CN106413248B - Low-k resin base material processing copper foil and copper clad laminate and printing distributing board using the processing copper foil - Google Patents

Low-k resin base material processing copper foil and copper clad laminate and printing distributing board using the processing copper foil Download PDF

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Publication number
CN106413248B
CN106413248B CN201610258241.5A CN201610258241A CN106413248B CN 106413248 B CN106413248 B CN 106413248B CN 201610258241 A CN201610258241 A CN 201610258241A CN 106413248 B CN106413248 B CN 106413248B
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Prior art keywords
copper foil
base material
resin base
treatment layer
low
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CN106413248A (en
Inventor
冈本健
真锅久德
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Fukuda Metal Foil and Powder Co Ltd
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Fukuda Metal Foil and Powder Co Ltd
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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils

Abstract

The invention discloses a kind of low-k resin base material processing copper foil and using the copper clad laminate and printing distributing board of the processing copper foil, which also has high peel strength relative to low-k substrate, and transmission characteristic is excellent.Has roughening treatment layer in at least one side of untreated copper foil, has anti-oxidant treatment layer on the roughening treatment layer, the dielectric loss angle tangent of the 1GHz frequencies above of the low-k resin is 0.005 or less, wherein, the roughening treatment layer is formed by the copper particle that partial size is 300~600nm, the anti-oxidant treatment layer contains molybdenum and cobalt, 10 mean roughness Rz of the process face Nian Jie with resin base material are 0.6~2.0 μm, and the untreated copper foil and the color difference Δ E*ab of the process face are 35~55.

Description

Low-k resin base material processing copper foil and the copper clad layers using the processing copper foil Pressing plate and printing distributing board
Technical field
Also has high peel strength relative to low-k resin base material and transmission characteristic is excellent the present invention relates to a kind of Different processing copper foil.
Background technique
Printing distributing board for information communication device etc. is formed with conductive Wiring pattern on resin base material. As the resin base material, can enumerate: impregnation has the phenolic resin or epoxy of insulating properties on the reinforcing materials such as glass cloth or paper The rigid printing distributing board of resin, polyphenylene oxide resin, bismaleimide-triazine resin etc. is used, by polyimide resin or cyclenes The flexible printed wiring board of the compositions such as hydrocarbon polymer resin is used.
On the other hand, the material as conductive Wiring pattern, usually using copper foil.
The printing distributing board can make as follows: being made and resin base material and copper foil are heated, pressurizeed and cover copper After laminate, the unnecessary portion of copper foil is removed by etching to form Wiring pattern.
Copper foil be roughly divided into according to its preparation method electrolytic copper foil and rolled copper foil both, according to respective feature and according to Purposes, which is distinguished, to be used.In addition, any copper foil nearly all cannot be used directly, use is equipped with heat-resisting place based on roughening treatment layer Manage the copper foil (copper foil for being equipped with various process layers is referred to as " processing copper foil " below) of the various process layers such as layer, antirust treatment layer.
Nearest information communication device is because of multifunction or the expansion of networking etc., to the signal high speed communicated for information Change, high frequency, the demand for capableing of printing distributing board corresponding with Gao Su, high frequency sharply increases.
But the printing distributing board of reply high speed, high frequency, in addition to characteristic required by printing distributing board so far Outside, it also requires using transmission loss as " transmission characteristic " of representative.
Transmission loss indicates the degree that the electric current flowed in printing distributing board is waited according to distance and is decayed, and usually has transmission The trend increased as frequency is got higher is lost.So-called transmission loss refers to greatly rated current, and some is passed to load-side It passs, therefore, in order to which there is no problem in practical, ground is used, it is necessary to inhibit transmission loss lower.
The transmission loss of printing distributing board is the loss that dielectric loss is added (summing) with conductor losses.Dielectric Loss is originated from resin base material, due to dielectric constant and dielectric loss angle tangent.On the other hand, conductor losses is from electric conductor Copper foil, due to conductor resistance.Therefore, transmission loss is reduced, the dielectric constant or dielectric loss angle for reducing resin base material are just It is cut from needless to say, it is also necessary to reduce the conductor resistance of copper foil.
As described above, transmission loss has with the trend that the frequency of electric current increases and increases, this is because conductor losses I.e. conductor resistance is got higher, and " skin effect " and " surface shape of processing copper foil " has relationship.
Skin effect refers to that the electric current flowed in electric conductor flows through near the surface of electric conductor as frequency improves Effect.Moreover, being defined as until the electric current relative to electric conductor surface becomes the skin depth of the distance of the point of 1/e times of electric current δ is indicated with formula (1).
