CN204598463U - A kind of high-peeling strength flexibility coat copper plate - Google Patents
A kind of high-peeling strength flexibility coat copper plate Download PDFInfo
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Abstract
The utility model discloses a kind of high-peeling strength flexibility coat copper plate.Described copper-clad plate comprises with understructure: macromolecule membranous layer, be arranged on this macromolecule membranous layer at least one side on enhancement layer, the transition zone be arranged on this enhancement layer surface, the layers of copper be arranged on transition zone surface; Wherein, the number of plies of described transition zone is more than one deck.The utility model particularly by be arranged on macromolecule membranous layer at least one side on enhancement layer, make the copper-clad plate of this practicality have higher peel strength.
Description
Technical field
The utility model relates to a kind of high-peeling strength flexibility coat copper plate.
Background technology
Flexible printed circuit (FPC) is as a kind of special basic material connecting electronic devices and components, and it has gently, thin, various structures, the excellent properties such as resist bending.Can be widely used in folding cell phone, liquid crystal display, notebook computer, band carries the high-end fields such as IC base plate for packaging.
Traditional FCCL mainly has glue-type product, and primarily of copper, adhesive, the three-decker of PI film composition, is called for short 3L-FCCL.In 3L-FCCL, adhesive mostly is epoxies, and thermal stability is poor relative to PI base material, and cause the thermal stability of FCCL, dimensional stability declines all thereupon, and the thickness of base material is larger.In recent years, along with developing rapidly of electronics industry, electronic product is further to miniaturization, and lightweight, assembling densification develops, and industry starts the research and apply paying close attention to non-gel flexible copper-clad plate.And have compared with glue-type copper-clad plate, non-gel flexible copper-clad plate does not need binding agent, therefore good heat resistance, good stability of the dimension, and reliability is high; Meanwhile, non-gel flexible copper-clad plate is very thin, and resistance to bend(ing) is high.
Be the structure of several non-gel flexible copper-clad plate below:
Publication number is CN 1579754 A, name is called that the patent of invention of " a kind of preparation method around property copper-clad plate " discloses a kind of non-gel flexible copper-clad plate, its structure is at polymer film surface Vacuum Deposition conductor layer, then continuous Composite Coatings metal level, the advantage of the copper-clad plate in this invention is that metal level is very thin, thickness is even, but peel strength is lower, cannot meet instructions for use.
Publication number is CN 1189125 A, product structure disclosed in the patent of invention that name is called " adhesive-free flexible layer combination product and preparation method thereof " is at least one side and the Plasma contact comprised by the ionized oxygen produced without plating negative electrode at polymer film, form plasma treated surface, at plasma surface nickel deposited or nickel alloy tack coat, copper layer on nickel tack coat.The peel strength of the copper-clad plate of this invention is still undesirable, cannot meet instructions for use, and the surface simultaneously processed is unstable, is not suitable for web-like in enormous quantities and produces.
Publication number is CN 102717554 A, name is called that the patent of invention of " a kind of two stratotype flexibility coat copper plates " discloses a kind of double-layer structure flexibility coat copper plate in organic polymer thin film surface coverage layers of copper, the peel strength of the copper-clad plate of this invention only has 6-7N/cm, cannot use.
In the structure of above mentioned copper-clad plate, or directly form conductor prime coat at polymer film surface, then form layers of copper, the peel strength of the copper-clad plate of this structure is extremely low, only 3-5N/cm; In order to improve the adhesion between organic polymer films and metal level, or adopting shaggy polymer film, on this film, forming prime coat and metal level; Or before formation metal level, increase ion injecting process, but the peel strength of the final copper-clad plate formed is still very low.
The non-gel flexible copper-clad plate obtaining a kind of high-peeling strength be when and need the problem of solution badly.
Utility model content
The purpose of this utility model is to provide a kind of high-peeling strength flexibility coat copper plate.
Technical solution adopted in the utility model is:
A kind of high-peeling strength flexibility coat copper plate, comprises with understructure: macromolecule membranous layer, be arranged on enhancement layer, the transition zone that be arranged on this enhancement layer surface on, the layers of copper that be arranged on transition zone surface on of this macromolecule membranous layer at least on one side; Wherein, the number of plies of described transition zone is more than one deck.
The thickness of described macromolecule membranous layer is 5-125 micron; The material of described macromolecule membranous layer is at least one in polyimides, PETG, polybutylene terephthalate (PBT), polysulfones, polyphenylene sulfide, polyether-ether-ketone, polyphenylene oxide, polytetrafluoroethylene, liquid crystal polymer, polyparabanic acid.
Described enhancement layer is following I)-V) cited by one:
I) material of described enhancement layer is selected from the one in thermoplastic polyimide class, modified epoxy class, modified acrylic acid, modified polyurethane, modified phenolic resin resin;
II) material of described enhancement layer is selected from particles filled polymer composite;
III) material of described enhancement layer is selected from the one in coupling agent, surfactant, organosilicon, organic oligomer surface modifier;
IV) described enhancement layer is I) with III) overlapping layers of two class enhancement layers;
V) described enhancement layer is II) with III) overlapping layers of two class enhancement layers.
The material of described enhancement layer is I) described in time, the thickness of enhancement layer is 0.05-30 micron.
The material of described enhancement layer is II) described in time, the thickness of enhancement layer is 0.05-30 micron.
The material of described enhancement layer is III) described in time, the thickness of enhancement layer is 10-100 nanometer.
The formation of described enhancement layer is IV) described in time, the thickness of enhancement layer is 0.05-30 micron; The formation of described enhancement layer is V) described in time, the thickness of enhancement layer is 0.05-30 micron.
When described transition zone is individual layer, its thickness is 0.01-0.5 micron; When the number of plies of transition zone is more than one deck, its gross thickness is 0.01-0.5 micron; One in the material selected from metal material of transition zone, ferrite, carbon nano-tube; Wherein, described metal material is the one in these metal simple-substances: aluminium, titanium, zinc, iron, nickel, chromium, cobalt, copper, silver, gold, molybdenum; Or be at least two kinds of alloys formed in these metal simple-substances.
