CN111995832B - Resin composition, adhesive and flexible copper-clad plate - Google Patents
Resin composition, adhesive and flexible copper-clad plate Download PDFInfo
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- CN111995832B CN111995832B CN202010525000.9A CN202010525000A CN111995832B CN 111995832 B CN111995832 B CN 111995832B CN 202010525000 A CN202010525000 A CN 202010525000A CN 111995832 B CN111995832 B CN 111995832B
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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- 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
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- 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
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- 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
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- 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
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09J109/02—Copolymers with acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
- C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J127/12—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09J127/18—Homopolymers or copolymers of tetrafluoroethene
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- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- 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
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
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Abstract
The invention provides a resin composition, an adhesive and a flexible copper-clad plate. The resin composition comprises the following components in percentage by weight: 35-45% of epoxy resin, wherein the epoxy resin is selected from one or more of dicyclopentadiene novolac epoxy resin, biphenyl epoxy resin and naphthalene ring epoxy resin; 1-3.5% of a curing agent; 25-35% of a toughening agent; 15-25% of fluororesin; 10-20% of a flame retardant; and 1-3% of a curing accelerator. When the components of the resin composition are mixed and applied to the flexible copper clad laminate as an adhesive, firm bonding of polyimide and other low-dielectric and low-loss films can be realized, and further, other low-dielectric and low-loss films with smaller difference with the thermal expansion coefficient of the copper foil can be arranged on the polyimide film, so that the thickness of the dielectric layer on the copper foil is increased, and the formed flexible copper clad laminate meets the requirements of 5G high-frequency and high-speed wireless transmission.
Description
Technical Field
The invention relates to the technical field of flexible circuit boards, in particular to a resin composition, an adhesive and a flexible copper-clad plate.
Background
In recent years, as the function integration of the terminal application products is stronger and stronger, the response speed must be faster and faster, and the trend of high frequency/high speed of the flexible printed circuit board is more and more important. Since the high dielectric constant (Dk) slows down the signal transmission speed and the high dielectric loss (Df) converts part of the signal into heat energy to be dissipated in the substrate material, the trend of the material Dk/Df to become flexible substrate material is reduced, and various new technologies and new materials with low Dk/Df are emerging.
In response to these material requirements, substrate films of Liquid Crystal Polymer (LCP), syndiotactic polystyrene, polyphenylene sulfide, and the like having low dielectric characteristics have been proposed as substrate films for flexible printed circuit boards (FPCs) instead of conventional polyimide, polyethylene terephthalate, and the like. Most commonly LCP has emerged from the water surface due to its low dielectric constant and low dielectric loss required for high frequency transmission. However, the LCP process requires high temperature equipment and conditions, which are significantly different from the conventional process of the current FPC, so that the LCP is used as the substrate film, not only the equipment needs to be replaced, but also the production speed is affected. The traditional polyimide copper-clad substrate does not need to replace FPC production equipment, and the production process accords with the current soft board production. Therefore, reduction of dielectric constant and loss are the primary goals of polyimide copper clad substrate development.
The production of polyimide copper-clad substrate is mainly characterized by that the polyimide acid is coated on the copper foil, then the solvent is removed and the polyimide copper-clad substrate is formed by heating treatment. However, in the copper clad laminate production process, due to the thermal expansion coefficient difference between the polyimide and the copper foil, the coated polyimide is easy to be baked, so that the copper clad laminate is wound, and the production and manufacturing obstacles are formed, especially the stacked combination of the thin copper and thick polyimide, for example, the specification of 1/3Oz copper foil (12 μm) coated with 1.5mil (about 38 μm) polyimide layer which can be achieved by the existing manufacturing process. However, in order to meet the requirement of 5G high frequency/high speed wireless transmission application, the flexible printed circuit board must meet the impedance matching (100ohm) of the circuit design, and the thickness of the polyimide needs to be designed to a thicker thickness to meet the design requirement.
Chinese patent application publication No. CN104691066A discloses a method for producing a multilayer polyimide film with a low dielectric constant, which discloses a three-layer polyimide film, wherein the first layer is formed by polymerizing at least two aromatic diamines and at least two aromatic tetracarboxylic acid dianhydrides, and additionally adding tetrafluoroethylene; the second layer and the third layer are formed by polymerizing at least two kinds of aromatic diamines and at least two kinds of aromatic tetracarboxylic acid dianhydrides, and an organosilicon compound is additionally added to increase the adhesion between the polyimide film and the metal layer. However, the polyimide film manufactured by this technique has a porous structure, so that the mechanical strength thereof is reduced, which is not favorable for the development of high frequency substrates.
