CN106332458A - Copper foil with carrier, copper-clad laminate and printed circuit board - Google Patents
Copper foil with carrier, copper-clad laminate and printed circuit board Download PDFInfo
- Publication number
- CN106332458A CN106332458A CN201610100065.2A CN201610100065A CN106332458A CN 106332458 A CN106332458 A CN 106332458A CN 201610100065 A CN201610100065 A CN 201610100065A CN 106332458 A CN106332458 A CN 106332458A
- Authority
- CN
- China
- Prior art keywords
- copper foil
- carrier
- 5cbta
- 4cbta
- peel ply
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
- C25D1/00—Electroforming
- C25D1/20—Separation of the formed objects from the electrodes with no destruction of said electrodes
- C25D1/22—Separating compounds
-
- 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
-
- 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 copper foil with carrier, which may still restrain the increase of peeling strength of carrier foil even though given high temperature and long-term thermal history, that is, with stabilized peeling strength. The copper foil with carrier according to the present invention is a copper foil with carrier sequentially comprising a carrier foil, a release layer, and an ultra-thin copper foil. The release layer contains 5-carboxyl benzotriazole (5CBTA) and/or 4-carboxyl benzotriazole (4CBTA), in which the ratio of the adhesion amount of 5-carboxyl benzotriazole to the adhesion amount of 4-carboxyl benzotriazole in the release layer, namely the ratio OF 5CBTA/4CBTA, is above 3.0.
Description
Technical field
The present invention relates to the Copper Foil of band carrier, copper-coated laminated board and printed substrate.
Background technology
As the material for manufacturing printed substrate, the Copper Foil of band carrier is widely used.Copper Foil with carrier and glass-
The insulating resin base materials such as epoxy base material, phenolic group material, polyimides are fitted by hot forming formation copper-coated laminated board, are used for making
Make printed substrate.
Copper Foil with carrier typically has the structure setting gradually carrier foils, peel ply and ultrathin copper foil.As
This peel ply, patent documentation 1 (Japanese Unexamined Patent Publication 11-317574 publication) proposes containing organic compound such as nitrogen-containing compounds
Organic peel ply, and disclose there is following various advantage: (1) is easily formed peel ply；(2) ultrathin copper foil and support gold
Belong to the peel strength (A) between layer (be carrier below) uniformly, compared with the peel strength (B) being stacked on the ultrathin copper foil after base material
It is shown as low value；(3) owing to not using inorganic material, so without for the inorganic material of ultrathin copper foil remained on surface is removed
Mechanical grinding processes and pickling process, therefore the formation of wiring pattern due to manufacturing procedure number reduce and simplify；(4) although shelling
Little from intensity (A), but be enough to prevent composite copper foil ultrathin copper foil when processing from separating from carrier；(5) composite copper foil is being stacked on
Having sufficient peel strength (B) after base material, ultrathin copper foil will not be peeled off from base material when processing and manufacturing printed substrate；(6)
Even if carrier is after high temperature lamination, it is also possible to separate from ultrathin copper foil；(7) it is prone to remove the peel ply of residual on carrier, therefore
It is prone to carry out the recycling of carrier.
It addition, patent documentation 2 (Japanese Unexamined Patent Publication 2003-328178 publication) discloses the manufacture of the Copper Foil of a kind of band carrier
Method, the method includes using the Acidwash solution containing 50ppm ~ 2000ppm organic agent (having), to carrier foils
Organic agent is adsorbed on surface while carrying out pickling dissolving, thus forms pickling absorption organic envelope as organic peel ply.
Patent documentation 1 and 2 all discloses carboxyl benzotriazole (CBTA) as forming the organic of organic peel ply
The purposes of inorganic agent.About carboxyl benzotriazole (CBTA), it is known that there is 5-carboxyl benzotriazole (5CBTA) and 4-carboxyl benzo
Two kinds of chemical constitutions of triazole (4CBTA), but entirely without the record about 5CBTA and 4CBTA in patent documentation 1 and 2.
