CN107663369A - Resin combination, cover layer and flexible printed wiring board - Google Patents

Resin combination, cover layer and flexible printed wiring board Download PDF

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Publication number
CN107663369A
CN107663369A CN201610609075.9A CN201610609075A CN107663369A CN 107663369 A CN107663369 A CN 107663369A CN 201610609075 A CN201610609075 A CN 201610609075A CN 107663369 A CN107663369 A CN 107663369A
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China
Prior art keywords
weight
parts
epoxy resin
resin
cover layer
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Granted
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CN201610609075.9A
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CN107663369B (en
Inventor
丘建华
土桥秀
黄黎明
吴俊明
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Thinflex Corp
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Thinflex Corp
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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
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • B32B27/06—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
    • B32B27/08—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 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
    • 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
    • B32B27/10—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 of paper or cardboard
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • 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
    • B32B27/36—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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/72—Complexes of boron halides
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • 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
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
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    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention provides a kind of resin combination, and it includes epoxy resin (A), curing agent (B), catalyst (C), flame retardant (D), toughener (E) and solvent (F).The cover layer with single layer structure can be made in above-mentioned resin combination, and it can be directly arranged on the copper circuit wiring layer of flexible printed wiring board.Above-mentioned cover layer has good peel strength, welding heat resistance, bendability, flame resistance, anti-ion transport and fills out the property covered.

Description

Resin combination, cover layer and flexible printed wiring board
Technical field
The present invention is to provide a kind of resin combination, cover layer and flexible printed wiring board, and particularly one kind can The resin combination of the cover layer with single layer structure is made.The obtained cover layer with single layer structure can be directly arranged at On the copper circuit wiring layer of flexible printed wiring board.
Background technology
Flexible printed wiring board is element indispensable in electronic product.Scientific and technological industry now emphasize it is light, thin, short, Under small development trend, the R＆D direction of each element also tends to above-mentioned target in flexible printed wiring board.
In general, the flexible printed wiring board being currently known can comprise at least polyimide base material, located at polyimides Copper circuit wiring layer on the surface of base material, and the cover layer on copper circuit wiring layer.Known cover layer is by height The double-decker of molecular layer and adhesion layer is formed, macromolecule layer be usually heat reactive resin (such as：Polyimide resin), To protect copper circuit wiring layer to be hardly damaged.And above-mentioned adhesion layer is to help macromolecule layer to fit in copper circuit wiring layer On.
The thickness of above-mentioned double-decker is thicker, does not meet the lightening development trend of current electronic industry.
The shortcomings that to improve above-mentioned double-decker, it is known to which a technology is to propose a kind of resin combination, and it includes epoxy Resin, hardening accelerator, crosslinking agent and phosphorous phenolic resin.The semi-solid preparation film formed using above-mentioned resin combination can It is directly arranged on copper foil.However, above-mentioned semi-solid preparation film and the tack of copper foil are bad, and its fill out the property covered, welding heat resistance, Bendability, flame resistance and anti-ion transport can not still meet the needs of industry.
It is known separately to there is a technology to be to provide a kind of resin combination, its include halogen-free epoxy resin, thermoplastic resin and/ Or synthetic rubber, curing agent and nitrogenous flame ratardant.However, the peel strength of film layer obtained by above-mentioned resin combination, Fill out the property covered and anti-ion transport is bad.
Therefore, need badly at present and propose a kind of resin combination, it, which can be made, has good stripper-resistance concurrently, fills out the property covered, welding Heat resistance, bendability, the cover layer of flame resistance and anti-ion transport, and above-mentioned cover layer is single layer structure, can directly be set It is placed on copper circuit wiring layer, without helping to be bonded via adhesion layer.
The content of the invention
Therefore, a purpose of the invention is to propose a kind of resin combination, and it includes specific epoxy resin and toughness reinforcing Agent, the peel strength of obtained cover layer can be increased, fill out the property covered, welding heat resistance, bendability, flame resistance and anti-ion Migration.
It is another object of the present invention to propose a kind of cover layer, it is that it can have using obtained by above-mentioned resin combination There is single layer structure.
A further object of the present invention is to propose a kind of flexible printed wiring board, and it can have above-mentioned cover layer.
According to the above-mentioned purpose of the present invention, a kind of resin combination is proposed first.In one embodiment, resin combination can Include epoxy resin (A), curing agent (B), catalyst (C), flame retardant (D), toughener (E) and solvent (F).Wherein, epoxy Resin (A) includes the first epoxy resin (a-1) and the second epoxy resin (a-2), and the first epoxy resin (a-1) can have such as following formula (I) structure shown in：
In formula (I), R1 isR2 is A is 0 to 2 integer, and * is represented at bond.