Taiwan patent No. TW I591100B discloses a method for manufacturing a low dielectric constant polyimide copper-clad substrate, which discloses dissolving a fluorine-containing polymer dispersion in a solvent and an aromatic diamine, adding an aromatic dianhydride to polymerize to obtain a poly-sulfanilic acid solution, coating in a conventional coating manner, removing the solvent, and performing a subsequent imidization process to obtain a low dielectric/low loss polyimide copper-clad substrate. Although this method can produce polyimide copper clad substrate with low dielectric/low loss, it is limited to produce 1/3Oz (12 μm) copper clad laminate coated with 38 μm polyimide due to the difference of thermal expansion coefficient between polyimide and copper clad, and it is difficult to coat polyimide with thicker coating layer.
In order to meet the impedance matching requirement of 5G high frequency/high speed wireless transmission flexible printed circuit board, it is necessary to thicken the dielectric layer of the single-sided copper-clad substrate to 50 μm, and the substrate material characteristics must maintain excellent mechanical characteristics, heat resistance, electrical properties, etc., but the current dielectric layer of the copper-clad substrate is easy to be peeled off from the copper foil when the thickness is increased to 50 μm.
Disclosure of Invention
The invention mainly aims to provide a resin composition, an adhesive and a flexible copper-clad plate, and aims to solve the problem that a polyimide copper-clad plate in the prior art cannot meet the requirement of high-frequency/high-speed wireless transmission of 5G.
In order to achieve the above object, according to one aspect of the present invention, there is provided a resin composition comprising, in weight percent: 35-45% of epoxy resin, wherein the epoxy resin is selected from one or more of dicyclopentadiene novolac epoxy resin, biphenyl epoxy resin and naphthalene ring epoxy resin; 1-3.5% of a curing agent; 25-35% of a toughening agent; 15-25% of fluororesin; 10-20% of a flame retardant; and 1-3% of a curing accelerator.
Furthermore, the epoxy equivalent of the epoxy resin is 160-2000 g/eq, the preferred molar volume of the epoxy resin is more than or equal to 200mL/mol, and the molecular polarizability is less than or equal to 85 C.m2Preferably, the epoxy resin is selected from a mixture of one or more dicyclopentadiene phenol-aldehyde epoxy resins, more preferably a mixture of an HP-7200 series of dicyclopentadiene phenol-aldehyde epoxy resins of DIC corporation and an SEV-3408 series of dicyclopentadiene phenol-aldehyde epoxy resins of Santa east industry, and further preferably the weight ratio of the HP-7200 series of dicyclopentadiene phenol-aldehyde epoxy resins to the SEV-3408 series of dicyclopentadiene phenol-aldehyde epoxy resins is 3-5: 4.
The fluororesin is preferably a resin powder having an average particle diameter of preferably 10 μm or less, more preferably 0.1 to 10 μm, even more preferably 0.1 to 7 μm, even more preferably 0.1 to 5 μm, and is preferably one or more selected from the group consisting of polytetrafluoroethylene, chlorotrifluoroethylene, perfluoroalkoxy polymer, fluorinated ethylene-propylene copolymer, and polyperfluorovinylene polymer.
Further, the curing agent is selected from one or more of polyamine curing agent, phthalic anhydride curing agent and ester curing agent, preferably the polyamine curing agent is diethylenetriamine, diaminodiphenylmethane, 3-diaminodiphenylsulfone, 4, 4-diaminodiphenylsulfone and dinitrile amine, and the ester curing agent is SHC-4314M65, SHC-5620TM65 and SAP-641 of Shandong industry.
Further, the toughening agent is selected from any one of polyimide resin, polyester resin, nitrile rubber, styrene-butadiene rubber, and styrene-butadiene-styrene block copolymer.
Further, the flame retardant is selected from a phosphorus flame retardant and a metal compound-containing flame retardant, preferably, the metal compound-containing flame retardant is a metal oxide or a metal hydroxide, and preferably, the average particle size of the metal oxide is 1 to 5 μm.
