CN106332458B - Copper foil, copper-coated laminated board and printed wiring board with carrier - Google Patents
Copper foil, copper-coated laminated board and printed wiring board with carrier Download PDFInfo
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- CN106332458B CN106332458B CN201610100065.2A CN201610100065A CN106332458B CN 106332458 B CN106332458 B CN 106332458B CN 201610100065 A CN201610100065 A CN 201610100065A CN 106332458 B CN106332458 B CN 106332458B
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- China
- Prior art keywords
- copper foil
- carrier
- peeling layer
- 5cbta
- carboxyl benzotriazole
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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
- 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
- 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
- C25D1/00—Electroforming
- C25D1/20—Separation of the formed objects from the electrodes with no destruction of said electrodes
- C25D1/22—Separating compounds
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- 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
-
- 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
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- 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
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/308—Heat stability
-
- 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
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/12—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2386/00—Specific polymers obtained by polycondensation or polyaddition not provided for in a single one of index codes B32B2363/00 - B32B2383/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- 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
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/01—Tools for processing; Objects used during processing
- H05K2203/0147—Carriers and holders
- H05K2203/0152—Temporary metallic carrier, e.g. for transferring material
Abstract
The present invention provides a kind of stabilized copper foil with carrier of rising, i.e. peel strength of peel strength that can inhibit carrier foils applying high temperature and prolonged thermal process.Copper foil with carrier, it is the copper foil with carrier for being disposed with carrier foils, peeling layer and ultrathin copper foil, wherein, peeling layer includes 5- carboxyl benzotriazole (5CBTA) and/or 4- carboxyl benzotriazole (4CBTA), and the ratio between the adhesion amount of the adhesion amount of 5- carboxyl benzotriazole relative to 4- carboxyl benzotriazole, i.e. 5CBTA/4CBTA ratio are 3.0 or more in peeling layer.
Description
Technical field
The present invention relates to the copper foil with carrier, copper-coated laminated board and printed wiring board.
Background technique
As the material for manufacturing printed wiring board, the copper foil with carrier is widely used.Copper foil with carrier and glass-
The insulating resins substrates such as epoxy substrate, phenolic group material, polyimides are bonded to form copper-coated laminated board by hot forming, for making
Make printed wiring board.
Copper foil with carrier typically has structure made of setting gradually carrier foils, peeling layer and ultrathin copper foil.As
The peeling layer, patent document 1 (Japanese Unexamined Patent Publication 11-317574 bulletin) are proposed containing organic compounds such as nitrogenous compounds
Organic peeling layer, and disclose have the advantages that it is following various: (1) be easily formed peeling layer；(2) ultrathin copper foil and support gold
Belong to layer (the following are carriers) between peel strength (A) uniformly, compared with the peel strength (B) for being stacked on the ultrathin copper foil after substrate
It is shown as low value；(3) since inorganic material is not used, so being removed without the need for by ultrathin copper foil inorganic material remained on surface
Mechanical grinding processes and pickling process, therefore the formation of wiring pattern due to manufacturing procedure number reduce and simplify；(4) although stripping
It is small from intensity (A), but be enough to prevent composite copper foil ultrathin copper foil in processing from separating from carrier；(5) composite copper foil is being stacked on
There is sufficient peel strength (B) after substrate, ultrathin copper foil will not be removed when fabricating printed wiring board from substrate；(6)
Even if carrier after high temperature lamination, can also be separated from ultrathin copper foil；(7) it is easy to remove remaining peeling layer on carrier, therefore
It is easy to carry out the recycling of carrier.
In addition, patent document 2 (Japanese Unexamined Patent Publication 2003-328178 bulletin) discloses a kind of manufacture of copper foil with carrier
Method, this method include using the pickling solution for containing 50ppm ~ 2000ppm organic agent (organic drug), to carrier foils
Surface carries out adsorbing organic agent while pickling dissolution, to form pickling absorption organic envelope as organic peeling layer.
Carboxyl benzotriazole (CBTA) is disclosed in patent document 1 and 2 as being used to form the organic of organic peeling layer
The purposes of inorganic agent.About carboxyl benzotriazole (CBTA), it is known that there are 5- carboxyl benzotriazoles (5CBTA) and 4- carboxyl benzo
Two kinds of chemical structures of triazole (4CBTA), but the record in patent document 1 and 2 absolutely not about 5CBTA and 4CBTA.