Above-mentioned toughener (E) can include polyester resin.Usage amount based on epoxy resin (A) is 100 parts by weight, the first ring The usage amount of oxygen tree fat (a-1) is 30 parts by weight to 50 parts by weight, the usage amount of the second epoxy resin (a-2) for 50 parts by weight extremely 70 parts by weight, the usage amount of curing agent (B) are 16 parts by weight to 20 parts by weight, the usage amount of catalyst (C) for 0.8 parts by weight extremely 1 parts by weight, the usage amount of flame retardant (D) is 50 parts by weight to 60 parts by weight, and the usage amount of toughener (E) is 70 parts by weight to 90 Parts by weight, and the usage amount of solvent (F) is 75 parts by weight to 85 parts by weight.
According to one embodiment of the invention, the first epoxy resin (a-1) is selected from by following formula (I-1) to formula (I-3) institute At least one of one group of the structure shown：
According to one embodiment of the invention, above-mentioned second epoxy resin (a-2) includes novolac epoxy resin, bisphenol-A type ring Oxygen tree fat, alicyclic type epoxy resin, heterocyclic-type epoxy resin, glycidyl ester type epoxy resin or above-mentioned any combination.
According to one embodiment of the invention, curing agent (B) can include more amine compounds, acid phthalic anhydride compound or above-mentioned times Meaning combination.
According to one embodiment of the invention, catalyst (C) can include imidazolium compounds, three-level phosphine, boron fluoride misfit thing or Above-mentioned any combination.
According to one embodiment of the invention, flame retardant (D) can be made up of phosphorus-containing compound and metal-containing compound, its Middle metal-containing compound can include metal oxide or metal hydroxides.
According to one embodiment of the invention, the average particle size range of above-mentioned metal-containing compound is 1 μm to 5 μm.
According to one embodiment of the invention, polyester resin can be polyurethane.
According to the above-mentioned purpose of the present invention, a kind of cover layer is separately proposed, it is by above-mentioned resin combination, by applying Cloth step, baking procedure and maturation stage, are formed on the surface of base material.
According to the above-mentioned purpose of the present invention, a kind of flexible printed wiring board is proposed again, and it is comprising base material, on base material Copper circuit wiring layer and foregoing cover layer, wherein cover layer be provided on copper circuit wiring layer, and cover layer is individual layer Structure, without adhesion layer.
Using the resin combination of the present invention, it can make obtained cover layer that there is single layer structure, and cover layer can be direct On copper circuit wiring layer, and then the integral thickness of flexible printed wiring board can be reduced.In addition, above-mentioned cover layer can have concurrently it is good Stripper-resistance well, fill out the property covered, welding heat resistance, bendability, flame resistance and anti-ion transport.
Brief description of the drawings
For allow the present invention above and other purpose, feature, advantage and embodiment can become apparent, appended accompanying drawing it is detailed Carefully it is described as follows：
Fig. 1 is the encapsulation product for illustrating the cover layer comprising the present invention；
Fig. 2A to Fig. 2 F is the intermediate process profile for the manufacture method for illustrating the flexible printed wiring board of the present invention；
Fig. 3 is the flexible printed wiring board for illustrating the cover layer formed using the resin combination of the embodiment of the present invention 3 Insulation impedance variation diagram；And
Fig. 4 is to illustrate the cover layer that the resin combination of the embodiment of the present invention 3 is formed to be applied to make soft printing electricity The section electron microscope picture of road plate.
Embodiment
The purpose of the present invention is to propose a kind of resin combination, and it is comprising epoxy resin (A), curing agent (B), catalysis Agent (C), flame retardant (D), toughener (E) and solvent (F).By the cover layer obtained by above-mentioned resin combination, have single Rotating fields can be simultaneously directly arranged on copper circuit wiring layer, to reduce the thickness of obtained flexible printed wiring board.It is in addition, described Cover layer has good stripper-resistance concurrently, fills out the property covered, welding heat resistance, bendability, flame resistance and anti-ion transport.
Present invention single layer structure referred to herein, refer to that cover layer (it is glutinous to imply that cover layer does not include without the use of adhesive agent Layer), and can be directly arranged on copper circuit wiring layer.
Each composition of the resin combination of the detailed description below present invention.
Resin combination
Epoxy resin (A)
Present invention epoxy resin (A) referred to herein includes the first epoxy resin (a-1) and the second epoxy resin (a-2).
First epoxy resin (a-1)
The present invention the first epoxy resin (a-1) referred to herein can include the structure as shown in following formula (I)：
In above-mentioned formula (I), R1 isR2 is A is 0 to 2 integer, and * is represented at bond.
Specifically, the first epoxy resin (a-1) can be the change with the structure as shown in following formula (I-1) to formula (I-3) Any combination of compound or above-claimed cpd：
In an example, such as Ka Delai companies (Cardolite Corporation) can be used in the first epoxy resin (a-1) Made model NC-513, NC-514, NC-547 commodity or above-mentioned any combination.