Described layers of copper is shaggy layers of copper.
Described layers of copper surface is provided with oxidation resistant protective layer.
The beneficial effects of the utility model are: the utility model particularly by be arranged on macromolecule membranous layer at least one side on enhancement layer, make the copper-clad plate of this practicality have higher peel strength.
Accompanying drawing explanation
Fig. 1 is the Rotating fields schematic diagram of a kind of flexibility coat copper plate of the utility model.
Fig. 2 is the utility model another kind of high-peeling strength flexibility copper-clad board structure schematic diagram.
Fig. 3 is the utility model another kind of high-peeling strength flexibility copper-clad board structure schematic diagram.
Fig. 4 is the utility model another kind of high-peeling strength flexibility copper-clad board structure schematic diagram.
Fig. 5 is the utility model another kind of high-peeling strength flexibility copper-clad board structure schematic diagram.
Embodiment
A kind of high-peeling strength flexibility coat copper plate, forms by with understructure: macromolecule membranous layer, be arranged on enhancement layer, the transition zone that be arranged on this enhancement layer surface on, the layers of copper that be arranged on transition zone surface on of this macromolecule membranous layer at least on one side; Wherein, the number of plies of described transition zone is more than one deck; Preferably, described layers of copper is shaggy layers of copper.
Or, form by with understructure: macromolecule membranous layer, be arranged on enhancement layer, the transition zone that be arranged on this enhancement layer surface on, the layers of copper that be arranged on transition zone surface on of this macromolecule membranous layer at least on one side, be arranged on the oxidation resistant protective layer on layers of copper surface; Wherein, the number of plies of described transition zone is more than one deck; Preferably, described layers of copper is shaggy layers of copper.
The thickness of described macromolecule membranous layer is 5-125 micron; The material of described macromolecule membranous layer is at least one in polyimides, PETG, polybutylene terephthalate (PBT), polysulfones, polyphenylene sulfide, polyether-ether-ketone, polyphenylene oxide, polytetrafluoroethylene, liquid crystal polymer, polyparabanic acid; Preferably, the thickness of described macromolecule membranous layer is 5-50 micron.
Described enhancement layer is following I)-V) cited by one:
I) material of described enhancement layer is selected from the one in thermoplastic polyimide class, modified epoxy class, modified acrylic acid, modified polyurethane, modified phenolic resin resin, and the thickness of described enhancement layer is 0.05-30 micron; Be preferably 0.5-5 micron;
II) material of described enhancement layer is selected from particles filled polymer composite, and its thickness is 0.05-30 micron; Be preferably 0.5-6 micron;
III) material of described enhancement layer is selected from the one in coupling agent, surfactant, organosilicon, organic oligomer surface modifier, and the thickness of described enhancement layer is 10-100 nanometer; Be preferably 10-50 nanometer;
IV) described enhancement layer is I) with III) overlapping layers of two class enhancement layers, thickness is 0.05-30 micron; Be preferably 0.5-5 micron;
V) described enhancement layer is II) with III) overlapping layers of two class enhancement layers, thickness is 0.05-30 micron; Be preferably 0.5-6 micron.
When described transition zone is individual layer, its thickness is 0.01-0.5 micron; Be preferably 0.05-0.3 micron; When the number of plies of transition zone is more than one deck, its gross thickness is 0.01-0.5 micron; Be preferably 0.05-0.3 micron; Transition zone is that the one in metal material, ferrite, carbon nano-tube is made; Wherein, described metal material is the one in these metal simple-substances: aluminium, titanium, zinc, iron, nickel, chromium, cobalt, copper, silver, gold, molybdenum; Or be at least two kinds of alloys formed in these metal simple-substances;
The generation type of described transition zone is selected from chemical plating mode, PVD, CVD, evaporation plating, sputtering plating, plating or its combination process; The generation type of described layers of copper is selected from chemical plating mode, PVD, CVD, evaporation plating, sputtering plating, plating or its combination process;
The thickness of layers of copper is 0.5-50 micron; Be preferably 5-20 micron.
Preferably, described macromolecule membranous layer and/or the surface of enhancement layer are coarse or are connected to polar group.
Corresponding, a kind of manufacture method of high-peeling strength flexibility coat copper plate, comprises the following steps:
1) at least simultaneously enhancement layer is formed at macromolecule membranous layer;
2) the above transition zone of one deck is formed on enhancement layer surface;
3) metal copper layer is formed on the surface of transition zone.
Preferably, a kind of manufacture method of high-peeling strength flexibility coat copper plate, comprises the following steps:
1) at least one side of macromolecule membranous layer is carried out surface modification, macromolecule membranous layer after modification at least one side forms enhancement layer; Preferably, the modification face of macromolecule membranous layer after modification forms enhancement layer;
2) the above transition zone of one deck is formed on enhancement layer surface;
3) metal copper layer is formed on the surface of outermost layer transition zone.
Preferably, a kind of manufacture method of high-peeling strength flexibility coat copper plate, comprises the following steps:
1) at least simultaneously enhancement layer is formed at macromolecule membranous layer;
2) described enhancement layer is carried out surface modification;
3) the above transition zone of one deck is formed on the enhancement layer surface of modification;
4) metal copper layer is formed on the surface of transition zone.
Preferably, a kind of manufacture method of high-peeling strength flexibility coat copper plate, comprises the following steps:
1) at least one side of macromolecule membranous layer is carried out surface modification;
2) macromolecule membranous layer after modification at least one side form enhancement layer; Preferably, the modification face of macromolecule membranous layer after modification forms enhancement layer;
3) described enhancement layer is carried out surface modification;
4) the above transition zone of one deck is formed on the enhancement layer surface of modification;
5) metal copper layer is formed on the surface of transition zone.