δ=(2/ (ω σ μ))1/2(formula 1)
ω is angular frequency, and σ is conductivity, and μ is magnetic conductivity.
In a case of copper, according to its conductivity and relative permeability, formula (1) becomes as follows.
δ=0.066/f1/2(formula 2)
F is frequency.
According to formula (2) it is found that electric current is flowed as frequency is got higher at the position on the surface closer to electric conductor, for example, Skin depth when frequency is 10MHz is about 20 μm, and in contrast, skin depth when frequency is 40GHz is about 1 μm, almost Only in surface flow.
Therefore, in order to improve adaptation with resin base material and at the place for being equipped with roughening treatment layer as prior art In the case where flowing through high-frequency current in reason copper foil, electric current is flowed along the surface shape of roughening treatment layer, and mainly always in The case where center portion flows is compared, and propagation distance increases, therefore, it is considered that conductor resistance increases, so as to cause the increasing of transmission loss Greatly.
Therefore, it as reply high speed, the processing copper foil of the printing distributing board of high frequency transmitting, needs to inhibit conductor resistance To be lower, it is therefore contemplated that it is preferred that reducing the partial size for constituting the roughening particle of roughening treatment layer, to reduce surface roughness.
In addition, in resin base material, in order to inhibit dielectric loss, it is also preferred that it is high to reduce the polarity for increasing transmission loss Functional group.
Commonly referred to as the resin base material of low-k resin base material includes liquid crystal polymer, polyvinyl fluoride, isocyanic acid Ester compounds etc., the functional group for keeping polarity high reduce or disappear.
If being only conceived to transmission characteristic, do not have the untreated copper foil of roughening treatment layer since surface roughness is small, so The propagation distance of electric current can be shortened, as a result, it is possible to reduce resistance, result, it is believed that it is most excellent as conductor, but be conceived to In the case where the adaptation of copper foil and resin base material, do not have the untreated copper foil of roughening treatment layer since anchor effect is small, with The closing force of resin base material is weak, so cannot ensure peel strength, it is difficult to be used for printing distributing board.
Especially low-k resin base material due to the high functional group's reduction of the polarity for facilitating adaptation or disappears, It could not be expected that chemical bonding bring closing force, so needing the anchor effect generated by roughening particle to ensure closing force. Moreover, the peel strength of high closing force, that is, high in order to obtain, needs to increase the roughening particle diameter.
If roughening treatment layer is arranged on untreated copper foil, further make the attached of the roughening particle for constituting roughening treatment layer Amount increase or increase partial size, then anchor effect improve, therefore, can be improved peel strength, but as described above, if set Roughening treatment layer is set, then the propagation distance of electric current is elongated, and conductor resistance increases, and transmission loss increases.
In this way, following dilemma can be generated in the case where coping with the printing distributing board of high speed, high-frequency signal: if Reduce the high functional group of polarity to inhibit the transmission loss of resin base material, then it cannot be with the high adhesion of processing copper foil； If making to pass because of skin effect to improve resin base material and handle the adaptation of copper foil and increase the partial size of roughening particle Defeated loss increases.
But it needs to meet these all situations, phase in practical with high speed, the corresponding printing distributing board of high frequency transmitting Even the few low-k resin base material of the functional group for hoping exploitation polarity high, can also obtain sufficient peel strength, and Processing copper foil as the printing distributing board that can inhibit transmission loss.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2013-155415 bulletin；
Patent document 2: international publication number WO2003/102277.
Summary of the invention
Disclosed in patent document 1 it is a kind of in order to improve and cope with high frequency transmitting insulating resin cementability and be provided with The processing copper foil of roughening treatment layer and resistance to thermal treatment layer.
The disclosed processing copper foil of patent document 1 ensures peel strength by increasing the particle of composition roughening treatment layer.
But when roughening particle is larger, current spread distance will be elongated, therefore asks there are transmission loss is increased Topic.
In addition, being further increased in transmission loss because of resistance to thermal treatment layer, antirust treatment layer and silane coupling agent layer, especially It is in the case that resistance to thermal treatment layer contains Ni, skin depth shoals, therefore, so that current convergence is shunted in the surface element of copper foil It is dynamic, it is easier to be subject to processing the concave-convex influence of layer surface, there are problems that transmission loss further increases.