But, make its miniaturization to improve the packing density of printed substrate in recent years, the multiple stratification of printed substrate
The most prevailing.For lightweight and the purpose of miniaturization, portable electric appts is used mostly this multilayered printed circuit
Plate.And, it is desirable to this multilayer printed circuit board reduces the thickness of interlayer insulating film further, and the lightest as wiring board
Quantify.Therefore, the manufacture method of multilayer printed circuit board does not use so-called core substrate (core substrate) in recent years,
But employing utilizes the insulating resin layer centreless stacking (coreless buildup method) with conductor layer alternative stacked
Manufacture method.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 11-317574 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2003-328178 publication.
Summary of the invention
But, applied multiple high temp and long thermal process by the repeatedly lamination of centreless stacking etc. if existing,
The problem that then peel strength between carrier foils and ultrathin copper foil may be substantially increased.Therefore, though expect apply high temperature and long time
Between thermal process, the peel strength between carrier foils and ultrathin copper foil is also difficult to rise, i.e. the band carrier of peel strength stabilisation
Copper Foil.
The present inventor etc. this time obtain following opinion: in the peel ply of the Copper Foil of band carrier, by making 5-carboxyl benzene
And the adhesion amount of triazole is more than 3.0 relative to the ratio i.e. 5CBTA/4CBTA ratio of the adhesion amount of 4-carboxyl benzotriazole, even if executing
Increase temperature and the rising of peel strength that for a long time thermal process also can suppress carrier foils, i.e. can make peel strength stabilisation.
Therefore, it is an object of the invention to, it is provided that even if applying high temperature and for a long time thermal process also can suppress carrier foils
The rising of peel strength, i.e. the Copper Foil of the band carrier of peel strength stabilisation.
A mode according to the present invention, it is provided that the Copper Foil of a kind of band carrier, the Copper Foil of this band carrier is disposed with load
Body paper tinsel, peel ply and ultrathin copper foil, wherein,
Above-mentioned peel ply comprises 5-carboxyl benzotriazole (5CBTA) and/or 4-carboxyl benzotriazole (4CBTA), above-mentioned peel ply
The adhesion amount of middle 5-carboxyl benzotriazole is 3.0 relative to the ratio i.e. 5CBTA/4CBTA ratio of the adhesion amount of 4-carboxyl benzotriazole
Above.
Another mode according to the present invention, it is provided that make what the Copper Foil of band carrier in fashion described above obtained to cover copper lamination
Plate.
Another mode according to the present invention, it is provided that a kind of copper-coated laminated board, it is provided with the band carrier of aforesaid way
Copper Foil.
Another mode according to the present invention, it is provided that make the printed wire that the Copper Foil of band carrier in fashion described above obtains
Plate.
Another mode according to the present invention, it is provided that the manufacture method of printed substrate, it is characterised in that use above-mentioned side
The Copper Foil of the band carrier of formula manufactures printed substrate.
Detailed description of the invention
Copper Foil with carrier
The Copper Foil of the band carrier of the present invention is disposed with carrier foils, peel ply and ultrathin copper foil.Peel ply comprises 5-carboxyl benzene
And triazole (hereinafter referred to as 5CBTA) and/or 4-carboxyl benzotriazole (hereinafter referred to as 4CBTA).The chemistry knot of 4CBTA and 5CBTA
Structure formula is as follows,
。
In the peel ply of the Copper Foil of the band carrier of the present invention, the ratio of the adhesion amount of the 5CBTA adhesion amount relative to 4CBTA is i.e.
5CBTA/4CBTA ratio is more than 3.0.Therefore, it can be said that 5CBTA is essential component, and 4CBTA is any composition.In a word, band carries
The Copper Foil of body is in addition to using the distinctive peel ply of the present invention, it is also possible to use known Rotating fields.