But make its miniaturization, the multiple stratification of printed wiring board in recent years in order to improve the packing density of printed wiring board
It is gradually prevailing.For the purpose of lightweight and miniaturization, this multilayered printed circuit has been used in portable electronic device mostly
Plate.And, it is desirable that the multilayer printed circuit board further decreases the thickness of interlayer insulating film, and further light as wiring board
Quantization.Therefore, so-called core substrate (core substrate) is not used in the manufacturing method of multilayer printed circuit board in recent years,
But it uses and utilizes the centreless stacking (coreless buildup method) of insulating resin layer and conductor layer alternative stacked
Manufacturing method.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 11-317574 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2003-328178 bulletin.
Summary of the invention
If however, apply multiple high temp and prolonged thermal process in the presence of the multiple lamination by centreless stacking etc.,
The problem of then peel strength between carrier foils and ultrathin copper foil may be substantially increased.Therefore, though expect apply high temperature and it is long when
Between thermal process, the peel strength between carrier foils and ultrathin copper foil is also difficult to rise, i.e. peel strength is stabilized with carrier
Copper foil.
The inventors of the present invention this time obtain following opinion: in the peeling layer of the copper foil with carrier, by making 5- carboxyl benzene
And it is 3.0 or more that the ratio between the adhesion amount of the adhesion amount of triazole relative to 4- carboxyl benzotriazole, which is 5CBTA/4CBTA ratio, even if applying
It increases temperature and thermal process can also inhibit the rising of the peel strength of carrier foils for a long time, peel strength can be made to stabilize.
Therefore, the object of the present invention is to provide can inhibit carrier foils applying high temperature and prolonged thermal process
Peel strength the stabilized copper foil with carrier of rising, i.e. peel strength.
According to one method of the present invention, a kind of copper foil with carrier is provided, which is disposed with load
Body foil, peeling layer and ultrathin copper foil, wherein
Above-mentioned peeling layer includes 5- carboxyl benzotriazole (5CBTA) and/or 4- carboxyl benzotriazole (4CBTA), above-mentioned stripping
The ratio between the adhesion amount of the adhesion amount of 5- carboxyl benzotriazole relative to 4- carboxyl benzotriazole is that 5CBTA/4CBTA ratio is in absciss layer
More than 3.0.
Another mode according to the present invention provides and covers copper lamination using what the copper foil with carrier of aforesaid way obtained
Plate.
Another mode according to the present invention, provide a kind of copper-coated laminated board, be provided with aforesaid way with carrier
Copper foil.
Another mode according to the present invention provides the printed wire obtained using the copper foil with carrier of aforesaid way
Plate.
Another mode according to the present invention, provides the manufacturing method of printed wiring board, which is characterized in that uses above-mentioned side
The copper foil with carrier of formula manufactures printed wiring board.
Specific embodiment
Copper foil with carrier
Copper foil with carrier of the invention is disposed with carrier foils, peeling layer and ultrathin copper foil.Peeling layer includes 5- carboxylic
Base benzotriazole (hereinafter referred to as 5CBTA) and/or 4- carboxyl benzotriazole (hereinafter referred to as 4CBTA).The change of 4CBTA and 5CBTA
It is as follows to learn structural formula,
。
The ratio between the adhesion amount of the adhesion amount of 5CBTA relative to 4CBTA is in the peeling layer of copper foil with carrier of the invention
5CBTA/4CBTA ratio is 3.0 or more.Therefore, it can be said that 5CBTA is essential component, and 4CBTA is any ingredient.In short, with load
The copper foil of body can also use well known layer structure other than using the distinctive peeling layer of the present invention.
As a result, in the peeling layer of the copper foil of the invention with carrier, by making 5CBTA/4CBTA ratio 3.0 or more, enable
People's will other places can inhibit the rising of the peel strength of carrier foils applying high temperature and prolonged thermal process, can make
Peel strength stabilizes.About this point, although previous CBTA is also used for organic peeling layer as described above, not yet know
5CBTA/4CBTA ratio is 3.0 or more.This is because as far as the applicant is aware, commercially available CBTA mixture is with the ratio of about 6:4
(5CBTA:4CBTA ratio) contains 5CBTA and 4CBTA, and the 5CBTA/4CBTA ratio of the mixture is only about 1.5.It uses
5CBTA/4CBTA has the following problems than the peeling layer of so low CBTA mixture: if passing through the multiple of centreless stacking etc.