Usage amount based on epoxy resin (A) is 100 parts by weight, and the usage amount of the first epoxy resin (a-1) can be 30 weights Part is measured to 50 parts by weight.If the first epoxy resin (a-1) is free of in epoxy resin (A), or its usage amount is very few, obtained covers The peel strength of epiphragma, flame resistance and welding heat resistance are bad.On the other hand, if the usage amount of the first epoxy resin (a-1) Excessively, because the first epoxy resin (a-1) belongs to the epoxy resin of low-viscosity, when carrying out the processing procedure of cover layer, resin composition Thing has the problem of formability is bad.
Second epoxy resin (a-2)
The present invention the second epoxy resin (a-2) described herein can include novolac epoxy resin, bisphenol A type epoxy resin, Alicyclic type epoxy resin, heterocyclic-type epoxy resin, glycidyl ester type epoxy resin or above-mentioned any combination.
Foregoing novolac epoxy resin can for example be using the marque of Nanya Plastic Cement Industry Co., Ltd NPPN-431A70 or NPEB-454A80 product, the marque of Changchun artificial resin limited company are CNE- The product or above-mentioned any combination of the product of 200EL series, the marque of Dow Chemical for D.E.N438, so originally Invention not limited to this.
Foregoing bisphenol A type epoxy resin may be, for example, that the marque of Changchun artificial resin limited company is BE-188 product, the marque of Dow Chemical are DER671 product, Huntsman Corporation (Huntsman) system Trade name GT-7071 or GT-7072 product, the product or above-mentioned that the marque of Kukdo chemical companies is KD-211G Any combination, so the invention is not restricted to this.
Foregoing alicyclic type epoxy resin can be for example using 3,4- epoxycyclohexyl-methyls -3 ', 4 ' -7-oxa-bicyclo[4.1.0 carboxylic acid Dimer addition product, the 1,2,8,9- bis- of ester, 3,4- epoxycyclohexyl-methyls -3 ', 4 '-epoxycyclohexane carboxylate and caprolactone Epoxy hesperidene or above-mentioned any combination.The marque that may be, for example, specifically DAICEL company systems is CELLOXIDE 2021st, 2081 or 3000 product, so the invention is not restricted to this.
Foregoing heterocyclic-type epoxy resin can for example step the trade name AralditePT810 of advanced material using Hensel Product, Nissan Chemical Industries society trade name TEPIC product or combinations of the above, so the invention is not restricted to this.
It is epoxy resin, ring that foregoing glycidyl ester type epoxy resin, which can include the copolymerization of glycidyl propyl diester, The copolymerization epoxy resin or combinations of the above of hexyl maleimide and glycidyl propyl diester, so the invention is not restricted to This.
, can be for example by the first epoxy resin (a-1) and novolac epoxy resin and bisphenol type epoxy in a preferable example Resin uses simultaneously.
Usage amount based on epoxy resin (A) is 100 parts by weight, and the usage amount of the second epoxy resin (a-2) can be 50 weights Part is measured to 70 parts by weight.If the second epoxy resin (a-2) is not used in resin combination, the formability of resin combination is not It is good, it is not easy to form cover layer.
Curing agent (B)
Present invention curing agent (B) referred to herein can include more amine compounds, acid phthalic anhydride compound or above-mentioned any group Close.
Specifically, above-mentioned more amine compounds may be, for example, diethyl support group triamine, two aminodiphenylmethane, 3,3 '- Two amido diphenyl sulfones, 4,4 '-two amido diphenyl sulfones, dicyanamide or above-mentioned any combination.
Specifically, above-mentioned acid phthalic anhydride compound may be, for example, acid phthalic anhydride, tetrahydrochysene acid phthalic anhydride or above-mentioned any combination.
In a preferable example, the hardening with different operative temperatures is optionally used in resin combination Agent, such as：Two amido diphenyl sulfones and dicyanamide are used simultaneously, resin combination can be made under different temperatures, is had different Heat cure degree.
Usage amount based on above-mentioned epoxy resin (A) is 100 parts by weight, and the usage amount of curing agent (B) can be 16 parts by weight To 20 parts by weight.If the usage amount of curing agent (B) is not fallen within the scope of above-mentioned opinion, cover layer have flame resistance, welding it is resistance to The problem of hot and/or peel strength is bad.
Catalyst (C)
Present invention catalyst (C) referred to herein can include imidazolium compounds, three-level phosphine, boron fluoride misfit thing or above-mentioned Any combination.
In a specific example, above-mentioned imidazolium compounds may include but be not limited to 1- methylimidazoles, 2-methylimidazole, 2- Ethyl -4-methylimidazole or combinations of the above.
In a specific example, above-mentioned three-level phosphine can be triphenylphosphine, tributylphosphine or combinations of the above.
In a specific example, above-mentioned boron fluoride misfit thing may be, for example, boron trifluoride and MEA misfit thing, Misfit thing, fluorine boronation zinc or the combinations of the above of the boron trifluoride and misfit thing of n-butylamine, boron trifluoride and aniline.
In a preferable example, catalyst (C) can be the combination of boron fluoride misfit thing and imidazolium compounds.