Further, the curing accelerator is selected from one or more of lewis base curing accelerators and lewis acid curing accelerators, the lewis base curing accelerator is a complex of imidazole and boron trifluoride amine, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole and 4-dimethylaminopyridine, and the lewis acid curing accelerator is an organic metal salt compound, preferably an organic salt of manganese, iron, cobalt, nickel, copper and zinc.
According to another aspect of the present invention, there is provided an adhesive, which is prepared by mixing a solvent with any one of the above resin compositions, wherein the solid content of the adhesive is 35 to 60%.
According to another aspect of the invention, a flexible copper clad laminate is provided, which comprises a copper substrate and a dielectric layer arranged on the copper substrate, wherein the dielectric layer comprises: a polyimide film disposed on a surface of the copper substrate; the adhesive layer is prepared from the adhesive; the low dielectric/low loss film is bonded with the polyimide film through the bonding layer, the absolute value of the difference between the thermal expansion coefficients of the low dielectric/low loss film and the copper substrate is A, the absolute value of the difference between the thermal expansion coefficients of the polyimide and the copper substrate is B, and A is smaller than B.
Further, the thickness of the dielectric layer is more than 50 μm, preferably the thickness of the polyimide film is 20-30 μm, and preferably the low dielectric/low loss film is a polyetheretherketone film.
By applying the technical scheme of the invention, any one or more of dicyclopentadiene novolac epoxy resin, biphenyl type epoxy resin and naphthalene ring type epoxy resin is adopted as the epoxy resin of the resin composition, the resins have low dielectric and low loss performance, and meanwhile, the fluororesin adopted in the composition has low dielectric and low loss performance, so that the requirements of 5G high-frequency and high-speed wireless transmission on dielectric performance and loss level can be met. When the components of the resin composition are mixed and applied to the flexible copper clad laminate as an adhesive, firm bonding of polyimide and other low-dielectric and low-loss films can be realized, and further, other low-dielectric and low-loss films with smaller difference with the thermal expansion coefficient of the copper foil can be arranged on the polyimide film, so that the thickness of the dielectric layer on the copper foil is increased, and the formed flexible copper clad laminate meets the requirements of 5G high-frequency and high-speed wireless transmission.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background technology of the application, the thickness of the polyimide film of the polyimide copper clad substrate in the prior art can only reach 38 micrometers, if the thickness is continuously increased, the polyimide film can be stripped from the copper substrate, and the requirement of 5G high-frequency/high-speed wireless transmission is difficult to meet.
In a typical embodiment of the present application, a resin composition is provided, which comprises, by weight, 35 to 45% of an epoxy resin, 1 to 3.5% of a curing agent, 25 to 35% of a toughening agent, 15 to 25% of a fluororesin, 10 to 20% of a flame retardant, and 1 to 3% of a curing accelerator, wherein the epoxy resin is selected from any one or more of dicyclopentadiene novolac epoxy resin, biphenyl epoxy resin, and naphthalene ring-type epoxy resin.
Any one or more of dicyclopentadiene novolac epoxy resin, biphenyl type epoxy resin and naphthalene ring type epoxy resin is/are adopted as the epoxy resin of the resin composition, the resins have low dielectric and low loss performance, and meanwhile, the fluororesin adopted in the composition has low dielectric and low loss performance, so that the requirements of 5G high-frequency and high-speed wireless transmission on dielectric performance and loss level can be met. When the components of the resin composition are mixed and applied to the flexible copper clad laminate as an adhesive, firm bonding of polyimide and other low-dielectric and low-loss films can be realized, and further, other low-dielectric and low-loss films with smaller difference with the thermal expansion coefficient of the copper foil can be arranged on the polyimide film, so that the thickness of the dielectric layer on the copper foil is increased, and the formed flexible copper clad laminate meets the requirements of 5G high-frequency and high-speed wireless transmission.
Specifically, Dk and Df of the conventional epoxy resin are about 3.3-3.6 and about 0.023-0.035, respectively. The Dk of the epoxy resin selected by the application is about 3.0-3.1, and the Df is about 0.008-0.01. However, the Low Dk/Df epoxy resin alone is not sufficient to achieve Dk 3.0 and Df 0.007. The fluororesin has excellent Low Dk/Df electrical performance, and the fluororesin is added into the formulation system in an additive-like manner to achieve the goal of lower Dk/Df. However, since the polarity of the fluororesin is relatively Low, generally, the epoxy resin with high polarity is easily mixed with the fluororesin to cause phase separation, and the Low Dk/Df epoxy resin of the present application adopts a benzene ring or naphthalene ring structure with Low polarity, so that the Low Dk/Df epoxy resin is easily compatible with the fluororesin with Low polarity, so as to achieve better dispersion of the fluororesin and obtain better electrical performance.