Lamination applies multiple high temp and prolonged thermal process, then the peel strength between carrier foils and ultrathin copper foil may substantially on
It rises.In this regard, according to the present invention people this time opinion, in the peeling layer of the copper foil with carrier, by making 5CBTA/4CBTA ratio
3.0 or more, it can unexpectedly solve the above problems.Therefore, the copper foil of the invention with carrier by multiple lamination come
Repeatedly apply in the laminated process of printed wiring board such as high temperature and the centreless stacking of prolonged thermal process, peel strength is opposite
The climbing of peel strength is low under normality (before applying high temperature and prolonged thermal process), and the removing that can be played stably is strong
It spends (such as 10 ~ 20gf/cm).Therefore, the copper foil of the invention with carrier is to fold to printed wiring board such as centreless stacking
Layer process is extremely useful.
Peeling layer is to guarantee the stability of the intensity, in turn with the peel strength weakened between carrier foils and ultrathin copper foil
Inhibit at high temperature press molding when carrier foils and copper foil between generable phase counterdiffusion function layer.The usual shape of peeling layer
At in the one side of carrier foils, but the two sides of carrier foils can also be formed in.Peeling layer is organic peeling layer, containing 5CBTA, and
Contain 4CBTA as needed.Peeling layer is other than containing 5CBTA and 4CBTA, also containing the ingredient as organic peeling layer
Known other compositions.
5CBTA/4CBTA ratio in peeling layer is 3.0 or more, preferably 3.5 ~ 30.If 5CBTA/4CBTA ratio is in the model
In enclosing, then the peel strength for being easy to further play stably.It should be noted that peeling layer can contain only 5CBTA (without 4CBTA).
In peeling layer, preferably to add up to 3mg/m2Above adhesion amount contain 5CBTA and in the presence of
4CBTA, the adhesion amount are more preferably 5mg/m2More than, further preferably 8mg/m2More than.The upper limit value of adhesion amount is without spy
Do not limit, for the raising of the copper foil operability with carrier and the further stabilisation of peel strength, in peeling layer, preferably with
Total 80mg/m2Adhesion amount below contain 5CBTA and in the presence of 4CBTA, the adhesion amount is more preferably
50mg/m2It below, is more preferably 30mg/m2Below.
The formation of peeling layer can carry out in the following manner: make comprising the 5CBTA's and 4CBTA contained as needed
CBTA ingredient, is fixed on the surface etc. of carrier foils by least one surface of CBTA solution contact carrier foil.CBTA solution is preferred
The concentration ratio of 4CBTA, 5CBTA/4CBTA of 5CBTA, 0 ~ 3000ppm containing 50 ~ 6000ppm are 2 or more, further preferably
The 5CBTA of 300 ~ 800ppm, the concentration ratio of 4CBTA, 5CBTA/4CBTA of 0 ~ 150ppm are 2 ~ 8.The fluid temperature of CBTA solution
Preferably 20 ~ 60 DEG C of range, more preferably 30 ~ 40 DEG C.It is preferably 5 ~ 120 seconds ranges with the processing time of CBTA solution,
More preferably 30 ~ 60 seconds.Carrier foils can be by being impregnated in CBTA solution, spraying CBTA solution, stream with the contact of CBTA solution
Down or CBTA solution is added dropwise to carry out.In addition, fixation of the CBTA on carrier foils surface can be by the absorption of CBTA solution or dry
Dry, CBTA ingredient in CBTA solution electro-deposition etc. carries out.For example, in the case where using copper foil as carrier foils, removing
The formation of layer preferably adsorbs CBTA ingredient while carrying out pickling processes to carrier foils, and in the case, CBTA solution is excellent
Select 2 ~ 20g/L of 50 ~ 250g/L of sulfuric acid concentration and copper concentration, more preferable 100 ~ 200g/L of sulfuric acid concentration and 5 ~ 15g/ of copper concentration
L.Thus, it is possible on one side dissolve the surface acid-washing of carrier foils, the metal ion of elution and CBTA ingredient is made to form metal on one side
Complex compound, by its precipitation adsorption in carrier foils.As a result, the absorption tissue of the CBTA ingredient of precipitation adsorption becomes fine, and
And compared with the case where contact is only dispersed with the aqueous solution of CBTA ingredient and precipitation adsorption, CBTA ingredient uniform adsorption can be made.