A kind of processing copper foil is disclosed in patent document 2, in order to improve the bonding for the resin base material that reply high frequency transmits Property, the antirust treatment layer equipped with roughening treatment layer and containing zinc and nickel is equipped with chromate coating on antirust treatment layer, in chromate Layer is equipped with silane coupling agent adsorption layer, wherein by inhibiting the surface roughness modulation of process face in certain range Transmission loss.
But since the roughening particle of roughening treatment layer is larger, so current spread, apart from elongated, there are transmission loss increasings The problem of adding.
In addition, so skin depth shoals, current convergence is shunted in the surface element of copper foil since antirust treatment layer contains Ni It is dynamic, there are problems that transmission loss further increases.
The multiple examination for trying mistake is repeated to solve the problems point as technical task in the inventors of the present invention Make, experiment, the opinion as a result to be attracted people's attention realizes the technical task, the opinion are as follows: if it is roughening treatment layer by The copper particle of 300~600nm of partial size is formed, and anti-oxidant treatment layer contains molybdenum and cobalt, Nian Jie with low-k resin base material 10 mean roughness Rz of process face are 0.6~2.0 μm, and untreated copper foil and the color difference Δ E*ab of process face are 35~55 Processing copper foil, then in the case where being equipped with roughening treatment layer, also to be sent with untreated copper foil with transmission loss, that is, Den of degree The conductor of excellent, meanwhile, high peel strength can be also obtained relative to low-k resin base material.
The technical task is as follows, can solve through the invention.
The present invention provides a kind of low-k resin base material processing copper foil, has in at least one side of untreated copper foil Roughening treatment layer has anti-oxidant treatment layer, 1GHz or more the frequency of the low-k resin on the roughening treatment layer The dielectric loss angle tangent of rate is 0.005 or less, wherein the copper particle shape that the roughening treatment layer is 300~600nm by partial size At, the anti-oxidant treatment layer contains molybdenum and cobalt, and 10 mean roughness Rz of the process face Nian Jie with resin base material are 0.6~ 2.0 μm, and the untreated copper foil and the color difference Δ E*ab of the process face are 35~55 (first aspects).
In addition, low-k resin base material of the invention is resisted with copper foil is handled on the basis of first aspect described Have the layer (second aspect) of more than one following a, b on oxidation processes layer:
A. chromate coating
B. silane coupling agent layer.
In addition, the present invention provides a kind of copper clad laminate, processing copper foil described in first or second aspect is fitted in The dielectric loss angle tangent of 1GHz frequencies above is to form (third party on 0.005 low-k resin base material below Face).
In addition, copper clad laminate of the invention is on the basis of the third aspect, with the 1GHz or more containing liquid crystal polymer The dielectric loss angle tangent of frequency is that the peel strength of 0.005 low-k resin base material below is 0.6kN/m or more ( Four aspects).
In addition, the present invention provides a kind of processing method for handling copper foil, for the processing described in first or second aspect Copper foil is handled, which is characterized in that adds starch decomposition product (the 5th aspect) in the electrolytic solution.
In addition, the present invention provides a kind of manufacturing method of copper clad laminate, for manufacturing described in third or fourth aspect Copper clad laminate, which is characterized in that the dielectric loss angle tangent to processing copper foil and 1GHz frequencies above is 0.005 below low Dielectric constant resin base material pressurizes while heating makes its fitting (the 6th aspect).
In addition, the present invention provides a kind of printing distributing board, formed using copper clad laminate described in third or fourth aspect (the 7th aspect).
In addition, the present invention provides a kind of manufacturing method of printing distributing board, match for manufacturing printing described in the 7th aspect Line plate (eighth aspect).
In the present specification, the roughening treatment layer in the present invention is specially called resin induction sometimes and is impregnated with layer.
In processing copper foil of the invention, the roughening particle for constituting roughening treatment layer (resin induction is impregnated with layer) is partial size 300 The copper particle of~600nm, 10 mean roughness Rz of the process face Nian Jie with resin base material are 0.6~2.0 μm, and it is described not The color difference Δ E*ab for handling copper foil and the process face is 35~55, therefore, heated with resin base material, press molding When, which is equably impregnated between roughening particle, copper foil surface and resin large area solid bonding is handled, even if contributing to The few low-k resin base material of the high functional group of the polarity of peel strength, also can be realized strong peel strength.
In particular, being 0.005 below for the dielectric loss angle tangent of the 1GHz frequencies above containing liquid crystal polymer Low-k resin base material can obtain the peel strength of 0.6kN/m or more.