Thus, in the peel ply of the Copper Foil of the band carrier of the present invention, by making 5CBTA/4CBTA ratio be more than 3.0, order
People unexpectedly, even if applying high temperature and for a long time thermal process also can suppress the rising of the peel strength of carrier foils, i.e. can make
Peel strength stabilisation.About this point, although CBTA was also used for organic peel ply, but not yet knew the most in the past
5CBTA/4CBTA ratio is more than 3.0.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) is only about 1.5 containing 5CBTA and 4CBTA, the 5CBTA/4CBTA ratio of this mixture.Use
If 5CBTA/4CBTA there is problems in that by centreless stacking etc. repeatedly than the peel ply of the lowest CBTA mixture
Lamination applies multiple high temp and long thermal process, then the peel strength between carrier foils and ultrathin copper foil may significantly go up
Rise.To this, according to this time opinion of the present inventor, in the peel ply of the Copper Foil of band carrier, by making 5CBTA/4CBTA ratio be
More than 3.0, it is possible to solve the problems referred to above unexpectedly.Therefore, the Copper Foil of the band carrier of the present invention is by repeatedly lamination
Repeatedly applying in the laminated process of high temperature and the long printed substrate such as centreless stacking of thermal process, peel strength is relative
Under normality (before applying high temperature and long thermal process), the climbing of peel strength is low, and the stripping that can play stably is strong
Degree (such as 10 ~ 20gf/cm).Therefore, the Copper Foil of the band carrier of the present invention is to fold the printed substrates such as centreless stacking
Layer process is extremely useful.
Peel ply is to have the peel strength weakening between carrier foils and ultrathin copper foil, it is ensured that the stability of this intensity, and then
The layer of the function of generable phase counterdiffusion between carrier foils and Copper Foil when suppressing at high temperature press molding.The usual shape of peel ply
Become the one side of carrier foils but it also may be formed at the two sides of carrier foils.Peel ply is organic peel ply, containing 5CBTA, and
Contain 4CBTA as required.Peel ply, also can be containing the composition as organic peel ply in addition to containing 5CBTA and 4CBTA
Other compositions known.
5CBTA/4CBTA ratio in peel ply is more than 3.0, preferably 3.5 ~ 30.If 5CBTA/4CBTA ratio is at this model
In enclosing, then it is prone to the peel strength played stably further.Should illustrate, peel ply can only contain 5CBTA (without 4CBTA).
In peel ply, preferably to add up to 3mg/m2Above adhesion amount contain 5CBTA and in the presence of
4CBTA, described adhesion amount is more preferably 5mg/m2Above, more preferably 8mg/m2Above.The higher limit of adhesion amount does not has spy
Do not limit, for the raising of Copper Foil operability and the further stabilisation of peel strength of band carrier, in peel ply, preferably with
Add up to 80mg/m2Following adhesion amount contain 5CBTA and in the presence of 4CBTA, described adhesion amount is more preferably
50mg/m2Below, more preferably 30mg/m2Below.
The formation of peel ply can be carried out in the following manner: makes to comprise 5CBTA's and the 4CBTA that contains as required
At least one surface of CBTA solution contact carrier paper tinsel, is fixed on the surface etc. of carrier foils by CBTA composition.CBTA solution is preferred
5CBTA containing 50 ~ 6000ppm, the concentration ratio of 4CBTA, 5CBTA/4CBTA of 0 ~ 3000ppm are more than 2, more preferably contain
The 5CBTA of 300 ~ 800ppm, the concentration ratio of 4CBTA, 5CBTA/4CBTA of 0 ~ 150ppm are 2 ~ 8.The temperature of liquid of CBTA solution
The scope of preferably 20 ~ 60 DEG C, more preferably 30 ~ 40 DEG C.The process time with CBTA solution is preferably the scope of 5 ~ 120 seconds,
More preferably 30 ~ 60 seconds.Carrier foils can be by impregnated in CBTA solution, spraying CBTA solution, stream with contacting of CBTA solution
Lower or dropping CBTA solution is carried out.It addition, CBTA can be by the absorption of CBTA solution or dry at the fixing of carrier foils surface
In dry, CBTA solution, the electro-deposition etc. of CBTA composition is carried out.Such as, in the case of using Copper Foil as carrier foils, peel off
The formation of layer preferably makes CBTA composition adsorb while carrier foils is carried out pickling processes, and in the case, CBTA solution is excellent
Select sulfuric acid concentration 50 ~ 250g/L and copper concentration 2 ~ 20g/L, more preferably sulfuric acid concentration 100 ~ 200g/L and copper concentration 5 ~ 15g/
L.Thus, it is possible to while making the surface acid-washing of carrier foils dissolve, make the metal ion of eluting form metal with CBTA composition
Complex, by its precipitation adsorption in carrier foils.Its result, the absorption tissue of the CBTA composition of precipitation adsorption becomes fine, and
And be only dispersed with the aqueous solution of CBTA composition with contact and compared with the situation of precipitation adsorption, it is possible to make CBTA composition uniform adsorption.