Usage amount based on above-mentioned epoxy resin (A) is 100 parts by weight, and the usage amount of catalyst (C) can be 0.8 parts by weight To 1 parts by weight.The catalyst of the present invention is used as hardening accelerator, and it contributes to the solidification of resin combination.If catalysis The usage amount of agent (C) is very few, then bad as the flame resistance and welding heat resistance of the cover layer obtained by resin combination.
Flame retardant (D)
Present invention flame retardant (D) referred to herein can be made up of phosphorus-containing compound and metal-containing compound.It is above-mentioned to contain Metallic compound includes metal oxide or metal hydroxides.It is preferred that its average grain diameter of metal-containing compound is 1 μm to 5 μ m。
Specifically, above-mentioned phosphorus-containing compound include but is not limited to bis-phenol biphenyl phosphate, APP, hydroquinones- Double-(biphenyl based phosphates), potassium phosphite, sodium phosphite, diethylphosphate aluminium or above-mentioned any combination.
Specifically, above-mentioned metal oxide can include antimony trioxide.
Specifically above-mentioned metal hydroxides may be, for example, aluminium hydroxide, magnesium hydroxide or combinations of the above.
Usage amount based on above-mentioned epoxy resin (A) is 100 parts by weight, and the usage amount of flame retardant (D) can be 50 parts by weight To 60 parts by weight.In a preferable example, the usage amount based on flame retardant (D) is 100 parts by weight, and metal-containing compound makes Dosage is 30 parts by weight to 50 parts by weight.
Supplementary notes, if the average grain diameter of metal-containing compound is not less than 5 μm, flame retardant (D) can not uniformly divide Dissipate in resin combination so that resin combination can not be spread evenly across on base material.
Toughener (E)
Present invention toughener (E) referred to herein comprises at least polyester resin.In an example, above-mentioned polyester resin is preferable It can be polyamine group methyl ester.
In one embodiment, toughener (E) can further include other toughener, such as：Nitrile rubber, phenoxy resin, gather Amide imide resin or above-mentioned any combination.
In an example, nitrile rubber may be, for example, carboxyl propenyl cyanide butadiene rubber, butadiene-acrylonitrile copolymer Thing, epoxy denaturation butadiene rubber or above-mentioned any combination.
Usage amount based on above-mentioned epoxy resin (A) is 100 parts by weight, and toughener (E) is except that can strengthen resin combination Outside the bendability of obtained cover layer, the flame resistance of cover layer also can be further lifted.Usage amount can be for 70 parts by weight extremely 90 parts by weight.The present invention is herein from polyester resin as toughener (E), therefore, if polyester resin is not used as toughener (E) or toughener (E) usage amount it is very few, the flame resistance of cover layer is bad.If however, the toughener (E) that addition is excessive, covering The bendability of film is also bad.
Solvent (F)
There is no particular restriction for present invention solvent (F) referred to herein, only to can dissolve epoxy resin (A), and cluster hardening Agent (B), catalyst (C), flame retardant (D) and toughener (E), but be not advisable with mentioned component reactor.
In a specific example, solvent (F) may include but be not limited to acetone, butanone, toluene, dimethylbenzene, dimethyl methyl Acid amides, glycol monoethyl ether, methyl proxitol or above-mentioned any combination.
Usage amount based on above-mentioned epoxy resin (A) is 100 parts by weight, and the usage amount of solvent (F) can be for 75 parts by weight extremely 85 parts by weight.
Additive (G)
The resin combination of the present invention can further include additive (G).Above-mentioned additive (G) may include but be not limited to anti-oxidant Agent, cation capture agent, anion catching agent, dispersant, levelling agent or above-mentioned any combination.
Above-mentioned antioxidant may be, for example, distearyl pentaerythrityl diphosphite, the isodecyl ester of one benzene of phosphorous acid two and Different fork-fatty alcohol-phosphorous acid chelate compounds the polymer of carbon alkyl -4,4 two or above-mentioned any combination.Specifically, it is anti-oxidant The product of the model STAB PEP-8T (AR-2) as manufactured by ADEKA companies can be used in agent.
Above-mentioned dispersant may be, for example, the polydimethylsiloxane of polyester modification.Specifically, dispersant can be used by Bi Ke The model BYK-310 of chemical assistant and instrument manufacturing product.Above-mentioned levelling agent can for example using by Bi Ke chemical assistants with The model BYK-W903 of instrument manufacturing product.
Special instruction, although cation capture agent and/or anion catching agent can additionally be added in the tree of the present invention In fat composition, to increase anti-ion transport.However, in the present invention, cation capture agent and/or anion catching agent are simultaneously Inessential addition, representing the resin combination of the present invention has the good anti-ion transport for meeting existing market demand.