Described macromolecule membranous layer or the surface modifying method of enhancement layer are selected from chemical etching, plasma treatment, ion implantation, surface grafting, ion beam irradiation, excimer laser etching or its combination process.
The object of surface modification increases or surface grafting polar group to make the roughness of respective layer.
A manufacture method for high-peeling strength flexibility coat copper plate, according to actual needs, also can comprise step: after forming metal copper layer, forms oxidation resistant protective layer on metal copper layer surface; Or, by metal copper layer roughening.
Above-described method step is common practise.
The wherein structure of five kinds of the utility model copper-clad plate is described below in conjunction with accompanying drawing:
As shown in Figure 1, be a kind of Rotating fields schematic diagram of the utility model copper-clad plate, a side surface of macromolecule membranous layer 1 is provided with enhancement layer 2, and the opposite side surface of described enhancement layer 2 is provided with one deck transition zone 3, and the opposite side surface of described transition zone 3 is provided with layers of copper 4; Namely enhancement layer, transition zone, layers of copper is formed with successively on the surface in the side of macromolecule membranous layer.
The material of each layer, thickness are as the description of front (embodiment) part.
As shown in Figure 2, it is the another kind of Rotating fields schematic diagram of the utility model copper-clad plate, one side surface of macromolecule membranous layer 1 is provided with the first enhancement layer 21, the opposite side surface of described first enhancement layer 21 is provided with the second enhancement layer 22, the opposite side surface of the second enhancement layer 22 is provided with transition zone 3, and the opposite side surface of described transition zone 3 arranges layers of copper 4; Namely the first enhancement layer, the second enhancement layer, transition zone, layers of copper is formed with on the surface successively in the side of macromolecule membranous layer.
The material of each layer, thickness are as the description of front (embodiment) part.
Especially, the first enhancement layer 21 is selected from aforementioned I) described by enhancement layer, the second enhancement layer 22 is aforementioned III) described by enhancement layer; Or conversely, the first enhancement layer 21 is aforementioned III) described by enhancement layer, the second enhancement layer is aforementioned I) described by enhancement layer;
Or the first enhancement layer 21 is selected from aforementioned II) described by enhancement layer, the second enhancement layer 22 is aforementioned III) described by enhancement layer; Or conversely, the first enhancement layer 21 is aforementioned III) described by enhancement layer, the second enhancement layer 22 is aforementioned II) described by enhancement layer.
As shown in Figure 3, it is the another kind of Rotating fields schematic diagram of the utility model copper-clad plate, one side surface of macromolecule membranous layer 1 is provided with the first enhancement layer 211, the opposite side surface of described first enhancement layer 211 is provided with the second enhancement layer 212, the opposite side surface of the second enhancement layer 212 is provided with First Transition layer 31, and the opposite side surface of described First Transition layer 31 arranges the first layers of copper 41; The opposite side surface of macromolecule membranous layer 1 is provided with the 3rd enhancement layer 221, the opposite side surface of described 3rd enhancement layer 221 is provided with the 4th enhancement layer 222, the opposite side surface of the 4th enhancement layer 222 is provided with the second transition zone 32, and the opposite side surface of described second transition zone 32 arranges the second layers of copper 42.
The material of each layer, thickness are as the description of front (embodiment) part.
Special instruction, the first enhancement layer 211, second enhancement layer 212 forms the enhancement layer be superimposed together, and its situation meets in preceding sections (embodiment) IV) or V);
Same, the 3rd enhancement layer 211, the 4th enhancement layer 212 form the enhancement layer be superimposed together, and its situation meets in preceding sections (embodiment) IV) or V).
As shown in Figure 4, it is the another kind of Rotating fields schematic diagram of the utility model copper-clad plate, one side surface of macromolecule membranous layer 1 is provided with enhancement layer 2, the opposite side surface of described enhancement layer 2 is provided with First Transition layer 31, the opposite side surface of described transition zone 31 is provided with the second transition zone 32, second transition zone 32 opposite side surface and is provided with layers of copper 4; Namely enhancement layer, First Transition layer, the second transition zone, layers of copper is formed with on the surface successively in the side of macromolecule membranous layer.
The material of each layer, thickness are as the description of front (embodiment) part.
As shown in Figure 5, it is the another kind of Rotating fields schematic diagram of the utility model copper-clad plate, one side surface of macromolecule membranous layer 1 is provided with enhancement layer 2, and the opposite side surface of described enhancement layer 2 is provided with one deck transition zone 3, and the opposite side surface of described transition zone 3 is provided with layers of copper 4; The opposite side surface of layers of copper 4 is provided with oxidation resistant protective layer 5, is namely formed with enhancement layer, transition zone, layers of copper, oxidation resistant protective layer successively on the surface in the side of macromolecule membranous layer.
The material of each layer, thickness are as the description of front (embodiment) part.
Below in conjunction with specific embodiment, the utility model is described further:
embodiment 1:
A kind of high-peeling strength flexibility coat copper plate: comprise macromolecule membranous layer, macromolecule membranous layer is at least provided with enhancement layer on one side, and the opposite side of described enhancement layer is provided with the transition zone of more than one deck, and the opposite side of described transition zone is provided with layers of copper.Wherein, described enhancement layer can improve the peel strength of macromolecule membranous layer and metal level.