Carrier foils are the foils for being used to support ultrathin copper foil and improving its operability.As the example of carrier foils, aluminium can be enumerated
Foil, copper foil, stainless steel (SUS) foil, surface are coated with resin film of metal etc., preferably copper foil.Copper foil can for rolled copper foil and
Electrolytic copper foil it is any.The thickness of carrier foils is typically 250 μm hereinafter, preferably 9 μm ~ 200 μm.
Ultrathin copper foil can be known features used by the ultrathin copper foil with carrier, be not particularly limited.For example, very thin copper
Foil can using the dry types membrane formation process such as wet type membrane formations, sputtering and the chemical vapor deposition such as electroless copper method and electrocoppering or this
The combinations of a little methods is formed.The thickness of ultrathin copper foil is preferably 0.1 ~ 7.0 μm, and more preferably 0.5 ~ 5.0 μm, further preferably
It is 1.0 ~ 3.0 μm.
Ultrathin copper foil is preferably roughening face with the face of peeling layer opposite side.That is, an it is preferred that face to ultrathin copper foil
It is roughened.Thereby, it is possible to improve manufacture copper-coated laminated board or when printed wiring board and the adaptation of resin layer.This is thick
Roughening processing is preferably carried out according to well known coating method, and the known coating method is via including being precipitated fine copper particle and adhering to
Plating (baked け め っ I) process and the coating plating for preventing the fine copper particle from falling off are burnt on ultrathin copper foil
At least two kinds of plating process of (by せ め っ I) process.
Other function layer can be set between peeling layer and carrier foils and/or ultrathin copper foil.As other such function
The example of ergosphere can enumerate auxiliary metal layer.Auxiliary metal layer preferably comprises nickel and/or cobalt.Pass through the surface side in carrier foils
And/or the surface side of ultrathin copper foil forms the auxiliary metal layer, when being able to suppress high temperature or Long Time Thermal pressing formation carrier foils with
The phase counterdiffusion that may occur between ultrathin copper foil, guarantees the stability of the peel strength of carrier foils.The thickness of auxiliary metal layer
Preferably 0.001 ~ 3 μm.
As needed, antirust treatment can be implemented to ultrathin copper foil.Antirust treatment preferably includes the plating using zinc.
Using the plating of zinc any, particularly preferred zinc-nickel of galvanized alloy processing can be handled for zinc-plated processing and galvanized alloy
Alloy treatment.As long as zinc-nickel alloy handle the plating comprising at least Ni and Zn, can further include Sn, Cr,
The other elements such as Co.The Ni/Zn attachment ratio plated in zinc-nickel alloy is preferably 1.2 ~ 10, more preferably 2 ~ 7 by quality ratio,
Further preferably 2.7 ~ 4.In addition, antirust treatment preferably further includes chromic acid salt treatment.The chromic acid salt treatment more preferably exists
After the plating of zinc, carried out in the coating surface containing zinc.Thereby, it is possible to further increase rust-preventing characteristic.Particularly preferably
Antirust treatment be the combination for plating zinc-nickel alloy processing and chromic acid salt treatment thereafter.
As needed, silane coupling agent processing can be implemented to the surface of ultrathin copper foil, forms silane coupling agent layer.By
This, can be improved moisture-proof, chemical-resistant and with the adaptation of adhesive etc. etc..Silane coupling agent layer can pass through by
Silane coupling agent is suitably diluted, is coated and dried to be formed.As the example of silane coupling agent, 4- glycidyl fourth can be enumerated
Silanes' coupling agents such as base trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane；Gamma-amino third
Base trimethoxy silane, N- β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-3- (4- (3- amino propoxyl group) fourth oxygen
Base) amino-functional silanes such as propyl -3- TSL 8330, N- phenyl-gamma-amino propyl trimethoxy silicane
Coupling agent；The Mercaptofunctionals silane coupling agent such as γ mercaptopropyitrimethoxy silane；Vinyltrimethoxysilane, ethylene
The alkene functional silanes coupling agent such as base phenyltrimethoxysila,e；γ-methacryloxypropyl trimethoxy silane etc.
Acrylic functional's silane coupling agent；The imidazoles functional silanes coupling agent such as imidazoles base silane；Or the triazines official such as triazine silane
Energy property silane coupling agent etc..