The manufacture method of resin combination
The manufacture method of the resin combination of the present invention is first by curing agent (B), catalyst (C), selectively add Additive (G) and solvent (F), add in reactor and mix.Afterwards, in above-mentioned reactor add epoxy resin (A) and Flame retardant (D), and mixed.Then, toughener (E) is added in above-mentioned reactor, and is mixed in room temperature, with system Obtain resin combination of the invention.Wherein, at 25 DEG C, the viscosity of resin combination is preferably 1000cps to 2000cps.
The manufacture method of cover layer
The manufacture method of the cover layer of the present invention herein, it is that above-mentioned resin combination is coated into step, baking step After rapid and maturation stage, cover layer is formed on the surface of base material.
Optionally, release liners can be set in another surface of cover layer (one side not contacted with base material), in order to The transport and preservation of obtained cover layer.
Specifically, above-mentioned manufacture method is that resin combination is coated on the surface of base material first.In an example In, above-mentioned base material may be, for example, polyethylene terephthalate (Polyethylene Terephthalate；PET plastic cement base) Material.Baking procedure is carried out to the base material after coating, to remove the solvent in resin combination.Afterwards, with 70 DEG C of temperature and 1.6kgf/cm2Pressure pressed, so that encapsulation product 100 as shown in Figure 1 are made.Fig. 1 is to illustrate the covering for including the present invention The encapsulation product 100 of film.In Fig. 1, cover layer 110 is provided between plastic rubber substrate 120 and release liners 130, to protect cover layer 110 is easily damaged during transport.To control glue overflow amount, cover layer to be cured at a temperature of passing through 50 DEG C to 70 DEG C, you can system Obtain cover layer of the invention.
Supplementary notes, encapsulation product 100 shown in Fig. 1 have trilamellar membrane (cover layer 110, plastic rubber substrate 120 and release Paper 130), but when applied to manufacture flexible printed wiring board, protect copper circuit wiring layer using only cover layer 110.Change Yan Zhi, when cover layer 110 of the invention is applied to manufacture flexible printed wiring board, there is single layer structure, be not required to pass through adhesion layer Can is directly arranged on the copper circuit wiring layer of flexible printed wiring board.
The manufacture method of flexible printed wiring board
Next Fig. 2A to Fig. 2 F is refer to, it is the centre for the manufacture method for illustrating the flexible printed wiring board of the present invention Processing procedure profile.First, as shown in Figure 2 A, there is provided include the present invention cover layer encapsulation product 200, its include cover layer 210, Plastic rubber substrate 220 and release liners 230.Next, as shown in Figure 2 B, release liners 230 are removed, to expose cover layer 210. Afterwards, as shown in Figure 2 C, by cover layer 210 on the copper circuit wiring layer 241 of flexible printed wiring board semi-finished product 240, and Progress is pasted up to 10 seconds in advance, and wherein copper circuit wiring layer 241 is provided on substrate 243.In one embodiment, substrate 243 can be poly- Acid imide substrate.Then, as shown in Figure 2 D, the base material 220 being overlying on cover layer 210 is removed.Afterwards, as shown in Figure 2 E, it is high Temperature carries out hot pressing, wherein fender resistance glue mould release membrance 250 can be used to separate cover layer 210 with pressing machine, to avoid covering Film 210 is impaired.Then, foregoing curing agent (B) hardening temperature is heated to, to carry out cure step, then can be made the present invention's Flexible printed wiring board 200F.
Special instruction, as Fig. 2 F understand that cover layer 210 of the invention can be in the case of without using adhesive agent, directly Connect and pressed with copper circuit wiring layer 241 and base material 243, therefore the cover layer 210 of the present invention is single layer structure.
In one embodiment, the step that punches can be carried out to encapsulation product 200, so that cover layer 210 can have through hole, in favor of Expose the copper circuit wiring layer (not illustrating) of specific portion, the application that increase flexible printed wiring board is combined with other plug-in units Property.
Next with several embodiments illustrate the present invention resin combination and its reach the effect of.
Embodiment 1
First by 4,4 '-two amido diphenyl sulfones (B-1) of 15.2 parts by weight, the diethyl support group triamine (B- of 3.0 parts by weight 2), the misfit thing (C-1) of the boron trifluoride of 0.5 parts by weight and MEA, the 2-methylimidazole (C-2) of 0.4 parts by weight, 1.6 The distearyl pentaerythrityl diphosphite (G-1) of parts by weight, dispersant (Bi Ke chemical assistants and the instrument of 0.04 parts by weight System, model BYK-310；G-2), levelling agent (Bi Ke chemical assistants and instrument system, the model BYK-W903 of 0.22 parts by weight； G-3), the butanone (F-1) of 69 parts by weight and the toluene (F-2) of 9 parts by weight, add in reactor and mixed.Afterwards, Yu Shang State and first epoxy resin (a-1-1) of 40 parts by weight as shown in formula (I-2), the bisphenol-A type ring of 40 parts by weight are added in reactor Oxygen tree fat (Changchun artificial resin limited company system, model BE-188；A-2-2), the novolac epoxy resin of 20 parts by weight (Changchun artificial resin limited company system, model CNE-200ELB；A-2-1), the diethylphosphate aluminium (D- of 33 parts by weight 1), and 27 parts by weight and average grain diameter are 3 μm of aluminium hydroxide (D-2), and are mixed.Then, 80 parts by weight are added Polyamine group methyl ester (TOYOBO systems, model SD-5000；E-1), and in room temperature mix, so that the resin group of embodiment 1 is made Into thing.Wherein, at 25 DEG C, the viscosity of the resin combination of embodiment 1 is 1450cps.