The general formula of the dicyclopentadiene novolac epoxy resin is as follows:
the general formula of the biphenyl epoxy resin is as follows:
the general formula of the naphthalene ring type epoxy resin is as follows:
preferably, the epoxy equivalent of the epoxy resin is 160 to 2000 g/eq. The epoxy resin is small in molecules before curing, and the surface structure of the copper foil is a rough structure, so that the small-molecule epoxy resin before curing can be easily filled into the surface of the copper foil with rough protrusions and recesses; when the temperature is increased to generate the action of the curing agent, the epoxy resin with smaller molecules starts to be cured and is inserted into the high molecular structure of the fluororesin with large molecular weight, so that the epoxy resin is tightly bonded with the surface of the copper foil to form the effect like a hook and anchor to achieve high bonding performance.
In addition to meeting the above requirements for low dielectric constant and low loss, the epoxy resin treatment used in the present application is preferably such that the molar volume of the epoxy resin is not less than 200mL/mol and the molecular polarization rate is not more than 85 Cm.m.2Preferably, the epoxy resin is selected from a mixture of one or more dicyclopentadiene phenol-aldehyde epoxy resins, more preferably a mixture of an HP-7200 series of dicyclopentadiene phenol-aldehyde epoxy resins of DIC corporation and an SEV-3408 series of dicyclopentadiene phenol-aldehyde epoxy resins of Santa east industry, and further preferably the weight ratio of the HP-7200 series of dicyclopentadiene phenol-aldehyde epoxy resins to the SEV-3408 series of dicyclopentadiene phenol-aldehyde epoxy resins is 3-5: 4.
The fluororesin of the present invention may be a fluororesin commonly used in the prior art, and in order to improve the dielectric properties of the fluororesin, it is preferable that the fluororesin be a resin powder. In order to allow the fluororesin to contact with other components more sufficiently for reaction, the resin powder preferably has an average particle diameter of 10 μm or less, preferably 0.1 to 10 μm, more preferably 0.1 to 7 μm, and still more preferably 0.1 to 5 μm, and the fluororesin is preferably one or more selected from the group consisting of Polytetrafluoroethylene (PTFE), Chlorotrifluoroethylene (CTFE), perfluoroalkoxy Polymer (PFA), fluorinated ethylene-propylene copolymer (FEP), and polyperfluorovinylidene Polymer (PVDF).
The curing agent used in the present application is selected from the curing agents having a curing promoting effect on the epoxy resin and the fluororesin, preferably, the curing agent is selected from any one or a combination of a plurality of polyamine-based curing agent, phthalic anhydride-based curing agent and ester-based curing agent, preferably, the polyamine-based curing agent is diethylene triamine, diaminodiphenylmethane, 3-diaminodiphenylsulfone, 4, 4-diaminodiphenylsulfone and dicyandiamide, the ester-based curing agent is SHC-4314M65, SHC-5620TM65 and SAP-641 of Shandong Kogyo, and the phthalic anhydride-based curing agent may be phthalic anhydride, tetrahydrophthalic anhydride or a combination of the phthalic anhydride and the tetrahydrophthalic anhydride. In order to provide different degrees of thermal curing at different temperatures of the resin composition of the present application, curing agents having different action temperatures may be selected, such as the simultaneous use of diaminodiphenyl sulfone and dicyandiamide.
The main purpose of using the toughening agent in the present application is to provide the composition with high flexibility after high temperature curing, and the toughening agent is preferably selected from any one of soluble polyimide resin, polyester resin, nitrile rubber, styrene-butadiene rubber (SBR), and styrene-butadiene-styrene block copolymer (SBS). Further preferred are the following toughening agents: soluble polyimide resin (PIAD, Japan, P260, jin chemical, PI-220), polyester resin (TOYOBO, BX-39SS), vinyl terminated nitrile rubber (VTBN 1300X33LC, CVC specialty Chemicals Co., Ltd., USA) and SBS rubber (Kesheng high Performance Polymer, D1192 ET).