The thickness of described macromolecule membranous layer is 5-125 micron, preferred 5-50 micron; The material of described macromolecule membranous layer is selected from the one in polyimides, PETG, polybutylene terephthalate (PBT), polysulfones, polyphenylene sulfide, polyether-ether-ketone, polyphenylene oxide, polytetrafluoroethylene, liquid crystal polymer, polyparabanic acid;
The formation of the material of described enhancement layer and thickness or enhancement layer is one of following five kinds of situations:
I) material making enhancement layer is selected from the one in following resins: thermoplastic polyimide class, modified epoxy class, modified acrylic acid, modified polyurethane, modified phenolic resin resin, and thickness is 0.05-30 micron, preferred 0.5-5 micron;
II) or, the material of described enhancement layer is selected from particles filled polymer composite, and its thickness is 0.05-30 micron, preferred 0.5-6 micron;
III) or, the material of described enhancement layer is selected from the one in coupling agent, surfactant, organosilicon, organic oligomer surface modifier, and thickness is 10-100 nanometer, preferred 10-50 nanometer;
IV) or, described enhancement layer is I) with III) overlapping layers of two class enhancement layers, thickness is 0.05-30 micron, preferred 0.5-5 micron;
V) or, described enhancement layer is II) with III) overlapping layers of two class enhancement layers, thickness is 0.05-30 micron, preferred 0.5-6 micron, is increased the peel strength of macromolecule membranous layer and transition zone by enhancement layer.
Described transition region thickness is that 0.01-0.5 micron is (when namely transition zone is individual layer, the thickness of individual layer transition zone is 0.01-0.5 micron, when transition zone is more than one deck, the gross thickness of transition zone is 0.01-0.5 micron, when the following examples relate to the thickness restriction of transition zone, all these implications), preferred 0.05-0.3 micron; Transition zone material therefor is the one in metal material, ferrite, carbon nano-tube; Wherein, described metal material is the one in these metal simple-substances: aluminium, titanium, zinc, iron, nickel, chromium, cobalt, copper, silver, gold, molybdenum; Or be at least two kinds of alloys formed in these metal simple-substances.
The thickness of described layers of copper is 0.5-50 micron, preferred 5-20 micron.
A manufacture method for high-peeling strength flexibility coat copper plate, it concrete making step comprised is as follows:
1) at least simultaneously enhancement layer is formed at macromolecule membranous layer;
2) the above transition zone of one deck is formed on enhancement layer surface; The generation type of described transition zone is selected from one of following manner: chemical plating mode, PVD, CVD, evaporation plating, sputtering plating, plating or its combination process.
3) metal copper layer is formed on transition zone surface.The generation type of described layers of copper is selected from chemical plating mode, PVD, CVD, evaporation plating, sputtering plating, plating or its combination process.
Preparation method is common practise in the industry.
embodiment 2:
A kind of high-peeling strength flexibility coat copper plate: comprise macromolecule membranous layer, macromolecule membranous layer is at least provided with enhancement layer on one side, and the opposite side of described enhancement layer is provided with the transition zone of more than one deck, and the opposite side of described transition zone is provided with layers of copper.Wherein, described enhancement layer can improve the peel strength of macromolecule membranous layer and metal level.
The thickness of described macromolecule membranous layer is 5-125 micron, preferred 5-50 micron; The material of described macromolecule membranous layer is selected from the one in polyimides, PETG, polybutylene terephthalate (PBT), polysulfones, polyphenylene sulfide, polyether-ether-ketone, polyphenylene oxide, polytetrafluoroethylene, liquid crystal polymer, polyparabanic acid; And and the surface of macromolecule membranous layer that contacts of enhancement layer be coarse or be connected to polar group.
The formation of the material of described enhancement layer and thickness or enhancement layer is one of following five kinds of situations:
I) material making enhancement layer is selected from the one in following resins: thermoplastic polyimide class, modified epoxy class, modified acrylic acid, modified polyurethane, modified phenolic resin resin, and thickness is 0.05-30 micron, preferred 0.5-5 micron;
II) or, the material of described enhancement layer is selected from particles filled polymer composite, and thickness is 0.05-30 micron, preferred 0.5-6 micron;
III) or, the material of described enhancement layer is selected from the one in coupling agent, surfactant, organosilicon, organic oligomer surface modifier, and thickness is 10-100 nanometer, preferred 10-50 nanometer;
IV) or, described enhancement layer is I) with III) overlapping layers of two class enhancement layers, thickness is 0.05-30 micron, preferred 0.5-5 micron;
V) or, described enhancement layer is II) with III) overlapping layers of two class enhancement layers, thickness is 0.05-30 micron, preferred 0.5-6 micron;
Described transition region thickness is 0.01-0.5 micron, preferred 0.05-0.3 micron; Transition zone material therefor is the one in metal material, ferrite, carbon nano-tube; Wherein, described metal material is the one in these metal simple-substances: aluminium, titanium, zinc, iron, nickel, chromium, cobalt, copper, silver, gold, molybdenum; Or be at least two kinds of alloys formed in these metal simple-substances;
The thickness of described layers of copper is 0.5-50 micron, preferred 5-20 micron.
A manufacture method for high-peeling strength flexibility coat copper plate, it concrete making step comprised is as follows:
1) at least one side of macromolecule membranous layer is carried out surface modification; The surface modifying method of described macromolecule membranous layer is chemical etching, plasma treatment, ion implantation, surface grafting, ion beam irradiation, excimer laser etching or its combination process, so that improve the peel strength of macromolecule membranous layer and enhancement layer.
2) on the modification face of the macromolecule membranous layer of modification, enhancement layer is formed;
3) the above transition zone of one deck is formed on enhancement layer surface; The generation type of described transition zone is selected from chemical plating mode, PVD, CVD, evaporation plating, sputtering plating, plating or its combination process.
4) metal copper layer is formed on transition zone surface.The generation type of described layers of copper is selected from chemical plating mode, PVD, CVD, evaporation plating, sputtering plating, plating or its combination process.
embodiment 3:
A kind of high-peeling strength flexibility coat copper plate: comprise macromolecule membranous layer, macromolecule membranous layer is at least provided with enhancement layer on one side, and the opposite side of described enhancement layer is provided with the transition zone of more than one deck, and the opposite side of described transition zone is provided with layers of copper.Wherein, described enhancement layer can improve the peel strength of macromolecule membranous layer and metal level.