Then, the resin combination of embodiment 1 is coated on plastic rubber substrate.Then, baking procedure is carried out to remove resin Solvent in constituent.Afterwards, hot pressing and maturation stage control glue overflow amount are carried out, you can the cover layer of embodiment 1 is made. The evaluation result of the cover layer of embodiment 1 is known as shown in table 1.
Embodiment 2 to 3 and comparative example 2 to 3
Embodiment 2 to 3 and comparative example 2 to 3 are carried out using method same as Example 1, unlike, embodiment 2 to 3 and comparative example 2 to 3 be change resin combination in each composition species or usage amount.On embodiment 2 to 3 and ratio Know as shown in table 1 compared with example 2 to 3 specific composition species, usage amount and evaluation result, do not repeat separately herein.
Comparative example 1
Comparative example 1 is that cover layer is made using method same as Example 1, unlike, on the cover layer of comparative example 1 It is further provided with polyimide layer.In other words, comparative example 1 is to belong to double-decker.On the resin covering film of comparative example 1 composition and Evaluation result is known as shown in table 1.Supplementary notes, if polyimide layer is not used in comparative example 1, its evaluation result is similar to Comparative example 2.
Evaluation method
1. structure
Present invention structure referred to herein is preferred with individual layer.Specifically, individual layer refers to that obtained cover layer can be straight Connect and be arranged on copper circuit wiring layer, be not necessary to via adhesion layer, cover layer is bonded with copper circuit wiring layer.On the other hand, it is double Layer then refers to that cover layer is to be bonded via adhesion layer with copper circuit wiring layer.The present invention is preferable using single layer structure.
2. cover film thickness
The covering film thickness of the present invention herein gets over Bao Yuejia.Supplementary notes, in above-mentioned alleged double-decker, cover Epiphragma thickness is the gross thickness of adhesion layer and cover layer.
3. glue overflow amount
Constituent semi-finished product are inserted in circular excessive glue groove, high temperature carries out hot pressing, is heated to the hard of curing agent (B) afterwards Change temperature, to carry out cure step, it is hardened film forming.The width that above-mentioned film overflows circular excessive glue groove is inspected, is alleged Glue overflow amount.In general, above-mentioned width is advisable with 0.1mm to 0.2mm.If glue overflow amount is not fallen within above range, can make Have insulation impedance excessive into the cover layer formed using resin combination or to base material tackness it is bad the shortcomings that.
4. peel strength (to copper or to polyimide resin)
Present invention peel strength referred to herein is respectively to form the resin by embodiment 1 to 3 and comparative example 1 to 3 The cover layer that thing is formed, it is formed on copper base material or polyimide resin base material, with the cover layer of the test present invention to upper State the tack of two kinds of base materials.
Specifically, the resin combination of previous embodiment 1 to 3 and comparative example 1 to 3 is coated on base material (copper first Matter base material or polyimide resin base material) on.Then, hot pressing is carried out to the base material after coating.And then hardened, with In forming cover layer on the surface of base material.Then, cover layer is cut into the test piece of 1 centimetre of width, 10 centimetres of length.Will be above-mentioned Test piece is pulled with the peeling force of the direction of 180 degree and 50mm/min speed, and detection cover layer peels off when institute in above-mentioned base material The pressure born.
5. weld heat resistance
The test of welding heat resistance is that the cover layer of the present invention is formed on copper base material first, its specific generation type As described in the evaluation method of foregoing peel strength, thus it is not elsewhere specified herein.
By the test piece that the base material cutting formed with cover layer is 5 centimetres of 5 cm x.Afterwards, above-mentioned test piece is impregnated in 288 DEG C tin liquor in up to 30 seconds.After taking out test piece, whether observation test piece has delamination or discoloration.The evaluation of the welding heat resistance of the present invention Standard is as follows：
○：Without delamination and without discoloration.
X：Delamination or discoloration.
6. bendability
The test of bendability is that the cover layer of the present invention is formed on copper base material first, and its forming method is known as foregoing It is not elsewhere specified herein shown in the method for testing of peel strength.Afterwards, by the copper base material cutting provided with cover layer be 30mm × 5mm test piece.Present invention bendability referred to herein is carried out according to MIT methods, wherein as the resistance to device for folding of MIT using Japan's essence Mechanism makees manufactured trough of belt film folding fatigue tester (model：549), with bending radius 0.38mm, loading 500g, to above-mentioned Test piece carries out alternating bending, untill circuit can not turn on.Number of bends, and to represent bendability better.