The flame retardant is used for playing a flame retardant role when the composition is applied to a circuit board, and flame retardants commonly used in the circuit board in the prior art can be considered to be applied to the composition, preferably the flame retardant is selected from phosphorus flame retardants and metal compound-containing flame retardants, preferably the metal compound-containing flame retardants are metal oxides or metal hydroxides, and preferably the average particle size of the metal oxides is 1-5 μm. The metal oxide may be antimony trioxide, the metal hydroxide may be aluminum hydroxide or magnesium hydroxide, and the phosphorus flame retardant may be any one or a combination of bisphenol biphenyl phosphate, ammonium polyphosphate, hydroquinone-bis- (biphenyl phosphate), potassium phosphite, sodium phosphite, and diethyl aluminum phosphate.
In order to lower the curing temperature, a curing accelerator is used, and in order to exert a better accelerating action on the curing of the epoxy resin, it is preferable that the curing accelerator is selected from one or more of lewis base curing accelerators and lewis acid curing accelerators, the lewis base curing accelerators are imidazole and boron trifluoride amine complex, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole and 4-dimethylaminopyridine, and the lewis acid curing accelerators are organic metal salt compounds, preferably organic salts of manganese, iron, cobalt, nickel, copper and zinc.
In another exemplary embodiment of the present disclosure, an adhesive is provided, which is prepared by mixing a solvent with any one of the resin compositions, and the solid content of the adhesive is 35 to 60%.
Among dicyclopentadiene novolac epoxy resin, biphenyl type epoxy resin and naphthalene ring type epoxy resin in the resin composition of the present application, fluororesin has low dielectric and low loss properties, and thus can satisfy the requirements of 5G high frequency, high speed wireless transmission for dielectric properties and loss level. When the components of the resin composition are mixed and applied to the flexible copper clad laminate as an adhesive, firm bonding of polyimide and other low-dielectric and low-loss films can be realized, and further, other low-dielectric and low-loss films with smaller difference with the thermal expansion coefficient of the copper foil can be arranged on the polyimide film, so that the thickness of the dielectric layer on the copper foil is increased, and the formed flexible copper clad laminate meets the requirements of 5G high-frequency and high-speed wireless transmission.
Solvents used in the above adhesives may include, but are not limited to, butanone, acetone, toluene, xylene, dimethylformamide, propylene glycol methyl ether, or any combination of the above.
In yet another exemplary embodiment of the present application, there is provided a flexible copper clad laminate comprising a copper substrate and a dielectric layer disposed on the copper substrate, the dielectric layer comprising a polyimide film, an adhesive layer and a low dielectric/low loss film, the polyimide film being disposed on a surface of the copper substrate; the adhesive layer is prepared from the adhesive; the low dielectric/low loss film is bonded to the polyimide film through the bonding layer, the absolute value of the difference between the thermal expansion coefficients of the low dielectric/low loss film and the copper substrate is A, and the absolute value of the difference between the thermal expansion coefficients of the polyimide and the copper substrate is B, wherein A is smaller than B.
When the components of the resin composition are mixed and then used as an adhesive to be applied to a flexible copper clad laminate, other low-dielectric and low-loss films with small difference with the thermal expansion coefficient of a copper foil can be arranged on a polyimide film, so that the thickness of the dielectric layer on the copper foil is increased, and the formed flexible copper clad laminate meets the requirements of 5G high-frequency and high-speed wireless transmission.
In order to further improve the wireless transmission performance of the flexible copper clad laminate, the thickness of the dielectric layer is preferably more than 50 μm, the thickness of the polyimide film is preferably 20-30 μm, and the low-dielectric/low-loss film is preferably a polyether-ether-ketone film. For example, low dielectric/low loss films such as polyetheretherketone films (KURABO, EX-PEEK, Dk ≈ 3.2; Df ≈ 0.002), and low dielectric/low loss polyimide films (Darma, LKA, Dk ≈ 2.8; Df ≈ 0.005, which is a commercial polyimide film having a CTE of 18.25 and close to copper foil (about 17), and thus the thermal expansion coefficient is very close to that of copper foil, and the expansion and contraction influence is small) are preferable.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
The preparation process of the adhesive comprises the following steps:
first, a fluorine-based resin (for example, various fluorine resins, i.e., perfluoroalkoxy polymer (EA-2000, ASAHI Glass): D50 ═ 2 to 3 μm, polytetrafluoroethylene (YA-4, Admatechs): D50 ═ 1.5 to 3 μm, and polyperfluorovinyl polymer (2801-00, akma): D50 ═ 3 to 5 μm) is dissolved in a solvent and stirred at a high speed (4000 to 5000rpm) for 1 hour to obtain a fluorine-based resin dispersion. In addition, a curing agent, a flame retardant and a curing accelerator are dissolved in a solvent, stirring and mixing are carried out, the mixing time is about 1.5 hours, then low-dielectric/low-loss epoxy resin is added, then a toughening agent is added, finally dispersed fluorine resin dispersion liquid is added, stirring and mixing are carried out for 3 hours, the adhesive can be obtained, the viscosity of the prepared adhesive is controlled to be 800-1200 cps, and the final solid content is about 50%.