The thickness of described macromolecule membranous layer is 5-125 micron, preferred 5-50 micron; The material of described macromolecule membranous layer is at least one in polyimides, PETG, polybutylene terephthalate (PBT), polysulfones, polyphenylene sulfide, polyether-ether-ketone, polyphenylene oxide, polytetrafluoroethylene, liquid crystal polymer, polyparabanic acid.
The formation of the material of described enhancement layer and thickness or enhancement layer is one of following five kinds of situations:
I) material making enhancement layer is selected from the one in following resins: thermoplastic polyimide class, modified epoxy class, modified acrylic acid, modified polyurethane, modified phenolic resin resin, and thickness is 0.05-30 micron, preferred 0.5-5 micron;
II) or, the material of described enhancement layer is particles filled polymer composite, and thickness is 0.05-30 micron, preferred 0.5-6 micron;
III) or, the material of described enhancement layer is selected from the one in coupling agent, surfactant, organosilicon, organic oligomer surface modifier, and thickness is 10-100 nanometer, preferred 10-50 nanometer;
IV) or, described enhancement layer is I) with III) overlapping layers of two class enhancement layers, thickness is 0.05-30 micron, preferred 0.5-5 micron;
V) or, described enhancement layer is II) with III) overlapping layers of two class enhancement layers, thickness is 0.05-30 micron, preferred 0.5-6 micron.
And and the surface of enhancement layer that contacts of transition zone be coarse or be connected to polar group.
Described transition region thickness is 0.01-0.5 micron, preferred 0.05-0.3 micron; Transition zone material therefor is the one in metal material, ferrite, carbon nano-tube; Wherein, described metal material is the one in these metal simple-substances: aluminium, titanium, zinc, iron, nickel, chromium, cobalt, copper, silver, gold, molybdenum; Or be at least two kinds of alloys formed in these metal simple-substances.
The thickness of described layers of copper is 0.5-50 micron, preferred 5-20 micron.
A manufacture method for high-peeling strength flexibility coat copper plate, concrete making step is as follows:
1) at least simultaneously enhancement layer is formed at macromolecule membranous layer;
2) described enhancement layer is carried out surface modification; The surface modifying method of described enhancement layer is chemical etching, plasma treatment, ion implantation, surface grafting, ion beam irradiation, excimer laser etching or its combination process, improves the peel strength of enhancement layer and transition zone.
3) transition zone is formed on the enhancement layer surface of modification; The generation type of described transition zone is selected from chemical plating mode, PVD, CVD, evaporation plating, sputtering plating, plating or its combination process.
4) metal copper layer is formed on transition zone surface.The generation type of described layers of copper is selected from chemical plating mode, PVD, CVD, evaporation plating, sputtering plating, plating or its combination process.
embodiment 4:
A kind of high-peeling strength flexibility coat copper plate: comprise macromolecule membranous layer, macromolecule membranous layer is at least provided with enhancement layer on one side, and the opposite side of described enhancement layer is provided with the transition zone of more than one deck, and the opposite side of described transition zone is provided with layers of copper.Wherein, described enhancement layer can improve the peel strength of macromolecule membranous layer and metal level.
The thickness of described macromolecule membranous layer is 5-125 micron, preferred 5-50 micron; The material of described macromolecule membranous layer is selected from the one in polyimides, PETG, polybutylene terephthalate (PBT), polysulfones, polyphenylene sulfide, polyether-ether-ketone, polyphenylene oxide, polytetrafluoroethylene, liquid crystal polymer, polyparabanic acid; The surface of described macromolecule membranous layer is coarse or is connected to polar group; And and the surface of macromolecule membranous layer that contacts of enhancement layer be coarse or be connected to polar group.
The material of described enhancement layer or be configured to one of following five kinds of situations:
I) material making enhancement layer is selected from the one in following resins: thermoplastic polyimide class, modified epoxy class, modified acrylic acid, modified polyurethane, modified phenolic resin resin, and thickness is 0.05-30 micron, preferred 0.5-5 micron;
II) or, described enhancement layer is particles filled polymer composite, and its thickness is 0.05-30 micron, preferred 0.5-6 micron;
III) or, the one that the material of described enhancement layer is selected from coupling agent, surfactant, organosilicon, organic oligomer surface modifier is made, and its thickness is 10-100 nanometer, preferred 10-50 nanometer;
IV) or, described enhancement layer is I) with III) overlapping layers of two class enhancement layers, thickness is 0.05-30 micron, preferred 0.5-5 micron;
V) or, described enhancement layer is II) with III) overlapping layers of two class enhancement layers, thickness is 0.05-30 micron, preferred 0.5-6 micron;
And and the surface of enhancement layer that contacts of transition zone be coarse or be connected to polar group.
Described transition region thickness is 0.01-0.5 micron, preferred 0.05-0.3 micron; Transition zone material therefor is the one in metal material, ferrite, carbon nano-tube; Wherein, described metal material is the one in these metal simple-substances: aluminium, titanium, zinc, iron, nickel, chromium, cobalt, copper, silver, gold, molybdenum; Or be at least two kinds of alloys formed in these metal simple-substances.
The thickness of described layers of copper is 0.5-50 micron, preferred 5-20 micron.
A manufacture method for high-peeling strength flexibility coat copper plate, it concrete making step comprised is as follows:
1) at least one side of macromolecule membranous layer is carried out surface modification; The surface modifying method of described macromolecule membranous layer is chemical etching, plasma treatment, ion implantation, surface grafting, ion beam irradiation, excimer laser etching or its combination process, so that improve the peel strength of macromolecule membranous layer and enhancement layer.
2) on the modification face of the macromolecule membranous layer of modification, enhancement layer is formed;
3) described enhancement layer is carried out surface modification; The surface modifying method of described enhancement layer is selected from chemical etching, plasma treatment, ion implantation, surface grafting, ion beam irradiation, excimer laser etching or its combination process, improves the peel strength of enhancement layer and transition zone.