In addition, 10 average roughness of the process face Nian Jie with low-k resin base material of processing copper foil of the invention Spending Rz is 0.6~2.0 μm, and anti-oxidant treatment layer contains molybdenum and cobalt, and the metal for increase transmission loss such as not nickeliferous, therefore, Copper clad laminate made of processing copper foil of the invention is bonded on low-k resin base material, such as even if being high frequency, Transmission loss can be inhibited with the copper clad laminate equal extent that is bonded with the untreated copper foil of not set roughening treatment layer.
In particular, the dielectric loss angle tangent for fitting in the 1GHz frequencies above containing liquid crystal polymer is 0.005 or less Low-k resin base material on transmission loss of the copper clad laminate under the high frequency of frequency 40GHz be -5.5dB/100mm More than, compared with untreated copper foil, transmission loss can be suppressed to lower than 5% and having resin induction and being impregnated with layer.
Detailed description of the invention
Fig. 1 is the schematic diagram in processing copper foil section of the invention；
Fig. 2 is 15,000 times of the electron scanning micrograph in processing copper foil section of the invention.
Wherein, the reference numerals are as follows:
1 copper foil；
The induction of 2 resins is impregnated with layer；
3 anti-oxidant treatment layers.
Specific embodiment
The untreated copper foil > of <
Copper foil (hereinafter referred to as " untreated copper foil ") before managing everywhere in use of the present invention is not particularly limited, and can also make With in no table point copper foil, be divided into any of copper foil in table.
The one side (hereinafter referred to as " process face ") for implementing surface treatment is not particularly limited, much less rolled copper foil can be Arbitrary face, any one side being also possible in precipitation face or glassy surface in electrolytic copper foil.
In addition, being preferably impregnated in hydrocarbon organic solvent when using rolled copper foil, removes rolling oil and be roughened later Processing.
The thickness of untreated copper foil is not particularly limited, as long as can be used for the thickness of printing distributing board after surface treatment , but preferably 6~300 μm, more preferably 9~70 μm.
In addition, the face of the implementation surface treatment of the untreated copper foil preferably color specification system L* defined in measurement JIS Z8781 It is the range of L*83~88, a*14~17, b*15~19 when a*b*.
The induction of < resin is impregnated with layer (roughening treatment layer) >
The partial size for constituting the copper particle that resin induction is impregnated with layer is preferably 300~600nm, more preferably 380~530nm.
In the present invention, lower limit value is set as 300nm, but be not excluded for containing 300nm particle below.But work as deficiency When the particle of 300nm is more, in the case where fitting on low-k resin base material, it is possible to cannot can be used in scratching Property printing distributing board sufficient peel strength, in addition, when more than 600nm, surface roughness increases, and transmission loss increases, Therefore, these situations are not preferred.
In addition, the range for being preferably spaced 350~450nm of the protrusion of copper particle.
It is preferably 370~810nm that resin induction, which is impregnated with the thickness of layer, more preferably 500~680nm.
When thickness is less than 370nm, it is possible to cannot get sufficient peel strength, when more than 810nm, transmission loss increases Greatly, these situations are not preferred.
Resin induces the interval of the protrusion of the partial size, copper particle that are impregnated with layer and thickness for example can be by aobvious with scanning electron Micro mirror etc. is amplified to 10,000~30,000 times of multiplying power under 40 ° of tilt angle and is observed, measured and be measured.
In the formation that resin induction is impregnated with layer, sulfuric acid is 90~110g/L's in preferably 50~150g/L of cupric sulfate pentahydrate Electrolyte.
When the concentration of cupric sulfate pentahydrate is 50g/L or less, particle of the partial size less than 300nm of copper particle diameter increases, in addition, When the concentration of cupric sulfate pentahydrate is 150g/L or more, then roughening particle cannot be formed, so not preferably.
Various additives can be added in above-mentioned electrolyte.
As the additive that can be properly added, starch decomposition product and metal sulfate, metal oxide can be enumerated.
The starch decomposition product added in above-mentioned electrolyte is not particularly limited, and can be times of decomposition completely, decomposed It is a kind of.
Average molecular weight is preferably 100~100,000, more preferably 100~10,000.
As the sulfate or oxide of metal, indium sulfate, vanadic anhydride, germanium dioxide etc. can be enumerated.
It is preferred that immersing the insoluble electrodes such as platinum group oxide cladding titanium in the electrolytic solution as anode and immerses untreated copper Foil is as cathode, according to 10~50A/dm of current density2, 80~100C/dm of electricity2, 35~45 DEG C of liquid temperature electrolytic condition carry out Electrolysis forms resin induction and is impregnated with layer.