Carrier foils is for supporting the paper tinsel that ultrathin copper foil makes its operability improve.As the example of carrier foils, aluminum can be listed
Paper tinsel, Copper Foil, rustless steel (SUS) paper tinsel, surface are coated with the resin molding etc. of metal, preferably Copper Foil.Copper Foil can be rolled copper foil and
Any one of electrolytic copper foil.The thickness of carrier foils is typically below 250 μm, preferably 9 μm ~ 200 μm.
The known features that ultrathin copper foil can be used by the ultrathin copper foil of band carrier, is not particularly limited.Such as, very thin copper
Paper tinsel can use the dry type membrane formation process such as wet type membrane formation process, sputtering and chemical vapor deposition such as electroless copper method and electrocoppering or this
The combination of a little methods is formed.The thickness of ultrathin copper foil is preferably 0.1 ~ 7.0 μm, more preferably 0.5 ~ 5.0 μm, further preferably
It is 1.0 ~ 3.0 μm.
The face with peel ply opposite side of ultrathin copper foil is preferably roughened face.I.e., a preferably face to ultrathin copper foil
It is roughened.Thereby, it is possible to improve when manufacturing copper-coated laminated board or printed substrate and the adaptation of resin bed.This is thick
Roughening processes and preferably carries out according to known coating method, and this known coating method makes fine shot copper separate out and adhere to via including
Ultrathin copper foil burns plating (け め っ I) operation and for preventing what this fine shot copper from coming off to be coated plating
At least 2 kinds of plating process of (by せ め っ I) operation.
Other functional layers can be set between peel ply and carrier foils and/or ultrathin copper foil.As other merits such
The example of ergosphere, can list auxiliary metal layer.Auxiliary metal layer preferably comprises nickel and/or cobalt.By the face side in carrier foils
And/or the face side of ultrathin copper foil forms this auxiliary metal layer, it is possible to suppression high temperature or during Long Time Thermal pressing formation carrier foils with
Contingent phase counterdiffusion between ultrathin copper foil, it is ensured that the stability of the peel strength of carrier foils.The thickness of auxiliary metal layer
It is preferably 0.001 ~ 3 μm.
As required, ultrathin copper foil can be implemented antirust treatment.Antirust treatment preferably includes to use the plating of zinc.
The plating of use zinc can be any one of zinc-plated process and galvanized alloy process, and galvanized alloy processes particularly preferred zinc-nickel
Alloy treatment.As long as zinc-nickel alloy processes comprises the plating of at least Ni and Zn, can comprise further Sn, Cr,
Other elements such as Co.Ni/Zn attachment ratio in plating zinc-nickel alloy is preferably 1.2 ~ 10, more preferably 2 ~ 7 by quality ratio,
More preferably 2.7 ~ 4.Process it addition, antirust treatment preferably further comprises chromate.This chromate processes and more preferably exists
After using the plating of zinc, carry out at the coating surface containing zinc.Thereby, it is possible to improve rust-preventing characteristic further.Particularly preferably
Antirust treatment be plating zinc-nickel alloy process with thereafter chromate process combination.
As required, silane coupler can be implemented in the surface of ultrathin copper foil and process, form silane coupling agent layer.By
This, can improve moisture-proof, chemical-resistant and the adaptation etc. with binding agent etc..Silane coupling agent layer can pass through will
Silane coupler suitably dilutes, be coated with, be dried and formed.As the example of silane coupler, 4-glycidyl fourth can be listed
Silanes's 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-aminopropan epoxide) fourth oxygen
Base) amino-functional silane such as propyl group-3-TSL 8330, N-phenyl-gamma-amino propyl trimethoxy silicane
Coupling agent；The Mercaptofunctional silane couplers such as γ mercaptopropyitrimethoxy silane；Vinyltrimethoxy silane, ethylene
The alkene functional silanes coupling agents such as base phenyltrimethoxysila,e；γ-methacryloxypropyl trimethoxy silane etc.