4) transition zone is formed on the enhancement layer surface of modification; The generation type of described transition zone is selected from chemical plating mode, PVD, CVD, evaporation plating, sputtering plating, plating or its combination process.
5) metal copper layer is formed on transition zone surface.The generation type of described layers of copper is selected from chemical plating mode, PVD, CVD, evaporation plating, sputtering plating, plating or its combination process.
embodiment 5:
A kind of high-peeling strength flexibility coat copper plate: comprise polymer film, macromolecule membranous layer side is provided with enhancement layer on the surface, and the opposite side of described enhancement layer is provided with one deck transition zone, and the opposite side of described transition zone is provided with layers of copper.Wherein, described enhancement layer can improve the peel strength of macromolecule membranous layer and metal level.
Described macromolecule membranous layer is the polyimide film of 12.5 microns, and described enhancement layer is modified polyurethane layer, and thickness is 1 micron;
Described transition zone is the layers of copper of 0.02 micron;
The thickness of described layers of copper is 8 microns.
A manufacture method for high-peeling strength flexibility coat copper plate, its concrete making step is as follows:
1) enhancement layer is formed by painting method on the surface in macromolecule membranous layer side;
2) transition zone is formed on enhancement layer surface; Described transition zone is formed by the method for sputtering.
3) form metal copper layer on transition zone surface, generation type is adopt sputtering to plate the combination process with plating.The peel strength of flexibility coat copper plate is 10N/cm, and after 288 DEG C of drift tin 10 seconds, peel strength is 9.2N/cm.
Wherein, step 1) changes the surface roughness of macromolecule membranous layer by the enhancement layer of 1 micron thickness, so that improve the peel strength of flexibility coat copper plate, compared with existing method (chemical etching, surface grafting etc.), peel strength become large while do not affect the physical and mechanical properties of product, and the surface of enhancement layer is highly stable, is applicable to web-like in enormous quantities and produces.
Simultaneously, inventor of the present utility model finds, before formation enhancement layer, to carry out surface treatment to macromolecule membranous layer, or carries out surface treatment to enhancement layer and all can improve peel strength further, carry out surface treatment to macromolecule membranous layer and enhancement layer, peel strength is larger simultaneously.
embodiment 6:
A kind of high-peeling strength flexibility coat copper plate: comprise polymer film, it is provided with enhancement layer at macromolecule membranous layer one side surface, and the opposite side of described enhancement layer is provided with one deck transition zone, and the opposite side of described transition zone is provided with layers of copper.Wherein, described enhancement layer can improve the peel strength of macromolecule membranous layer and metal level.
Described macromolecule membranous layer is the polyimide film of 12.5 microns;
Described enhancement layer is particles filled polyurethane, and the thickness of enhancement layer is 1 micron;
Described transition zone is the layers of copper of 0.02 micron;
The thickness of described layers of copper (i.e. the layers of copper of transition zone opposite side setting) is 8 microns.
A manufacture method for high-peeling strength flexibility coat copper plate, its concrete making step is as follows:
1) enhancement layer is formed at macromolecule membranous layer one side surface;
2) transition zone is formed on enhancement layer surface; Described transition zone is formed by the method for sputtering;
3) metal copper layer is formed on transition zone surface.Described layers of copper adopts sputtering plating to be formed with the combination process of plating.
The peel strength of flexibility coat copper plate is 11.5N/cm, and after 288 DEG C of drift tin 10 seconds, peel strength is 10N/cm.
The present embodiment compared with embodiment 5, because enhancement layer is particles filled polyurethane; The introducing of enhancement layer makes the surface roughness of macromolecule membranous layer larger, and the peel strength of flexibility coat copper plate is larger.
Simultaneously, inventor of the present utility model finds, before formation enhancement layer, to carry out surface treatment to macromolecule membranous layer, or carries out surface treatment to enhancement layer and all can improve peel strength further, carry out surface treatment to increase roughness to macromolecule membranous layer and enhancement layer, peel strength is larger simultaneously.
embodiment 7:
A kind of high-peeling strength flexibility coat copper plate: comprise polymer film, it is provided with enhancement layer at macromolecule membranous layer one side surface, and the opposite side of described enhancement layer is provided with one deck transition zone, and the opposite side of described transition zone is provided with layers of copper.Wherein, described enhancement layer can improve the peel strength of organic polymer films and metal level.
Described macromolecule membranous layer is the polyimide film of 12.5 microns;
The material of enhancement layer is selected from organic oligomer surface modifier, and thickness is 0.01 micron;
Described transition zone is the layers of copper of 0.02 micron;
The thickness of described layers of copper is 8 microns;
A manufacture method for high-peeling strength flexibility coat copper plate, it concrete making step comprised is as follows:
1) enhancement layer is formed on macromolecule membranous layer surface; By enhancement layer, increase the peel strength of macromolecule membranous layer and transition zone.
2) form transition zone on enhancement layer surface, described transition zone is formed by the method for sputtering;
3) metal copper layer is formed on transition zone surface.Described layers of copper adopts sputtering plating to be formed with the combination process of plating.
The peel strength of flexibility coat copper plate is 9.9N/cm, and after 288 DEG C of drift tin 10 seconds, peel strength is 8N/cm.
Wherein, step 1) is the organic oligomer class surface modifier macromolecule membranous layer surface-coated 0.01 micron, and its meaning is that the method by chemistry increases the surface polar groups of macromolecule membranous layer, and then improves the peel strength of flexibility coat copper plate.