If current density is 10A/dm2And electricity is lower than 80C/dm2, then copper particle cannot sufficiently adhere to, in addition, if Current density is 50A/dm2And electricity is higher than 100C/dm2, then partial size is more than that the ratio of the copper particle of 600nm increases, so not It is preferred that.
< anti-oxidant treatment layer >
Processing copper foil of the invention is impregnated on layer in resin induction has anti-oxidant treatment layer.
The adhesion amount of anti-oxidant treatment layer is preferably 30~300mg/m2, more preferably 50~120mg/m2。
The adhesion amount of anti-oxidant treatment layer is 30mg/m2When following, cannot completely coated with resin induction be impregnated with layer, in addition, The adhesion amount of anti-oxidant treatment layer is 300mg/m2When above, transmission loss is likely to increase, in addition, because even comparing 300mg/ m2It is above more, it can not it is expected the raising of antioxygenic property.
In addition, cobalt contained in anti-oxidant treatment layer is preferably 20~155mg/m2, molybdenum is preferably 10~145mg/m2。
When being unsatisfactory for each concentration of lower limit value, antioxygenic property is insufficient, in addition, passing when being more than each concentration of upper limit value Defeated loss is likely to increase.
Formed the electrolyte of anti-oxidant treatment layer preferably will in cobalt compound 10~100g/L aqueous solution containing 1~ The aqueous solution of the molybdate compound of 80g/L is modulated to the electrolyte of pH4~10.
As cobalt compound, for example, cobalt sulfate.
As molybdate compound, for example, Sodium Molybdate Dihydrate.
The insoluble electrodes such as platinum group oxide cladding titanium are immersed in the electrolytic solution as anode and immersion forms resin induction The copper foil of layer is impregnated with as cathode, according to 0.1~10A/dm of current density2, 5~20C/dm of electricity2, 20~50 DEG C of liquid temperature of item Part is electrolysed, and anti-oxidant treatment layer is capable of forming.
< chromate coating and silane coupling agent layer >
Processing copper foil of the invention can be arranged on anti-oxidant treatment layer as needed one layer or more selected from chromate Layer in layer and silane coupling agent layer.
The electrolyte for forming chromate coating is preferably that will contain chromic acid compound 10~100g/L aqueous solution to be modulated to pH2~12 Electrolyte.
As the compound containing chromic acid, such as sodium dichromate dihydrate can be enumerated.
Chromate coating can be formed: immerse the insoluble electrodes such as platinum group oxide cladding titanium in the electrolytic solution as sun The copper foil for forming anti-oxidant treatment layer is simultaneously immersed as cathode, according to 20~50 DEG C of liquid temperature, 0.1~10A/dm of current density in pole2、 0.5~20C/dm of electricity2Condition be electrolysed.
In addition, chromate coating can also contain zinc.
Silane coupling agent layer can be set on chromate coating or on anti-oxidant treatment layer.
Silane coupling agent for silane coupling agent layer is not particularly limited, and can be used containing vinyl, epoxy group, benzene Vinyl, methacrylic, acrylic, amino, urea groups and sulfydryl silane coupling agent, but contain amino, epoxy group or second The resistance to hygroscopicity of the silane coupling agent of alkenyl and the effect of rust-preventing characteristic are very high, can more preferably use.
Silane coupling agent can be one kind, can also combine two or more use.
It can be dissipated afterwards and with the methods of spraying in being impregnated in the silane coupling agent aqueous solution for being modulated to 20~50 DEG C of liquid temperature It is formed after cloth by washing.
< resin base material >
The low-k resin base material of laminating process copper foil of the invention is make to facilitate copper foil and resin base material viscous The resin base material that the big functional group of the polarity connect reduces or disappears, under the frequency of 1GHz or more, dielectric loss angle tangent is 0.005 or less.
As low-k resin base material, can be exemplified containing liquid crystal polymer, polyvinyl fluoride, isocyanates chemical combination The resin of object, Noryl.
The measurement > of < color difference Δ E*ab
It in the face before the processing for determining untreated copper foil and can handle defined in the JIS Z8781 of copper foil process face After color specification system L*a*b*, pass through ([Δ L*]2+[Δa*]2+[Δb*]2)1/2Shown in formula calculate color difference Δ E*ab.
Embodiment
The embodiment of the present invention described below, however, the present invention is not limited thereto.
The untreated copper foil > of <
As the untreated copper foil of Examples and Comparative Examples, 12 μm of thickness of rolled copper foil or electrolytic copper foil is used.