The adhesives of examples and comparative examples were prepared according to the above-described procedures, and the compositions of the adhesives of examples and comparative examples are shown in tables 1-1 and 1-2.
TABLE 1-1
Tables 1 to 2
HP-7200 Low dielectric/Low loss Dicyclopentadiene Novolac epoxy resin, Japan DIC corporation;
SEV-3408, namely low-dielectric/low-loss dicyclopentadiene novolac epoxy resin, manufactured by Shandong industries;
HP-5000, Low dielectric/Low loss Dicyclopentadiene Novolac epoxy resin, Japan DIC corporation;
EBA-65 low dielectric/low loss naphthalene ring type epoxy resin, Shanghai Huayi resin Co., Ltd;
4,4-DDS 4, 4-diaminodiphenyl sulfone, manufactured by Atul corporation under the trade name of Alul Sulpho 44 DDS;
DICY is diethylenetriamine, manufactured by enterprises in the public;
SHC-4314M65 ester curing agent, Shengdong Shikuai;
PIAD: soluble polyimide, chemical made in Sichuan;
p-260 is soluble polyimide, made by USM;
PI-22 is soluble polyimide, promoting chemical industry;
BX-39SS polyester, manufactured by Toyo Japan;
hycar-1042 is acrylonitrile-butadiene rubber, made by south emperor chemical industry;
EA-2000 perfluoroalkoxy Polymer, manufactured by Japan ASAHI GLASS;
YA-4 Polytetrafluoroethylene, manufactured by Admatechs, Japan
2801-00 Poly (perfluorovinylidene) Polymer, manufactured by Achima
OP-935 aluminium diethyl phosphate, manufactured by Crainen chemical Co;
H-42M is aluminium hydroxide, made by Showa chemical industry;
BF3MEA, boron trifluoride-monoethyl ammonium complex, manufactured by Dow-believed chemical Co., Ltd;
C11Z: 2-methylimidazole, manufactured by Siguo Kagaku.
Copper-clad plate manufacturing method
MPI used for manufacturing the copper-clad plate is formed by dissolving aromatic diamine (at least two of p-diphenylamine, diaminodiphenyl ether, methylenedianiline and bis-trifluoromethyl-diphenyldiamine) in N-methyl pyrrolidone (NMP) firstly, and then adding aromatic tetracarboxylic dianhydride (optional biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, diphenylether tetracarboxylic dianhydride and the like) to perform polymerization reaction to form polyamic acid. Then, polyamic acid was coated on a copper foil of 1/3Oz (12 μm) by coating method, and subjected to desolvation and high-temperature imidization to form an MPI copper-clad substrate, wherein the thickness of MPI was about 25 μm, the Dk of MPI was about 2.80(@10GHz), and the Df was about 0.006(@10 GHz). In order to increase the overall thickness, a thin film with low dielectric constant/low loss is selected for thickening, preferably a polyether ether ketone film (KURABO, EX-PEEK, Dk is approximately equal to 3.2; Df is approximately equal to 0.002), a low dielectric constant/low loss polyimide film (Dadamei, LKA, Dk is approximately equal to 2.8; Df is approximately equal to 0.005, LKA film CTE is approximately equal to 18.25, and the problem of expansion and contraction is improved by being close to a copper foil).
Coating low-dielectric/low-loss colloid on an LKA film with the film thickness of about 10 μm, heating the film by using an idler wheel to attach the film to an MPI film of an MPI copper-clad substrate to achieve the thickening effect, and finally curing at 150 ℃ for 2 hours, wherein the low-dielectric/low-loss colloid can be tightly combined with the MPI and the LKA to form a single dielectric layer on the copper substrate to achieve the thickening effect.