Acrylic functional's silane coupler；The imidazoles functional silanes coupling agents such as imidazole radicals silane；Or the triazine officials such as triazine silane
Energy property silane coupler etc..
Copper-coated laminated board
The Copper Foil of the band carrier of the present invention is preferred for making printed substrate copper-coated laminated board.That is, excellent according to the present invention
Select embodiment, it is provided that use the copper-coated laminated board that the Copper Foil of above-mentioned band carrier obtains.This copper-coated laminated board is provided with the present invention
The Copper Foil of band carrier and the ultrathin copper foil of the closely sealed Copper Foil being arranged at this band carrier on resin bed.Copper Foil with carrier
The one side of resin bed can be arranged on, it is also possible to be arranged on the two-sided of resin bed.Resin bed comprises resin, preferably comprises insulating properties
Resin.Resin bed is preferably prepreg and/or resin sheet.Prepreg refers to, makes synthetic resin be impregnated in synthetic resin board, glass
The general name of the composite in the base materials such as plate, glass fabric, glass non-woven fabric, paper.Preferred as insulative resin
Example, can list epoxy resin, cyanate ester resin, bismaleimide-triazine resin (BT resin), polyphenylene oxide resin, phenolic aldehyde tree
Fat etc..It addition, as the example of the insulative resin constituting resin sheet, epoxy resin, polyimide resin, polyester tree can be listed
The insulating resins such as fat.It addition, from improving the viewpoints such as insulating properties, can be containing each by silicon dioxide, aluminium oxide etc. in resin bed
Plant the filler grain etc. of inorganic particulate composition.The thickness of resin bed is not particularly limited, preferably 1 ~ 1000 μm, more preferably 2 ~
400 μm, more preferably 3 ~ 200 μm.Resin bed can be made up of multilamellar.The resin bed such as prepreg and/or resin sheet can be every
The bottom coating resin layer being pre-coated with in copper foil surface to be arranged on the ultrathin copper foil of band carrier.
Printed substrate
The Copper Foil of the band carrier of the present invention is preferred for making printed substrate.That is, according to the preferred embodiment of the present invention, carry
The printed substrate obtained for the Copper Foil of above-mentioned band carrier.The printed substrate of present embodiment comprises laminated resin successively
Layer and the Rotating fields of layers of copper.It addition, for resin bed, described above about copper-coated laminated board.In a word, printed substrate can
To use known Rotating fields.As relating to the concrete example of printed substrate, the single or double at prepreg can be listed and glue
Close the ultrathin copper foil of the present invention and be solidified into laminated body and then form the single or double printed substrate of circuit or by it
The multilayer printed circuit board etc. of multiple stratification.It addition, as other concrete examples, the formation present invention on resin molding can be listed
Ultrathin copper foil and form the flexible print circuit board of circuit, COF, TAB band etc..And then as other concrete examples, it is also possible to row
Enumerate: on the ultrathin copper foil of the present invention, be coated with above-mentioned resin bed form the Copper Foil (RCC) of resin, at above-mentioned printed substrate
Superimposed layer resin bed, as insulation bonding sheet material layers, then using ultrathin copper foil as whole or a part of wiring layer, uses modified form
The side such as half addition (MSAP, modified semi-additive process) method, subtractive method (subtractive method)
Method forms stacking (build up) wiring board of circuit；Ultrathin copper foil is removed, uses half addition (SAP) method to form the heap of circuit
Folded wiring board；Alternately and repeatedly carry out the Copper Foil of the resin lamination on semiconductor integrated circuit and straight on wafer that circuit is formed
Connect stacking (direct build up on wafer) wiring board etc..The Copper Foil of the band carrier of the present invention does not use so-called core base
Plate, it also may be preferable for for using the manufacture method of insulating resin layer Yu the centreless stacking of conductor layer alternative stacked.
Embodiment
Further the present invention is specifically described by example below.
Example 1 ~ 9
The making of the Copper Foil carrying out band carrier as follows and evaluation.
(1) preparation of carrier foils
Prepare 18 μ m-thick be not roughened electrolytic copper foil with antirust treatment (Mitsu Mining & Smelting Co., Ltd's system,
Class-III) as carrier foils.