In addition, rolled copper foil impregnates 60 seconds in hydrocarbon organic solvent and carries out each processing after removing rolling oil.
(Examples 1 to 6)
< resin induces the formation > for being impregnated with layer
Adjust the electrolyte that table 1 is recorded.Anode uses the titanium that surface has been coated by platinum group oxide, and cathode uses untreated Two electrodes are impregnated in each electrolyte by copper foil, are electrolysed with each electrolytic condition that table 1 is recorded, in each untreated copper foil It is respectively formed resin induction on one side and is impregnated with layer.
In addition, using the mixture for the decomposition product that molecular weight is 100~10,000 as starch decomposition product.
Anti-oxidant treatment layer > of the < containing cobalt-molybdenum
Containing cobalt sulfate 38g/L, Sodium Molybdate Dihydrate 23g/L, citrate trisodium dihydrate 45g/L, sodium sulphate In the pH5.6 of 80g/L, 30 DEG C of liquid temperature of aqueous solution, the titanium that surface has been coated by platinum group oxide is used as anode, as yin The processing copper foil that pole is impregnated with layer using having resin induction, for two electrodes with current density 7.0A/dm2, electricity 14C/dm2's Electrolytic condition is impregnated with anti-oxidant treatment layer of the setting containing cobalt-molybdenum on layer in resin induction.
< chromate coating >
In the chromic acid that 30 DEG C of liquid temperature of sodium dichromate dihydrate 40g/L aqueous solution is modulated to pH12.0 with sodium hydroxide In saline solution, the titanium for being coated surface by platinum group oxide is used as anode, and uses as cathode and to have resin and lure The processing copper foil for being impregnated with layer and the anti-oxidant treatment layer containing cobalt-molybdenum is led, for two electrodes with current density 2.0A/dm2, electricity 10C/dm2Electrolytic condition chromate coating is set on the anti-oxidant treatment layer containing cobalt-molybdenum.
< silane coupling agent layer >
The processing copper foils of treated layers be will be provided at 30 DEG C of liquid temperature containing gamma-aminopropyl-triethoxy-silane 5ml/L's It is impregnated 10 seconds in aqueous solution, forms silane coupling agent layer on chromate coating.
After forming silane coupling agent layer, is spontaneously dried at about 25 DEG C of temperature, the processing copper foil of each embodiment is made.
Table 1
(comparative example 1)
In addition to being not provided with resin induction and being impregnated with layer, made according to condition same as Example 1.
(comparative example 2)
It includes in the electrolyte of cupric sulfate pentahydrate 47g/L, sulfuric acid 100g/L, with current density that untreated copper foil, which is immersed, 50A/dm2, electricity 130C/dm2, 30 DEG C of liquid temperature of electrolytic condition be electrolysed, after forming microfine sublayer, immersing includes five water Copper sulphate 200g/L, sulfuric acid 100g/L electrolyte in, with current density 5A/dm2, electricity 400C/dm2, 40 DEG C of liquid temperature of electrolysis Condition is electrolysed, and resin induction is consequently formed and is impregnated with layer, in addition to this, makes according to condition same as Example 1.
(comparative example 3)
Electrolyte comprising cupric sulfate pentahydrate 55g/L, five sodium 100g/L of diethylene triamine pentacetic acid (DTPA) is modulated to sulfuric acid After pH4.5, untreated copper foil is immersed, with current density 1.4A/dm2, electricity 85C/dm2, 32 DEG C of liquid temperature electrolytic condition carry out electricity Solution forms resin induction and is impregnated with layer, in addition to this, makes according to condition same as Example 1.
(comparative example 4)
Including cupric sulfate pentahydrate 45g/L, sulfuric acid 80g/L, titanyl sulfate 2g/L, sodium tungstate dihydrate 0.045g/L Untreated copper foil is immersed in electrolyte, with current density 10A/dm2, electricity 50C/dm2, 35 DEG C of liquid temperature electrolytic condition carry out electricity Solution, formed microfine sublayer after, immerse containing cupric sulfate pentahydrate 200g/L, sulfuric acid 100g/L electrolyte in, with current density 10A/dm2, electricity 250C/dm2, 40 DEG C of liquid temperature electrolytic condition formed resin induction be impregnated with layer, in addition to this, according to implementation The production of the identical condition of example 1.