7. flame resistance
Present invention flame resistance referred to herein is carried out with UL94-V0 regulation.Specifically, to the covering of the present invention Film carries out the combustion testing that 2 times are respectively 10 seconds, if flame extinguished in 30 seconds and fallen without comburant, it is good to represent flame resistance.Instead Then flame resistance it is bad.Specific evaluation criterion is as follows：
○：Flame extinguished in 30 seconds and fallen without comburant, and flame resistance is good.
X：Flame did not extinguished in 30 seconds, or whether there is comburant and fall, and flame resistance is bad.
8. anti-ion transport
The resin combination of embodiment 3 is further formed cover layer by the present invention, to carry out the test of anti-ion transport. Cover layer is fitted on the copper circuit wiring layer of flexible printed wiring board first, wherein above-mentioned laminating step is with fast pressure side Formula is carried out.Then, hardening process is carried out to above-mentioned flexible printed wiring board, to be made needed for the test of anti-ion transport Test piece.Next, in the environment of 85 DEG C and relative humidity 85%, the voltage for applying 100V to above-mentioned test piece is small up to 1000 When, and note down the change situation of its insulation impedance.In general, after the test of 1000 hours, insulation impedance still maintains In 109 more than Ω, and test front and rear insulation impedance difference and be less than within 1 order of magnitude (101), i.e., up to specification (O, which is represented, to be closed Lattice；X represents unqualified), represent that anti-ion transport is good, and its evaluation result is known as shown in Figure 3.The meter of above-mentioned insulation impedance difference Shown in calculation mode such as following formula (II).
Insulation impedance formula (II) after insulation impedance/test before insulation impedance difference=test
9. fill out the property covered
The resin combination of embodiment 3 is further formed cover layer by the present invention, to carry out filling out the test for the property covered.Above-mentioned survey Examination is to use the test piece obtained by manufacture method identical with the test of anti-ion transport, but the test for filling out the property covered is used with not The copper circuit wiring layer of same spacing (25 μm, 30 μm, 35 μm, 40 μm, 45 μm and 50 μm).By the section of above-mentioned test piece with electronics Micro- sem observation, if the space between wiring can be filled up by the cover layer of the present invention, it is good that the property covered is filled out in representative.Fill out the property covered Evaluation result is known as shown in Figure 4.
Understand, using the cover layer obtained by the resin combination of the present invention, can have single according to the embodiment 1 to 3 of table 1 Rotating fields, and then can have relatively thin thickness.In addition, the cover layer of the present invention all has to copper base material and polyimide base material There are good peel strength (or tack) and welding heat resistance, and cover layer is with more good bendability, resistance to combustion Property and anti-ion transport.
In addition, it can be seen from Fig. 3, cover layer that resin combination of the invention is formed is passing through 1000 hours After the test of 100V voltages, integral insulation impedance still has 109 Ω, and tests front and rear insulation impedance difference and be less than 1 order of magnitude, Representing obtained cover layer has good anti-ion transport.Furthermore it can be seen from Fig. 4, cover layer (example of the invention Such as：Cover layer 310A to cover layer 310F) for spacing, at 25 μm to 50 μm, (space D 1 is 50 μm, space D 2 is 45 μm, spacing D3 is 40 μm, space D 4 is 35 μm, space D 5 is 30 μm and space D 6 is 25 μm) copper circuit wiring layer (such as copper circuit Wiring layer 320A to copper circuit wiring layer 320F) flexible printed wiring board, can have and good fill out the property covered.
On the other hand, it can be seen from the comparative example of table 1, when each composition in resin combination or its usage amount do not meet this During the advocated scope of invention, be unable to reach the predetermined thickness of the present invention, glue overflow amount, peel strength, bendability, flame resistance and/ Or welding heat resistance.Particularly, it can be seen from the comparative example 1 of table 1, the first epoxy resin (a-1) of the present invention is being not used In the case of, using known double-decker (polyimide layer adds adhesion layer) although cover layer can improve peel strength, and Pass through covered polyimide layer increase bendability, but the thickness of the cover layer of comparative example 1 is thicker, does not meet current pursuit Lightening target.In addition, if the cover layer of comparative example 1 does not form double-decker, it, which is formed, is similar to comparative example 2, therefore its Evaluation result is also similar to comparative example 2, is unable to reach the predetermined property of the present invention.
Using resin combination, cover layer and the flexible printed wiring board of the present invention, pass through resin combination specific group Into (such as：The specific usage amount ratio of first epoxy resin (a-1) and the second epoxy resin (a-2), and particular kind of toughness reinforcing Agent), obtained cover layer can be made to be directly arranged in the case where being not required to adhesive layer on copper circuit wiring layer, in other words, Cover layer has single layer structure and thinner thickness.In addition, cover layer has good peel strength, welding heat resistance, bending concurrently Property, flame resistance, anti-ion transport and fill out the property covered.