(2) formation of peel ply
Containing 5CBTA and/or 4CBTA of concentration, sulfuric acid concentration 150g/L and copper concentration 10g/L shown in lower list 1
In CBTA aqueous solution, by the electrode surface side of the carrier foils through pickling processes temperature of liquid 30 DEG C (example 1 ~ 4,7 and 8) or 40 DEG C
Impregnate 30 seconds under (example 5,6 and 9), make CBTA composition be adsorbed in the electrode surface of carrier foils.Thus, on the surface of carrier foils electrode surface
Form CBTA layer as organic peel ply.Should illustrate, the composition of example 7 is equivalent to patent documentation 2 (Japanese Unexamined Patent Publication 2003-
No. 328178 publications) disclosed embodiment 3.
[table 1]
。
(3) formation of auxiliary metal layer
The carrier foils defining organic peel ply be impregnated in the solution of the nickel concentration 20g/L using nickel sulfate to make, at liquid
Temperature 45 DEG C, pH3, electric current density 5A/dm2Under conditions of, make the nickel being equivalent to the adhesion amount of thickness 0.001 μm be attached to
On machine peel ply.Thus, organic peel ply is formed nickel dam as auxiliary metal layer.
(4) formation of ultrathin copper foil
The carrier foils defining auxiliary metal layer be impregnated in the copper solution of composition shown below, at solution temperature 45 DEG C, electricity
Current density 5 ~ 30A/dm2Lower electrolysis, forms the ultrathin copper foil of thickness 3 μm in auxiliary metal layer；
<composition of solution>
Copper concentration: 65g/L
Sulfuric acid concentration: 150g/L.
(5) roughening processes
The surface of the ultrathin copper foil being consequently formed is roughened.At this roughening, reason makes fine shot copper separate out and attached
And burn plating process and for preventing the plating process that is coated that this fine shot copper comes off to constitute on ultrathin copper foil.?
Burn in plating process, use containing 18g/L copper and the acid copper sulfate solution of 100g/L sulphuric acid, at temperature of liquid 25 DEG C, electricity
Current density 10A/dm2Under be roughened.Being coated in plating process later, uses containing 65g/L copper and 150g/L
The copper solution of sulphuric acid, in temperature of liquid 45 DEG C, electric current density 15A/dm2Steady plating conditions under carry out electro-deposition.
(6) antirust treatment
It is antirust that Copper Foil two-sided of the band carrier after processing roughening includes that inorganic antirust treatment and chromate process
Process.First, as inorganic antirust treatment, use pyrophosphoric acid bath, dense at potassium pyrophosphate concentration 80g/L, zinc concentration 0.2g/L, nickel
Degree 2g/L, temperature of liquid 40 DEG C, electric current density 0.5A/dm2Under carry out zinc-nickel alloy antirust treatment.Then, at as chromate
Reason, on the basis of zinc-nickel alloy antirust treatment, forms chromate coating further.It is 1g/ that this chromate processes in chromic acid concentration
L, pH 11, solution temperature 25 DEG C, electric current density 1A/dm2Under conditions of carry out.
(7) silane coupler processes
The copper foil water washing of above-mentioned antirust treatment will be implemented, carry out silane coupler process the most at once, make silane coupler inhale
It is attached to roughening process on the antirust treatment layer in face.This silane coupler processes and carries out in the following manner: with pure water as solvent,
Using 3-TSL 8330 concentration is the solution of 3g/L, is sprayed by this solution shower nozzle ring (シ ャ ワ リ Application グ)
It is coated on roughening process face and carries out adsorption treatment.After silane coupler adsorbs, finally with electric heater, moisture is vaporized, obtains
Copper Foil with carrier.
(8) evaluation of the Copper Foil of band carrier
Copper Foil for resulting tape carrier carries out following evaluation.
<analysis of peel ply>
Carrier foils is peeled off from the Copper Foil of band carrier.By stripped carrier foils and ultrathin copper foil 40 in the hydrochloric acid of 1mol/L
Impregnate 60 minutes at DEG C, extract CBTA.Now, by the face with peel ply opposition side of carrier foils and ultrathin copper foil is sheltered,
Only the face connected with peel ply is carried out CBTA extraction.By the high performance liquid chromatography (strain of the extract containing CBTA of thus gained
Shimadzu Seisakusho Ltd. of formula commercial firm system, HPLC LC10 series) it is analyzed, measure concentration and the respective concentration of 4CBTA of 5CBTA, meter
Calculate the adhesion amount (mg/m of 5CBTA2), the adhesion amount (mg/m of 4CBTA2), the adhesion amount sum (mg/m of CBTA2) and
5CBTA/4CBTA ratio.Result is as shown in table 2.