(comparative example 5)
Object 49g/L, sodium sulphate 80g/L will be closed containing cupric sulfate pentahydrate 61g/L, cobalt sulfate 29g/L, nickel sulfate hexahydrate Electrolyte be modulated to pH2.5 with sulfuric acid after, untreated copper foil is immersed, with current density 5A/dm2, electricity 45C/dm2, liquid temperature 30 DEG C electrolytic condition be electrolysed, formed resin induction is impregnated with layer, in addition to this, according to similarly to Example 1 condition make.
(comparative example 6)
Untreated copper foil is immersed, in the electrolyte of comparative example 5 with current density 5A/dm2, electricity 105C/dm2, liquid temperature 30 DEG C electrolytic condition be electrolysed, form resin induction and be impregnated with layer, in addition to this, made according to condition same as Example 1.
(comparative example 7)
Object 30g/L, sodium hypophosphite monohydrate 2.0g/L, sodium acetate trihydrate 10g/L will be closed containing nickel sulfate hexahydrate Electrolyte be modulated to pH4.5 with sulfuric acid after, with current density 5.0A/dm2, electricity 10C/dm2, 30 DEG C of liquid temperature of electrolytic condition It is electrolysed, forms anti-oxidant treatment layer, in addition to this, made according to condition same as Example 1.
(comparative example 8)
Object 55g/L will be closed containing nickel sulfate hexahydrate, the electrolyte of cobalt sulfate 22g/L is modulated to pH3.0 with sulfuric acid, system At electrolyte, with current density 5.0A/dm2, electricity 10C/dm2, 40 DEG C of liquid temperature of electrolytic condition be electrolysed, formed anti-oxidant In addition to this process layer makes according to condition same as Example 1.
(comparative example 9)
The processing copper foil of comparative example 3 is bonded with the polyimide resin of non-low-k.
(reference example 1~6)
The processing copper foil of Examples 1 to 6 is bonded with the polyimide resin of non-low-k.
< copper clad laminate A >
Reason face will be managed everywhere in copper foil everywhere in Examples 1 to 6 and comparative example 1~8 as glued face, and be based on three plates Liquid crystal polymer resin substrate (Kuraray Co., Ltd. that the dielectric loss angle tangent of the 25GHz of line resonator is 0.002 (Kuraray Co., Ltd.) system, the name of an article: 50 μm of CT-Z, thickness) be combined after, use vacuum hotpressing machine (Beichuan essence machine strain Formula commercial firm (Kitagawa Seiki Co., Ltd.) KVHC-II processed) it is preheated 15 minutes at vacuum (7torr), 260 DEG C of temperature, Heating, the extrusion forming for carrying out 10 minutes at vacuum (7torr), 300 DEG C of temperature, pressure 4MPa later, obtain copper clad layers pressure Plate A.
Copper clad laminate A is used for the measurement of peel strength.
< copper clad laminate B >
Face and liquid crystal polymer resin substrate (strain are managed everywhere in copper foil by managing everywhere in Examples 1 to 6 and comparative example 1~8 Formula commercial firm Kuraray system, the name of an article: 50 μm of CT-Z, thickness) it is combined, make earthy copper foil (70 μm) and above-mentioned each processing copper foil Another side be combined after, preheated 15 minutes at vacuum (7torr), 260 DEG C of temperature using vacuum hotpressing machine, later true Heating, the extrusion forming that 10 minutes are carried out under empty (7torr), 260 DEG C of temperature, pressure 4MPa, obtain copper clad laminate B.
Copper clad laminate B is used for transmission the measurement of loss.
< copper clad laminate C >
It will be managed everywhere in comparative example 9 and reference example 1~6 and manage face everywhere in copper foil as glued face, with polyimides tree After aliphatic radical material (Kanegafuchi Chemical Ind (Kaneka Corporation) system, the name of an article: 25 μm of FRS-142, thickness) is combined, make Preheat 15 minutes at vacuum (7torr), 260 DEG C of temperature with vacuum hotpressing machine, later vacuum (7torr), 300 DEG C of temperature, Heating, the extrusion forming that 10 minutes are carried out under pressure 4MPa, obtain copper clad laminate C.
The evaluation of untreated copper foil or processing copper foil is carried out by following method.
The measurement > of < surface roughness
For each face equipped with process layer of untreated copper foil or processing copper foil, advised using suitable JIS B0651-2001 Surface roughness tester (Surfcorder) SE1700 α (the small slope research of Co., Ltd. of fixed contact pin type surface roughness meter Institute (Kosaka Laboratory Ltd.) system), using stylus tip radius as contact pilotage is 2 μm of contact pilotage, if coarse write music Line with cutoff value be 0.8mm, measurement distance be 4.0mm, measure JISB0601-1994 defined in 10 mean roughness Rz.