Copper-coated laminated board
Copper foil with carrier of the invention is preferred for making printed wiring board copper-coated laminated board.That is, according to the present invention
Preferred embodiment, the copper-coated laminated board obtained using the above-mentioned copper foil with carrier is provided.The copper-coated laminated board is provided with this
Resin layer on the copper foil with carrier and the closely sealed ultrathin copper foil for being set to the copper foil with carrier of invention.With carrier
The single side in resin layer can be set in copper foil, also can be set in the two-sided of resin layer.Resin layer includes resin, is preferably comprised absolutely
Edge resin.Resin layer is preferably prepreg and/or resin sheet.Prepreg refers to, make synthetic resin be impregnated in synthetic resin board,
The general name of composite material made of in the substrates such as glass plate, glass fabric, glass non-woven fabric, paper.As insulative resin
Preference can enumerate epoxy resin, cyanate ester resin, bismaleimide-triazine resin (BT resin), polyphenylene oxide resin, phenol
Urea formaldehyde etc..In addition, the example as the insulative resin for constituting resin sheet, can enumerate epoxy resin, polyimide resin, gather
The insulating resins such as ester resin.In addition, from the viewpoints such as insulating properties are improved, it can be containing by silica, aluminium oxide in resin layer
Etc. the filler grain etc. of various inorganic particulates composition.The thickness of resin layer is not particularly limited, and preferably 1 ~ 1000 μm, more preferably
It is 2 ~ 400 μm, further preferably 3 ~ 200 μm.Resin layer can be made up of multiple layers.The resin layers such as prepreg and/or resin sheet can
To be arranged on the ultrathin copper foil with carrier across the bottom coating resin layer being pre-coated in copper foil surface.
Printed wiring board
Copper foil with carrier of the invention is preferred for making printed wiring board.That is, preferred implementation side according to the present invention
Formula provides the printed wiring board obtained using the above-mentioned copper foil with carrier.The printed wiring board of present embodiment includes successively to fold
Layer structure made of layer resin layer and layers of copper.In addition, for resin layer, it is as described above about copper-coated laminated board.In short, track
Road plate can use well known floor structure.As the concrete example of printed wiring board is related to, can enumerate prepreg single side or
Both-sided adhesive ultrathin copper foil of the invention and be solidified into laminated body so formed circuit single or double printed wiring board or
Person is by multilayer printed circuit board made of its multiple stratification etc..In addition, can enumerate and be formed on resin film as other concrete examples
Ultrathin copper foil of the invention simultaneously forms the flexible print circuit board of circuit, COF, TAB band etc..And then other concrete examples are used as, also
It can enumerate: the copper foil (RCC) that above-mentioned resin layer forms resin is coated on ultrathin copper foil of the invention, in above-mentioned printing
Wiring board superimposed layer resin layer, then using ultrathin copper foil as entire or a part of wiring layer, is used as insulating sticky composite layer
Half addition of modified form (MSAP, modified semi-additive process) method, subtractive method (subtractive
The methods of) method stacking (build up) wiring board of circuit is formed；Ultrathin copper foil is removed, using half addition (SAP) method
Form the stacking wiring board of circuit；Alternately and repeatedly carry out lamination and circuit shape of the copper foil of resin on semiconductor integrated circuit
At chip on directly stack (direct build up on wafer) wiring board etc..Copper foil with carrier of the invention does not make
With so-called core substrate, it also may be preferable for for using the manufacture of insulating resin layer and the centreless stacking of conductor layer alternative stacked
Method.
Embodiment
Further the present invention is specifically described by following example.
Example 1 ~ 9
The production and evaluation as follows for carrying out the copper foil with carrier.
(1) preparation of carrier foils
Prepare the electrolytic copper foil (Mitsu Mining & Smelting Co., Ltd of 18 μ m-thicks not being roughened with antirust treatment
System, Class-III) it is used as carrier foils.
(2) formation of peeling layer
In the 5CBTA containing concentration shown in following table 1 and/or 4CBTA, sulfuric acid concentration 150g/L and copper concentration 10g/L
CBTA aqueous solution in, by the electrode surface side of the carrier foils through pickling processes at 30 DEG C of fluid temperature (example 1 ~ 4,7 and 8) or 40 DEG C
It is impregnated 30 seconds under (example 5,6 and 9), CBTA ingredient is made to be adsorbed in the electrode surface of carrier foils.As a result, on the surface of carrier foils electrode surface
It forms CBTA layers and is used as organic peeling layer.It should be noted that the composition of example 7 is equivalent to (the Japanese Unexamined Patent Publication 2003- of patent document 2
No. 328178 bulletins) disclosed embodiment 3.