Although the present invention is disclosed above with several embodiments, so it is not limited to the present invention, belonging to the present invention Any tool usually intellectual in technical field, without departing from the spirit and scope of the present invention, when can make various changes with Retouching, therefore protection scope of the present invention is worked as the scope defined depending on institute's appended claims and is defined.
Table 1
Compound (the Ka Delai company systems of a-1-1 formulas (I-2)；NC-514)
A-2-1 novolac epoxy resins (Changchun artificial resin limited company system；Model CNE-200ELB；Epoxy is worked as Amount:200g/eq)
A-2-2 bisphenol A type epoxy resins (Changchun artificial resin limited company system；Model BE-188；Epoxy is worked as Amount:187g/eq)
A-3-1 bisphenol A type epoxy resins (Changchun artificial resin limited company system；Model BE-150X-75；Ring Oxygen equivalent:500g/eq)
Amido diphenyl sulfone (the Atul company systems of B-1 4,4 '-two；Trade name AtulSulpho 44DDS)
B-2 diethyl support groups triamine (Qin Yu enterprises system)
The misfit thing of C-1 boron trifluorides and MEA (Eastcom's chemistry system)
C-2 2-methylimidazoles (four countries' chemical conversion system)
D-1 diethylphosphates aluminium (Clariant chemical company system；Model OP935)
D-2 aluminium hydroxides (Showa chemical industry system；Model H-42M (FAL):Average grain diameter is 3 μm)
E-1 polyamine groups methyl ester (TOYOBO systems；Model SD-5000)
E-2 acrylonitrile-butadiene rubbers (southern Supreme Being's chemical industry system；Model Hycarl042)
F-1 butanone
F-2 toluene
G-1 distearyl pentaerythrityl diphosphite (antioxidants；ADEKA company systems；Model STAB PEP-8T (AR-2))
G-2 dispersants (Bi Ke chemical assistants and instrument system；Model BYK-310)
G-3 levelling agents (Bi Ke chemical assistants and instrument system；Model BYK-W903)

Claims (10)

1. a kind of resin combination, it is characterised in that include：
Epoxy resin (A), comprising：
One first epoxy resin (a-1), wherein first epoxy resin (a-1) have the structure as shown in following formula (I)：
In the formula (I), the R1 isThe R2 is The a is 0 to 2 integer, and the * is at bond；And
One second epoxy resin (a-2)；
One curing agent (B)；
One catalyst (C)；
One flame retardant (D)；
One toughener (E), the wherein toughener (E) include polyester resin；And
One solvent (F),
Wherein the usage amount based on the epoxy resin (A) is 100 parts by weight, and the usage amount of first epoxy resin (a-1) is 30 Parts by weight are to 50 parts by weight, and the usage amount of second epoxy resin (a-2) is 50 parts by weight to 70 parts by weight, the curing agent (B) Usage amount be 16 parts by weight to 20 parts by weight, the usage amount of the catalyst (C) is 0.8 parts by weight to 1 parts by weight, the flame retardant (D) usage amount is 50 parts by weight to 60 parts by weight, and the usage amount of the toughener (E) is 70 parts by weight to 90 parts by weight, and The usage amount of the solvent (F) is 75 parts by weight to 85 parts by weight.
2. resin combination according to claim 1, it is characterised in that first epoxy resin (a-1) be selected from by At least one for the group that structure shown in following formula (I-1) to formula (I-3) is formed：
3. resin combination according to claim 1, it is characterised in that second epoxy resin (a-2) includes phenolic aldehyde ring Oxygen tree fat, bisphenol A type epoxy resin, alicyclic type epoxy resin, heterocyclic-type epoxy resin, glycidyl ester type epoxy resin or on Any combination stated.
4. resin combination according to claim 1, it is characterised in that the curing agent (B) includes more amine compounds, phthalein Anhydridization compound or above-mentioned any combination.
5. resin combination according to claim 1, it is characterised in that the catalyst (C) includes imidazolium compounds, three-level Phosphine, boron fluoride misfit thing or above-mentioned any combination.
6. resin combination according to claim 1, it is characterised in that the flame retardant (D) be by a phosphorus-containing compound with And one metal-containing compound formed, and the metal-containing compound includes metal oxide or metal hydroxides.
7. resin combination according to claim 6 a, it is characterised in that average particle size range of the metal-containing compound For 1 μm to 5 μm.
8. resin combination according to claim 1, it is characterised in that the polyester resin is polyurethane.
9. a kind of cover layer, it is characterised in that it is by the resin combination as described in any one of claim 1 to 8, through one Application step, a baking procedure and a maturation stage, are formed on a surface of a base material.
10. a kind of flexible printed wiring board, it is characterised in that include：
One base material；
One copper circuit wiring layer, on a surface of the base material；And
Cover layer as claimed in claim 9, on the copper circuit wiring layer, wherein the cover layer is a single layer structure, no With an adhesion layer.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111800935A (en) * 2019-04-01 2020-10-20 新扬科技股份有限公司 Circuit board structure

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