The measurement > of < partial size
Using flying-spot microscope SEM (Jeol Ltd. (JEOL) JSM-6010LA processed), sample table is set to incline on one side It oblique 40 °, is observed on one side with 10,000~30,000 times of multiplying power, the copper particle of layer is impregnated with to the composition resin induction observed 10 points of linear measure longimetry of the particle of group, using measured 10 points of the average value as the value of partial size.
< color difference Δ E*ab >
Everywhere using spectral photometric colour measuring meter (Konica Minolta Opto Inc. (Konica Minolta) CM-600d processed) measurement Manage copper foil JIS Z8781 defined in color specification system L*a*b*, acquire with the color difference Δ E*ab of the L*a*b* of untreated copper foil (= ([ΔL*]2+[Δa*]2+[Δb*]2)1/2)。
The evaluation of copper clad laminate is carried out by following method.
< peel strength >
Using etching machine (two palace system of Co., Ltd. (Ninomiya System Co., Ltd.) SPE-40 processed), pass through erosion Scribe the copper circuit sample for making width 1mm.According to JIS C6481, peel strength is measured using universal testing machine.
< transmission loss >
Using etching machine, single-ended microstripline is formed by etching.In addition, being for the circuit width of this substrate In the case where copper clad laminate B, width is 110 μm, and in the case where being copper clad laminate C, width is 50 μm, so that characteristic impedance As 50 Ω.Using Network Analyzer (Japanese Anjelen Sci. & Tech. Inc (Agilent Technologies Japan, Ltd.) N5247A processed) to the S parameter (S21) of made circuit substrate measurement frequency 160MHz~40GHz.
Table 2 shows each evaluation result.
Table 2
It can be confirmed that the transmission loss of processing copper foil of the invention according to Examples 1 to 6 and do not have resin induction and be impregnated with layer Processing copper foil (comparative example 1) be equal extent, and processing copper foil of the invention has the height with low-k resin base material Peel strength.
Industrial applicibility
Processing copper foil of the invention is transmission loss and untreated copper foil is the excellent conductor of equal extent, also, i.e. The functional group for keeping the polarity for contributing to bonding big is less, it is difficult to the low-k resin base material of high peel strength is obtained, Also it can be realized high peel strength, it is, therefore, possible to provide can also be suitable for the copper clad laminate of flexible printed wiring board.
Therefore, processing copper foil of the invention is the high invention of industrial availability.

Claims (7)

1. a kind of low-k resin base material processing copper foil, has roughening treatment layer in at least one side of untreated copper foil, Have anti-oxidant treatment layer, the dielectric of the 1GHz frequencies above of the low-k resin base material on the roughening treatment layer Loss angle tangent is 0.005 or less, wherein
The roughening treatment layer is formed by the copper particle that partial size is 300~600nm, and the anti-oxidant treatment layer contains molybdenum and cobalt, 10 mean roughness Rz of the process face Nian Jie with resin base material are 0.6~2.0 μm, and the untreated copper foil and the place The color difference Δ E*ab in reason face is 35~55.
2. low-k resin base material according to claim 1 processing copper foil, wherein
Have more than one following a, b layer on the anti-oxidant treatment layer:
A. chromate coating；
B. silane coupling agent layer.
3. processing copper foil of any of claims 1 or 2 is fitted in the dielectric loss of 1GHz frequencies above by a kind of copper clad laminate Angle is just being cut on 0.005 low-k resin base material below and is being formed.
4. copper clad laminate according to claim 3, wherein
The dielectric loss angle tangent of the copper clad laminate and the 1GHz frequencies above containing liquid crystal polymer is 0.005 below The peel strength of low-k resin base material is 0.6kN/m or more.
5. a kind of low-k resin base material processing method of the roughening treatment layer of processing copper foil, for claim 1 Or low-k resin base material described in 2 is handled with the roughening treatment layer of processing copper foil, which is characterized in that
It is arranged at the roughening of low-k resin base material processing copper foil of any of claims 1 or 2 by electrolysis method The processing method of layer is managed, and adds starch decomposition product in the electrolyte of the electrolysis method.
6. a kind of manufacturing method of copper clad laminate, for copper clad laminate described in manufacturing claims 3 or 4, feature exists In,
Dielectric loss angle tangent to processing copper foil and 1GHz frequencies above is 0.005 low-k resin base material one below Pressurization makes its fitting on one side for side heating.
7. a kind of printing distributing board is formed using copper clad laminate described in claim 3 or 4.
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