Simultaneously, inventor of the present utility model finds, before formation enhancement layer, to carry out surface treatment to macromolecule membranous layer, or carries out surface treatment to enhancement layer and all can improve peel strength further, carry out surface treatment to macromolecule membranous layer and enhancement layer, peel strength is larger simultaneously.
embodiment 8:
A kind of high-peeling strength flexibility coat copper plate: comprise polymer film, it is provided with the first enhancement layer at macromolecule membranous layer one side surface, the opposite side of the first enhancement layer is provided with the second enhancement layer, the opposite side of described second enhancement layer is provided with one deck transition zone, and the opposite side of described transition zone is provided with layers of copper.Wherein, described enhancement layer can improve the peel strength of organic polymer films and metal level.
Described macromolecule membranous layer is the polyimide film of 12.5 microns;
First enhancement layer is the enhancement layer of 10 nanometer thickness with silane coupler formation;
Described second enhancement layer is modified polyurethane, and thickness is 3 microns;
Described transition zone is the layers of copper of 0.02 micron.
The thickness of described layers of copper is 8 microns.
A manufacture method for high-peeling strength flexibility coat copper plate, it concrete making step comprised is as follows:
1) the first enhancement layer is formed on macromolecule membranous layer surface; By the first enhancement layer, increase the peel strength of macromolecule membranous layer and the second enhancement layer.
2) the second enhancement layer is formed on the first enhancement layer surface; The peel strength of macromolecule membranous layer and transition zone is increased by first, second enhancement layer.
3) transition zone is formed on the second enhancement layer surface; Described transition zone is formed by the method for sputtering.
4) metal copper layer is formed on transition zone surface.Described layers of copper adopts sputtering plating to be formed with the combination process of plating.
The peel strength of flexibility coat copper plate is 12.5N/cm, and after 288 DEG C of drift tin 10 seconds, peel strength is 10N/cm.
Wherein, step 1) is that the silane coupler first applying 10 nanometer thickness on macromolecule membranous layer surface forms the first enhancement layer, again by step 2) at the surface coating modified polyurethane of the first enhancement layer, its meaning is the surface polar groups first being increased macromolecule membranous layer by the method for chemistry, increase the peel strength of itself and the second enhancement layer, and then the surface roughness of macromolecule membranous layer is changed by arranging the second enhancement layer, finally reach the object of the peel strength improving flexibility coat copper plate.
Simultaneously, inventor of the present utility model finds, before formation enhancement layer, to carry out surface treatment to macromolecule membranous layer, or carries out surface treatment to the second enhancement layer and all can improve peel strength further, carry out surface treatment to macromolecule membranous layer and the second enhancement layer, peel strength is larger simultaneously.
embodiment 9:
A kind of high-peeling strength flexibility coat copper plate: comprise polymer film, it is provided with the first enhancement layer at macromolecule membranous layer one side surface, the opposite side of the first enhancement layer is provided with the second enhancement layer, the opposite side of described second enhancement layer is provided with one deck transition zone, and the opposite side of described transition zone is provided with layers of copper.Wherein, described enhancement layer can improve the peel strength of macromolecule membranous layer and metal level.
Described macromolecule membranous layer is the polyimide film of 12.5 microns;
The material of described first enhancement layer is selected from silane coupler, and its thickness is 10 nanometers;
Described second enhancement layer is particles filled polyurethane;
Described transition zone is the layers of copper of 0.02 micron.
The thickness of described layers of copper is 8 microns.
A manufacture method for high-peeling strength flexibility coat copper plate, it concrete making step comprised is as follows:
1) the first enhancement layer is formed on macromolecule membranous layer surface; By the first enhancement layer, increase the peel strength of macromolecule membranous layer and the second enhancement layer.
2) the second enhancement layer is formed on the first enhancement layer surface; The peel strength of macromolecule membranous layer and transition zone is increased by first, second enhancement layer.
3) transition zone is formed on the second enhancement layer surface; Described transition zone is formed by the method for sputtering;
4) metal copper layer is formed on transition zone surface.Described layers of copper adopts sputtering plating to be formed with the combination process of plating.
The peel strength of flexibility coat copper plate is 13.2N/cm, and after 288 DEG C of drift tin 10 seconds, peel strength is 11N/cm.
Wherein, step 1) is that the silane coupler first applying 10 nanometer thickness on macromolecule membranous layer surface forms the first enhancement layer, again by step 2) at the particles filled polyurethane of the first enhancement layer surface-coated, so its meaning increases the surface polar groups of macromolecule membranous layer in the method first by chemistry, increase the peel strength of itself and the second enhancement layer, and then the surface roughness of macromolecule membranous layer is changed by arranging the second enhancement layer, owing to containing a small amount of granule particles in the second enhancement layer, compared with embodiment 8, the surface roughness of macromolecule membranous layer is larger, the peel strength of flexibility coat copper plate is higher.
Simultaneously, inventor of the present utility model finds, before formation enhancement layer, to carry out surface treatment to macromolecule membranous layer, or carries out surface treatment to the second enhancement layer and all can improve peel strength further, carry out surface treatment to macromolecule membranous layer and the second enhancement layer, peel strength is larger simultaneously.
In the above embodiment, any restriction is not done to the guard method of layers of copper, oxidation resistant protective layer can be set on described metal copper layer surface according to actual needs, or by metal copper layer roughening, be convenient to laser drilling.Any above embodiment is done according to technical spirit of the present utility model and layers of copper guard method any trickle amendment, equivalent variations and modification, all still belong in the scope of technical solutions of the utility model.
comparative example 1:
Adopt coating layer platen press: the thermoplastic polyimide solution (TPI) being coated with 5 microns at the copper foil surfaces of 12 microns, and then the PI of 12.5 microns and its pressing are solidified, the peel strength of gained flexible copper-clad panel products is up to 11.1N/cm, compared with embodiment 5 to embodiment 9, peel strength is than embodiment 6, embodiment 8 and embodiment 9 low, than embodiment 5 and embodiment 7 slightly high, but its copper thickness is the thinnest is 12 microns, easily gauffer is produced when coating or lamination because extra thin copper foil is expert at, even there is fracture, the thinner Copper Foil of very difficult use carries out being coated with or lamination, make it with HDI(high density interconnect substrate) technology and COF(Chip on Flex, flexible chip) liquid crystal (plasma) display based on technology, application in the medium-to-high grade precise electronic products such as liquid crystal (plasma) TV receives certain restriction, this is the technical bottleneck of coating and laminating.And the flexibility coat copper plate that embodiment 5 to embodiment 9 is produced not only peel strength is high, and copper thickness only 8 microns, is applicable to ultra fine-line, HDI wiring board.