[table 1]
。
(3) formation of auxiliary metal layer
The carrier foils for foring organic peeling layer are impregnated in using in the solution of nickel concentration 20g/L made of nickel sulfate,
In 45 DEG C of fluid temperature, pH3, current density 5A/dm2Under conditions of, make the nickel attachment for being equivalent to 0.001 μm of thickness of adhesion amount
On organic peeling layer.Nickel layer is formed on organic peeling layer as a result, as auxiliary metal layer.
(4) formation of ultrathin copper foil
The carrier foils for foring auxiliary metal layer are impregnated in the copper solution of composition as shown below, in solution temperature 45
DEG C, 5 ~ 30A/dm of current density2Lower electrolysis forms 3 μm of thickness of ultrathin copper foil in auxiliary metal layer；
<composition of solution>
Copper concentration: 65g/L
Sulfuric acid concentration: 150g/L.
(5) roughening treatment
The surface for the ultrathin copper foil being consequently formed is roughened.The roughening treatment is by being precipitated fine copper particle
And it is attached on ultrathin copper foil and burns plating process and the coating plating process structure for preventing the fine copper particle from falling off
At.In burning plating process, using the acid copper sulfate solution containing 18g/L copper and 100g/L sulfuric acid, in fluid temperature 25
DEG C, current density 10A/dm2Under be roughened.In coating plating process later, using containing 65g/L copper and
The copper solution of 150g/L sulfuric acid, in 45 DEG C of fluid temperature, current density 15A/dm2Steady plating conditions under carry out electro-deposition.
(6) antirust treatment
The two-sided of the copper foil with carrier after roughening treatment is carried out including inorganic antirust treatment and chromic acid salt treatment
Antirust treatment.Firstly, bathed as inorganic antirust treatment using pyrophosphoric acid, potassium pyrophosphate concentration 80g/L, zinc concentration 0.2g/L,
Nickel concentration 2g/L, 40 DEG C of fluid temperature, current density 0.5A/dm2Lower progress zinc-nickel alloy antirust treatment.Then, as chromic acid
Salt treatment is further formed chromate coating on the basis of zinc-nickel alloy antirust treatment.The chromic acid salt treatment is in chromic acid concentration
For 1g/L, pH 11,25 DEG C of solution temperature, current density 1A/dm2Under conditions of carry out.
(7) silane coupling agent is handled
The copper foil water washing of above-mentioned antirust treatment will be implemented, then carries out silane coupling agent processing at once, make silane coupled
Agent is adsorbed on the antirust treatment layer in roughening treatment face.Silane coupling agent processing carries out in the following manner: being with pure water
Solvent, the solution for the use of 3- TSL 8330 concentration being 3g/L, by solution spray head ring (シ ャ ワ ー リ Application
It グ) is sprayed on roughening treatment face and carries out adsorption treatment.After silane coupling agent absorption, finally moisture is waved with electric heater
It dissipates, obtains the copper foil with carrier.
(8) evaluation of the copper foil with carrier
Copper foil for gained with carrier carries out following evaluation.
<analysis of peeling layer>
By carrier foils from the copper foil removing with carrier.By the carrier foils being stripped and ultrathin copper foil in the hydrochloric acid of 1mol/L
It is impregnated 60 minutes at 40 DEG C, extracts CBTA.At this point, by the way that carrier foils and ultrathin copper foil and the face of peeling layer opposite side are covered
It covers, CBTA extraction only is carried out to the face to connect with peeling layer.By the thus resulting extract high performance liquid chromatography containing CBTA
(Shimadzu Scisakusho Ltd's system, HPLC LC10 series) is analyzed, and concentration and the 4CBTA for measuring 5CBTA are respective dense
Degree, calculates the adhesion amount (mg/m of 5CBTA2), the adhesion amount (mg/m of 4CBTA2), the sum of the adhesion amount of CBTA (mg/m2), with
And 5CBTA/4CBTA ratio.The results are shown in Table 2.
<measurement of peel strength>
Firstly, being measured as follows to the peel strength of the normality of the copper foil with carrier.Double faced adhesive tape is carried in band
The ultrathin copper foil side of the copper foil of body, is pasted and is fixed on substrate, and measurement sample is obtained.For the measurement sample, according to
The peel strength RS of normality when JIS C 6481-1996 measurement removing carrier foils0(gf/cm).At this point, measurement width is
50mm, measured length 20mm.
