8. the preparation method of flexible printed-circuit board cover film according to claim 7, which is characterized in that the preparation
Method is：It halogen-free resin composition will be coated on polyimide insulative film as described in any one of claim 1-6, it is dry,
Remove organic solvent, on polyimide insulative film formed the cured halogen-free resin composition coating in part, then by its with from
Type paper is pressed, and the flexible printed-circuit board cover film is obtained；
Preferably, the drying is realized by online dry baking oven；
Preferably, the drying is to be heated 2~8 minutes at 80-160 DEG C；
Preferably, the temperature of the pressing is 70-90 DEG C.
9. a kind of flexibility coat copper plate, which is characterized in that the flexibility coat copper plate includes polyimide insulative film, is coated on polyamides Asia
The coating of the halogen-free resin composition as described in any one of claim 1-6 on amine insulating film and it is pressed on Halogen tree
Copper foil on oil/fat composition coating；
Preferably, the thickness of the polyimide insulative film is 10-100 μm；
Preferably, the thickness of the halogen-free resin composition coating is 10-35 μm；
Preferably, the copper foil is rolled copper foil or electrolytic copper foil；
Preferably, the thickness of the copper foil is 9-50 μm.
10. the preparation method of flexibility coat copper plate according to claim 9, which is characterized in that the preparation method include with
Lower step：It halogen-free resin composition will be coated on polyimide insulative film as described in any one of claim 1-6, it is dry,
Organic solvent is removed, the cured halogen-free resin composition layer in part is formed on polyimide insulative film, then by itself and copper foil
It is pressed, is then cured, obtain the flexibility coat copper plate；
Preferably, the halogen-free resin composition is coated on polyimide insulative film as single side coating or dual coating；
Preferably, the drying is realized by online dry baking oven；
Preferably, the drying is to be heated 2-8 minutes at 80-160 DEG C；
Preferably, the temperature of the pressing is 80-100 DEG C；
Preferably, the cured temperature is 120-170 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040387A (en) * | 2019-12-28 | 2020-04-21 | 广东生益科技股份有限公司 | Halogen-free resin composition and flexible copper clad laminate comprising same |
| CN114085492A (en) * | 2021-12-07 | 2022-02-25 | 苏州生益科技有限公司 | Resin composition, prepreg and laminated board thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103555242A (en) * | 2013-10-17 | 2014-02-05 | 广东生益科技股份有限公司 | Halogen-free flame-retardant epoxy resin composition and high-flexibility halogen-free cover film prepared from same |
| CN104629342A (en) * | 2014-12-10 | 2015-05-20 | 广东生益科技股份有限公司 | Resin composition and covering film prepared from resin composition |
| CN105482442A (en) * | 2015-12-31 | 2016-04-13 | 广东生益科技股份有限公司 | Halogen-free resin composition and cover film prepared from the same |
| CN106700509A (en) * | 2016-12-29 | 2017-05-24 | 广东生益科技股份有限公司 | Halogen-free thermoplastic resin composition, prepared adhesive prepared by adopting compositon, insulating adhesive film for laminated busbar and preparation method of insulating adhesive film |
-
2018
- 2018-05-15 CN CN201810462519.XA patent/CN108676475B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103555242A (en) * | 2013-10-17 | 2014-02-05 | 广东生益科技股份有限公司 | Halogen-free flame-retardant epoxy resin composition and high-flexibility halogen-free cover film prepared from same |
| CN104629342A (en) * | 2014-12-10 | 2015-05-20 | 广东生益科技股份有限公司 | Resin composition and covering film prepared from resin composition |
| CN105482442A (en) * | 2015-12-31 | 2016-04-13 | 广东生益科技股份有限公司 | Halogen-free resin composition and cover film prepared from the same |
| CN106700509A (en) * | 2016-12-29 | 2017-05-24 | 广东生益科技股份有限公司 | Halogen-free thermoplastic resin composition, prepared adhesive prepared by adopting compositon, insulating adhesive film for laminated busbar and preparation method of insulating adhesive film |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040387A (en) * | 2019-12-28 | 2020-04-21 | 广东生益科技股份有限公司 | Halogen-free resin composition and flexible copper clad laminate comprising same |
| CN111040387B (en) * | 2019-12-28 | 2022-06-03 | 广东生益科技股份有限公司 | Halogen-free resin composition and flexible copper clad laminate comprising same |
| CN114085492A (en) * | 2021-12-07 | 2022-02-25 | 苏州生益科技有限公司 | Resin composition, prepreg and laminated board thereof |
| CN114085492B (en) * | 2021-12-07 | 2023-10-27 | 苏州生益科技有限公司 | Resin composition, prepreg and laminated board thereof |
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