<mensuration of peel strength>
First, the peel strength to the normality of the Copper Foil of band carrier as follows is measured.By double faced adhesive tape at band carrier
The ultrathin copper foil side of Copper Foil, is pasted and is fixed on substrate, obtains measuring sample.For this mensuration sample, according to JIS C
6481-1996 measures peel strength RS of normality when peeling off carrier foils0(gf/cm).Now, mensuration width is 50mm, measures
A length of 20mm.
Then, as follows peel strength after 1 time or 2 hot pressing is measured.Prepare the prepreg of thickness 100 μm
(Mitsubishi Gas Chemical Co., Ltd's system, GHPL830NX-A) is as resin base material.Copper at this resin base material superimposed layer band carrier
Paper tinsel, makes the ultrathin copper foil side of the Copper Foil of this band carrier abut with resin base material, carries out 1 time at pressure 2.5MPa, temperature 230 DEG C
Or the hot forming of 2 times 60 minutes, obtain the copper-coated laminated board sample after hot pressing.For copper-coated laminated board sample, according to JIS C
6481-1996, peels off carrier foils from the ultrathin copper foil being stacked on resin base material face, measures peel strength RS1(after hot pressing 1 time)
With peel strength RS2(after hot pressing 2 times) (gf/cm).Now, mensuration width is 50mm, and measured length is 20mm.After hot pressing 2 times
Peel strength RS2Peel strength RS relative to the normality before hot pressing0Ratio ((RS2-RS0)/RS0) it is multiplied by 100, calculate stripping
From intensity climbing (%).Result is as shown in table 2.
[table 2]
。
Claims (7)
1. the Copper Foil of band carrier, it is the Copper Foil of the band carrier being disposed with carrier foils, peel ply and ultrathin copper foil, wherein,
Described peel ply comprises 5-carboxyl benzotriazole (5CBTA) and/or 4-carboxyl benzotriazole (4CBTA), described peel ply
The adhesion amount of middle 5-carboxyl benzotriazole is 3.0 relative to ratio, i.e. the 5CBTA/4CBTA ratio of the adhesion amount of 4-carboxyl benzotriazole
Above.
The Copper Foil of band carrier the most according to claim 1, wherein, described 5CBTA/4CBTA ratio is 3.5 ~ 30.
The Copper Foil of band carrier the most according to claim 1 and 2, wherein, in described peel ply, to add up to 3mg/m2Above
Adhesion amount contain 5-carboxyl benzotriazole (5CBTA) and in the presence of 4-carboxyl benzotriazole (4CBTA).
The Copper Foil of band carrier the most according to any one of claim 1 to 3, wherein, in described peel ply, to add up to
80mg/m2Following adhesion amount contain 5-carboxyl benzotriazole (5CBTA) and in the presence of 4-carboxyl benzotriazole
(4CBTA)。
The Copper Foil of band carrier the most according to any one of claim 1 to 4, wherein, described peel ply and described carrier foils
And/or it is further provided with auxiliary metal layer between described ultrathin copper foil.
6. use the copper-coated laminated board that the Copper Foil of the band carrier according to any one of claim 1 to 5 obtains.
7. use the printed substrate that the Copper Foil of the band carrier according to any one of claim 1 to 6 obtains.
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 |
|---|---|
| CN106332458A true CN106332458A (en) | 2017-01-11 |
| CN106332458B 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) |
| TW (1) | TWI583268B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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
- 2016-04-27 PH PH12016000167A patent/PH12016000167A1/en unknown
- 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 |
| MY176516A (en) | 2020-08-12 |
| LU93050A1 (en) | 2017-01-25 |
| JP2017013385A (en) | 2017-01-19 |
| LU93050B1 (en) | 2017-06-08 |
| CN106332458B (en) | 2019-03-22 |
| 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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