Then, the peel strength after 1 time or 2 hot pressing is measured as follows.Prepare 100 μm of thickness of prepreg
(Mitsubishi Gas Chemical Co., Ltd's system, GHPL830NX-A) is used as resin base material.In the copper of the resin base material superimposed layer with carrier
Foil abuts the ultrathin copper foil side of the copper foil with carrier with resin base material, carries out 1 time at pressure 2.5MPa, 230 DEG C of temperature
Or 2 times 60 minutes hot formings, the copper-coated laminated board sample after obtaining hot pressing.For copper-coated laminated board sample, according to JIS C
Carrier foils are removed from the ultrathin copper foil for being stacked on resin base material face, measure peel strength RS by 6481-19961(after hot pressing 1 time)
With peel strength RS2(after hot pressing 2 times) (gf/cm).At this point, measurement width is 50mm, measured length 20mm.After hot pressing 2 times
Peel strength RS2Peel strength RS relative to the normality before hot pressing0The ratio between ((RS2-RS0)/RS0) multiplied by 100, calculate stripping
From intensity climbing (%).The results are shown in Table 2.
[table 2]
。
Claims (6)
1. the copper foil with carrier is the copper foil with carrier for being disposed with carrier foils, peeling layer and ultrathin copper foil, wherein
The peeling layer includes 5- carboxyl benzotriazole and 4- carboxyl benzotriazole, 5- carboxyl benzotriazole in the peeling layer
The ratio between the adhesion amount of adhesion amount relative to 4- carboxyl benzotriazole, i.e. 5CBTA/4CBTA ratio are 3.5 ~ 30,
The 5- carboxyl benzotriazole is denoted as 5CBTA, and the 4- carboxyl benzotriazole is denoted as 4CBTA.
2. the copper foil according to claim 1 with carrier, wherein in the peeling layer, to add up to 3mg/m2Above attachment
Amount contains 5- carboxyl benzotriazole and 4- carboxyl benzotriazole,
The 5- carboxyl benzotriazole is denoted as 5CBTA, and the 4- carboxyl benzotriazole is denoted as 4CBTA.
3. the copper foil according to claim 1 with carrier, wherein in the peeling layer, to add up to 80mg/m2It is below attached
Amount contain 5- carboxyl benzotriazole and 4- carboxyl benzotriazole,
The 5- carboxyl benzotriazole is denoted as 5CBTA, and the 4- carboxyl benzotriazole is denoted as 4CBTA.
4. the copper foil according to claim 1 with carrier, wherein the peeling layer and the carrier foils and/or the pole
Auxiliary metal layer is further provided between thin copper foil.
5. copper-coated laminated board is provided with the copper foil described in any one of Claims 1-4 with carrier.
6. the manufacturing method of printed wiring board, which is characterized in that using described in any one of any one of claims 1 to 44 with carrier
Copper foil manufactures printed wiring board.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015133105A JP5842077B1 (en) | 2015-07-01 | 2015-07-01 | Copper foil with carrier, copper-clad laminate and printed wiring board |
| JP2015-133105 | 2015-07-01 |
Publications (2)
| Publication Number | Publication Date |
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| CN106332458A CN106332458A (en) | 2017-01-11 |
| CN106332458B true CN106332458B (en) | 2019-03-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610100065.2A Active CN106332458B (en) | 2015-07-01 | 2016-02-24 | Copper foil, copper-coated laminated board and printed wiring board with carrier |
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| Country | Link |
|---|---|
| JP (1) | JP5842077B1 (en) |
| KR (2) | KR20170004826A (en) |
| CN (1) | CN106332458B (en) |
| LU (1) | LU93050B1 (en) |
| MY (1) | MY176516A (en) |
| PH (1) | PH12016000167A1 (en) |
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|---|---|---|---|---|
| JP5842077B1 (en) * | 2015-07-01 | 2016-01-13 | 三井金属鉱業株式会社 | Copper foil with carrier, copper-clad laminate and printed wiring board |
| JP6471140B2 (en) * | 2016-11-30 | 2019-02-13 | 福田金属箔粉工業株式会社 | Composite metal foil, copper-clad laminate using the composite metal foil, and method for producing the copper-clad laminate |
| JP6462940B1 (en) * | 2018-03-23 | 2019-01-30 | 三井金属鉱業株式会社 | Copper foil with carrier, copper-clad laminate and printed wiring board |