[ evaluation means ]
Measurement of dielectric constant (Dk) and dielectric loss (Df):
the dielectric layers, which were colloid-thickened with the resin compositions obtained in examples and comparative examples, were dried at 150 ℃ for 30min, and the dielectric constant and dielectric loss of each dielectric layer were measured by the split dielectric resonator (SPDR) method using a resonator (agilent E5071BENA) under the conditions of 25 ℃ and 50% RH.
Comparison of soldering heat resistance:
see IPC-TM650.2.6.8 standard. The thickened copper-clad substrate of 5 cm × 5 cm was immersed in a tin furnace at a temperature of 288 ℃ for 30 seconds, and after taking out the test piece, the surface was observed for blistering, discoloration, floating, peeling, and the like, and the change in appearance was evaluated on the basis described below.
O: no delamination and no discoloration
X: delamination and discoloration
Tensile strength:
the composite dielectric layer in which the resin composition gels obtained in examples and comparative examples were thickened was cut into a test piece having a size of 152.4 cm × 12.7 cm. Then, the tensile strength of these test pieces was measured by a universal tensile machine.
Flame resistance:
the flame resistance referred to herein in the present invention is defined in UL-94V 0. Specifically, the thickened dielectric layer of the present invention was subjected to 2 burning tests for 10 seconds each, which indicated good flame resistance if the flame was extinguished within 30 seconds and no combustibles dropped. On the contrary, the flame resistance is not good, and the specific evaluation criteria are as follows:
o: the flame is extinguished within 30 seconds, no combustible substance falls, and the flame resistance is good
X: the flame is not extinguished within 30 seconds, or the burning substances fall off, and the flame resistance is poor
The test results of the above examples and comparative examples are shown in Table 2.
TABLE 2
From the data in table 2, it can be seen that the adhesive formed by the resin composition of the present application can successfully perform bonding with thickened dielectric layer, and the thickness of the dielectric layer can exceed 2mil (50 μm). According to the comparison between the examples and the comparative examples, it is obvious that the properties of the low dielectric/low loss epoxy resin, the toughening agent, the fluorine-containing resin and the flame retardant are different to different degrees if the low dielectric/low loss epoxy resin, the toughening agent, the fluorine-containing resin and the flame retardant are not used in the ranges of the amounts as shown in the patent of the invention, and therefore, the importance of the low dielectric/low loss resin composition colloid in the flexible copper clad laminate can be seen.
For example, in comparative example 1, the added epoxy resin was insufficient, the solder float heat resistance was poor, and the tensile strength was reduced; the used reinforcing agent is acrylonitrile-butadiene rubber, and the dielectric and loss of the rubber are much higher than those of the soluble polyimide and polyester resin used in the embodiment, namely the dielectric and loss characteristics of the whole composite material are influenced. Comparative example 2 has insufficient addition of the fluorine-containing resin and also has high dielectric/loss of the whole material; meanwhile, the flame retardant is insufficient, and the flame retardant property can not pass UL-94 VTM-0. In comparative example 3, the addition of epoxy resin is insufficient in weight portion, the heat resistance of the tin bleaching is poor, and the weight of the reinforcing agent is increased, so that the overall tensile strength is greatly reduced.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
any one or more of dicyclopentadiene novolac epoxy resin, biphenyl type epoxy resin and naphthalene ring type epoxy resin is/are adopted as the epoxy resin of the resin composition, the resins have low dielectric and low loss performance, and meanwhile, the fluororesin adopted in the composition has low dielectric and low loss performance, so that the requirements of 5G high-frequency and high-speed wireless transmission on dielectric performance and loss level can be met. When the components of the resin composition are mixed and applied to the flexible copper clad laminate as an adhesive, firm bonding of polyimide and other low-dielectric and low-loss films can be realized, and further, other low-dielectric and low-loss films with smaller difference with the thermal expansion coefficient of the copper foil can be arranged on the polyimide film, so that the thickness of the dielectric layer on the copper foil is increased, and the formed flexible copper clad laminate meets the requirements of 5G high-frequency and high-speed wireless transmission.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (18)
1. A resin composition, characterized in that the resin composition comprises, in weight percent:
35-45% of epoxy resin;
1-3.5% of a curing agent;
25-35% of a toughening agent;
15-25% of fluororesin;
10-20% of a flame retardant; and
1-3% of a curing accelerator;
the epoxy resin is a mixture of 3-5: 4 of weight ratio of HP-7200 series dicyclopentadiene phenol-formaldehyde epoxy resin to SEV-3408 series dicyclopentadiene phenol-formaldehyde epoxy resin, or the epoxy resin is a mixture of 25:15 or 20:20 of weight ratio of HP-5000 series dicyclopentadiene phenol-formaldehyde epoxy resin to EBA-65 series naphthalene ring type epoxy resin, or the epoxy resin is a mixture of 20:20 of weight ratio of HP-7200 series dicyclopentadiene phenol-formaldehyde epoxy resin to EBA-65 series naphthalene ring type epoxy resin;
the fluororesin is one or more of polytetrafluoroethylene, chlorotrifluoroethylene, perfluoroalkoxy polymer, fluorinated ethylene-propylene copolymer and polyperfluoro vinylidene polymer,
the toughening agent is selected from any one of polyimide resin, polyester resin, nitrile rubber, styrene-butadiene rubber and styrene-butadiene-styrene block copolymer.