comparative example 2:
Adopt plating method: with the surface of the mode modified polyimide film of ion implantation, increase its surface activity, the thickness of polyimide film is 12.5 microns, then metal prime coat (nickel-copper alloy layer of 0.02 micron) is formed by sputtering method at the polyimide film surface of modification, the Copper Foil of final plating 8 microns, peel strength is 6N/cm only, compared with embodiment 5 to embodiment 9, peel strength is extremely low, cannot meet use.
Table 1 is the data result of related embodiment and comparative example:
table 1:
Claims (10)
1. a high-peeling strength flexibility coat copper plate, is characterized in that: comprise with understructure: macromolecule membranous layer, be arranged on this macromolecule membranous layer at least one side on enhancement layer, the transition zone be arranged on this enhancement layer surface, the layers of copper be arranged on transition zone surface; Wherein, the number of plies of described transition zone is more than one deck.
2. a kind of high-peeling strength flexibility coat copper plate according to claim 1, is characterized in that: the thickness of described macromolecule membranous layer is 5-125 micron; The material of described macromolecule membranous layer is the one in polyimides, PETG, polybutylene terephthalate (PBT), polysulfones, polyphenylene sulfide, polyether-ether-ketone, polyphenylene oxide, polytetrafluoroethylene, liquid crystal polymer, polyparabanic acid.
3. a kind of high-peeling strength flexibility coat copper plate according to claim 1, is characterized in that: described enhancement layer is following I)-V) cited by one:
I) material of described enhancement layer is selected from the one in thermoplastic polyimide class, modified epoxy class, modified acrylic acid, modified polyurethane, modified phenolic resin resin;
II) material of described enhancement layer is selected from particles filled polymer composite;
III) material of described enhancement layer is selected from the one in coupling agent, surfactant, organosilicon, organic oligomer surface modifier;
IV) described enhancement layer is I) with III) overlapping layers of two class enhancement layers;
V) described enhancement layer is II) with III) overlapping layers of two class enhancement layers.
4. a kind of high-peeling strength flexibility coat copper plate according to claim 3, is characterized in that: the material of described enhancement layer is I) described in time, the thickness of enhancement layer is 0.05-30 micron.
5. a kind of high-peeling strength flexibility coat copper plate according to claim 3, is characterized in that: the material of described enhancement layer is II) described in time, the thickness of enhancement layer is 0.05-30 micron.
6. a kind of high-peeling strength flexibility coat copper plate according to claim 3, is characterized in that: the material of described enhancement layer is III) described in time, the thickness of enhancement layer is 10-100 nanometer.
7. a kind of high-peeling strength flexibility coat copper plate according to claim 3, is characterized in that: the formation of described enhancement layer is IV) described in time, the thickness of enhancement layer is 0.05-30 micron; The formation of described enhancement layer is V) described in time, the thickness of enhancement layer is 0.05-30 micron.
8. a kind of high-peeling strength flexibility coat copper plate according to claim 1, is characterized in that: when described transition zone is individual layer, and its thickness is 0.01-0.5 micron; When the number of plies of transition zone is more than one deck, its gross thickness is 0.01-0.5 micron; One in the material selected from metal material of transition zone, ferrite, carbon nano-tube; Wherein, described metal material is the one in these metal simple-substances: aluminium, titanium, zinc, iron, nickel, chromium, cobalt, copper, silver, gold, molybdenum; Or be at least two kinds of alloys formed in these metal simple-substances.
9. a kind of high-peeling strength flexibility coat copper plate according to claim 1, is characterized in that: described layers of copper is shaggy layers of copper.
10. a kind of high-peeling strength flexibility coat copper plate according to claim 1, is characterized in that: described layers of copper surface is provided with oxidation resistant protective layer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112210749A (en) * | 2020-10-13 | 2021-01-12 | 廖斌 | Preparation method of MPI copper-clad plate and MPI copper-clad plate prepared by same |
| CN113068313A (en) * | 2021-03-05 | 2021-07-02 | 江西展耀微电子有限公司 | Manufacturing method of circuit board, circuit board manufactured by manufacturing method and electronic equipment |
| CN116240601A (en) * | 2022-12-28 | 2023-06-09 | 深圳惠科新材料股份有限公司 | Composite copper foil, preparation method thereof and battery |
-
2014
- 2014-12-02 CN CN201420748538.6U patent/CN204598463U/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112210749A (en) * | 2020-10-13 | 2021-01-12 | 廖斌 | Preparation method of MPI copper-clad plate and MPI copper-clad plate prepared by same |
| CN113068313A (en) * | 2021-03-05 | 2021-07-02 | 江西展耀微电子有限公司 | Manufacturing method of circuit board, circuit board manufactured by manufacturing method and electronic equipment |
| CN116240601A (en) * | 2022-12-28 | 2023-06-09 | 深圳惠科新材料股份有限公司 | Composite copper foil, preparation method thereof and battery |
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Address after: 510660, A5 building, No. 11, Kaiyuan Avenue, Guangzhou hi tech Industrial Development Zone, Guangdong, Guangzhou, Sixth Patentee after: GUANGZHOU FANGBANG ELECTRONICS CO., LTD. Address before: 510660, A5 building, No. 11, Kaiyuan Avenue, Guangzhou hi tech Industrial Development Zone, Guangdong, Guangzhou, Sixth Patentee before: Guangzhou Fangbang Electronic Co., Ltd. |