| WO2020031721A1 (en) * | 2018-08-10 | 2020-02-13 | 三井金属鉱業株式会社 | Roughened copper foil, copper foil with carrier, copper-clad laminate and printed wiring board |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1533450A (en) * | 2002-05-14 | 2004-09-29 | ���������kҵ��ʽ���� | Method of producing high temperature heat resistant electrolytic copper foil with carrier foil and electrolytic copper foil obtained by the method |
| JP2009180796A (en) * | 2008-01-29 | 2009-08-13 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element, and method for manufacturing printed wiring board |
| CN101892499A (en) * | 2010-07-24 | 2010-11-24 | 江西理工大学 | Peel-able ultra-thin copper foil using copper foil as carrier and preparation method thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6319620B1 (en) * | 1998-01-19 | 2001-11-20 | Mitsui Mining & Smelting Co., Ltd. | Making and using an ultra-thin copper foil |
| JP3392066B2 (en) * | 1998-01-19 | 2003-03-31 | 三井金属鉱業株式会社 | Composite copper foil, method for producing the same, copper-clad laminate and printed wiring board using the composite copper foil |
| JP3612594B2 (en) * | 1998-05-29 | 2005-01-19 | 三井金属鉱業株式会社 | Composite foil with resin, method for producing the same, multilayer copper-clad laminate using the composite foil, and method for producing multilayer printed wiring board |
| JP3812834B2 (en) * | 2002-08-12 | 2006-08-23 | 三井金属鉱業株式会社 | Electrolytic copper foil with carrier foil, method for producing the same, and copper-clad laminate using the electrolytic copper foil with carrier foil |
| EP2546387A1 (en) * | 2008-03-21 | 2013-01-16 | Enthone, Inc. | Adhesion promotion of metal to laminate with a multi-functional compound |
| JP5379528B2 (en) | 2009-03-24 | 2013-12-25 | 三井金属鉱業株式会社 | Electrolytic copper foil with carrier foil, method for producing electrolytic copper foil with carrier foil, and copper-clad laminate obtained using the electrolytic copper foil with carrier foil |
| EP2240005A1 (en) * | 2009-04-09 | 2010-10-13 | ATOTECH Deutschland GmbH | A method of manufacturing a circuit carrier layer and a use of said method for manufacturing a circuit carrier |
| WO2012118031A1 (en) * | 2011-03-03 | 2012-09-07 | ニチゴー・モートン株式会社 | Photosensitive resin composition, photoresist film using same, resist pattern forming method, and conductor pattern forming method |
| JP5842077B1 (en) * | 2015-07-01 | 2016-01-13 | 三井金属鉱業株式会社 | Copper foil with carrier, copper-clad laminate and printed wiring board |
-
2015
- 2015-07-01 JP JP2015133105A patent/JP5842077B1/en active Active
- 2015-12-10 TW TW104141527A patent/TWI583268B/en active
-
2016
- 2016-02-15 KR KR1020160016978A patent/KR20170004826A/en active Application Filing
- 2016-02-24 CN CN201610100065.2A patent/CN106332458B/en active Active
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- 2016-04-27 LU LU93050A patent/LU93050B1/en active IP Right Grant
- 2016-05-25 MY MYPI2016701902A patent/MY176516A/en unknown
- 2016-12-23 KR KR1020160177436A patent/KR102316978B1/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1533450A (en) * | 2002-05-14 | 2004-09-29 | ���������kҵ��ʽ���� | Method of producing high temperature heat resistant electrolytic copper foil with carrier foil and electrolytic copper foil obtained by the method |
| JP2009180796A (en) * | 2008-01-29 | 2009-08-13 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element, and method for manufacturing printed wiring board |
| CN101892499A (en) * | 2010-07-24 | 2010-11-24 | 江西理工大学 | Peel-able ultra-thin copper foil using copper foil as carrier and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI583268B (en) | 2017-05-11 |
| KR20170004924A (en) | 2017-01-11 |
| CN106332458A (en) | 2017-01-11 |
| MY176516A (en) | 2020-08-12 |
| LU93050A1 (en) | 2017-01-25 |
| JP2017013385A (en) | 2017-01-19 |
| LU93050B1 (en) | 2017-06-08 |
| PH12016000167B1 (en) | 2017-10-30 |
| JP5842077B1 (en) | 2016-01-13 |
| KR20170004826A (en) | 2017-01-11 |
| TW201622495A (en) | 2016-06-16 |
| PH12016000167A1 (en) | 2017-10-30 |
| KR102316978B1 (en) | 2021-10-25 |
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