2. The resin composition according to claim 1, wherein the fluororesin is a resin powder.
3. The resin composition according to claim 2, wherein the resin powder has an average particle diameter of 10 μm or less.
4. The resin composition according to claim 3, wherein the resin powder has an average particle diameter of 0.1 to 10 μm.
5. The resin composition according to claim 3, wherein the resin powder has an average particle diameter of 0.1 to 7 μm.
6. The resin composition according to claim 3, wherein the resin powder has an average particle diameter of 0.1 to 5 μm.
7. The resin composition according to claim 1, wherein the curing agent is selected from the group consisting of polyamine-based curing agents, phthalic anhydride-based curing agents, and ester-based curing agents.
8. The resin composition of claim 7, wherein the polyamine-based curing agent is diethylenetriamine, diaminodiphenylmethane, 3-diaminodiphenylsulfone, 4, 4-diaminodiphenylsulfone, and dicyandiamide, and the ester-based curing agent is SHC-4314M65, SHC-5620TM65, and SAP-641, which are commercially available from the Shandong province.
9. The resin composition according to claim 1, wherein the flame retardant is selected from the group consisting of a phosphorus-based flame retardant and a metal compound-containing flame retardant.
10. The resin composition according to claim 9, wherein the metal compound-containing flame retardant is a metal oxide or a metal hydroxide.
11. The resin composition according to claim 10, wherein the metal oxide has an average particle diameter of 1 to 5 μm.
12. The resin composition according to claim 1, wherein the curing accelerator is one or more selected from the group consisting of a Lewis base-based curing accelerator and a Lewis acid-based curing accelerator, the Lewis base-based curing accelerator being an imidazole and boron trifluoride amine complex, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole and 4-dimethylaminopyridine, and the Lewis acid-based curing accelerator being an organometallic salt-type compound.
13. The resin composition according to claim 12, wherein the lewis acid-based curing accelerator is an organic salt of manganese, iron, cobalt, nickel, copper, or zinc.
14. An adhesive prepared by mixing a solvent with the resin composition as defined in any one of claims 1 to 13, wherein the solid content of the adhesive is 35 to 60%.
15. The utility model provides a flexible copper-clad plate, flexible copper-clad plate includes the copper base plate and sets up dielectric layer on the copper base plate, its characterized in that, the dielectric layer includes:
a polyimide film disposed on a surface of the copper substrate;
an adhesive layer prepared from the adhesive of claim 14;
and the low-dielectric/low-loss film is bonded with the polyimide film through the bonding layer, the absolute value of the difference between the thermal expansion coefficients of the low-dielectric/low-loss film and the copper substrate is A, and the absolute value of the difference between the thermal expansion coefficients of the polyimide and the copper substrate is B, wherein A is smaller than B.
16. The flexible copper clad laminate according to claim 15, wherein the thickness of the dielectric layer is greater than 50 μm.
17. The flexible copper-clad plate according to claim 15, wherein the thickness of the polyimide film is 20 to 30 μm.
18. The flexible copper clad laminate according to claim 15 wherein the low dielectric/low loss film is a polyetheretherketone film.
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