CN102362559A - Copper foil for printed wiring board and method for producing same - Google Patents
Copper foil for printed wiring board and method for producing same Download PDFInfo
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- CN102362559A CN102362559A CN2010800134398A CN201080013439A CN102362559A CN 102362559 A CN102362559 A CN 102362559A CN 2010800134398 A CN2010800134398 A CN 2010800134398A CN 201080013439 A CN201080013439 A CN 201080013439A CN 102362559 A CN102362559 A CN 102362559A
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- copper foil
- copper
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- printed wiring
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- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- 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
- B32B15/16—Layered products comprising a layer of metal next to a particulate layer
-
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
-
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
-
- 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
- C25D7/12—Semiconductors
-
- 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
- H05K2203/03—Metal processing
- H05K2203/0307—Providing micro- or nanometer scale roughness on a metal surface, e.g. by plating of nodules or dendrites
-
- 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
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0723—Electroplating, e.g. finish plating
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Electroplating Methods And Accessories (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Laminated Bodies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Disclosed is a copper foil for a printed wiring board, which is characterized by comprising, on at least one surface thereof, a roughened layer that is composed of needle-like fine roughening particles each having a diameter of 0.1-2.0 [mu]m and an aspect ratio of not less than 1.5. Also disclosed is a method for producing a copper foil for a printed wiring board, which is characterized in that a roughened layer that is composed of needle-like fine roughening particles each having a diameter of 0.1-2.0 [mu]m and an aspect ratio of not less than 1.5 is formed on at least one surface of a copper foil, using an electrolytic bath that is composed of sulfuric acid/copper sulfate and contains at least one substance selected from among an alkyl sulfate salt, tungsten ions and arsenic ions. Consequently, a copper foil for a semiconductor package substrate, which is capable of preventing circuit erosion without deteriorating the other characteristics of the copper foil, can be obtained. In particular, a copper foil for a printed wiring board, which has an improved roughened layer and is thus increased in adhesion strength to a resin, can be obtained. The method for producing a copper foil for a printed wiring board enables the production of such a copper foil.
Description
Technical field
The present invention relates to good printed wiring board-use copper-clad of chemical-resistant and adhesivity and manufacturing approach thereof.Especially; The present invention provides and can the chemical treatments when forming fine pattern obtain high-peeling strength for the base plate for packaging that with BT (BMI-triazine) resin impregnation base material is representative, and can carry out meticulous etched Copper Foil and manufacturing approach thereof.In addition, the present invention is provided at the printed wiring board-use copper-clad and the manufacturing approach thereof that can significantly improve peel strength in the method through electroless plating formation copper pattern behind the whole facet etch of Copper Foil.
Background technology
Conductor package substrate is used Copper Foil, is commonly referred to as printed wiring board-use copper-clad, makes through following operation usually.At first, under HTHP, be glued on the base materials such as synthetic resin Copper Foil is range upon range of.Then, in order on substrate, to form the target electroconductive circuit, utilize material such as elching resistant resin on Copper Foil, print and the equal circuit of circuit.
And the part that do not need of the Copper Foil that will expose through etch processes is removed.After the etching, remove the Printing Department that forms by materials such as resins, on substrate, form electroconductive circuit.Element is stipulated in welding on the electroconductive circuit that forms at last, thereby forms the various printed circuit board (PCB)s of used for electronic device.At last, with etchant resist (レ ジ ス ト) or folded increase (PVC Le De ァ ッ プ) resin substrate and engage.Generally speaking, to the quality requirements of printed wiring board-use copper-clad, be different for gluing surface gluing (so-called matsurface) and non-gluing surface (so-called glassy surface) with resin base material, the two is satisfied simultaneously.
As the requirement to gloss, following requirement is arranged: the good and No oxidation discoloration when preserving of (1) outward appearance, (2) solder wettability are good, No oxidation discoloration during (3) heat, (4) are good with the adaptation of etchant resist; Deng.
On the other hand; For matsurface, major requirement: No oxidation discoloration when preserve (1), (2) are even also be fully after heat, wet processed, welding, the chemical treatments etc., do not producing so-called range upon range of stain after (3), etching range upon range of with base material with the peel strength of base material; Deng.
In addition, follow becoming more meticulous of pattern in recent years, require the low profileization (ロ one プ ロ Off ァ ィ Leization) of Copper Foil.This need increase the peel strength of Copper Foil matsurface.
In addition, in electronic equipments such as PC or mobile communication, follow high speed, the high capacity of communication, advancing the high frequencyization of the signal of telecommunication, thereby requirement can corresponding with it printed wiring board and Copper Foil.The frequency of the signal of telecommunication reaches 1GHz when above, and the influence of the kelvin effect that electric current only flows at conductive surface becomes significantly, thereby can not ignore because the concavo-convex influence that causes current delivery route change impedance increase on surface.Consider from this point, hope that the surface roughness of Copper Foil is little.
In order to tackle such requirement, many processing methods have been proposed printed wiring board-use copper-clad.
Generally speaking, in the processing method of printed wiring board-use copper-clad, use rolled copper foil or electrolytic copper foil, at first the adhesive tension (peel strength) in order to improve Copper Foil and resin carries out to copper foil surface the roughened that comprises copper and cupric oxide particulate being provided usually.Then, heat-resisting in order to have/rust-preventing characteristic, the heat-resisting processing layer (barrier layer) of formation brass or zinc etc.
And, for prevent in transit or preserve in produce surface oxidation etc., handle or electrolysis chromium-antirust processing such as zinc processing through implementing dipping or electrolytic chromate above that, and obtain goods.
Wherein, roughened layer is particularly born the important function of the adhesive tension (peel strength) that improves Copper Foil and resin.Thought in the past that for this roughened, (spherical) thrust with circularity (ball body ぁ Ru) was better.This thrust with circularity is grown through the inhibition dendritic crystalline and is realized.But this thrust with circularity is peeled off when etching, produces the phenomenon that is called " powder falls ".This phenomenon can be described as natural.This be because: the contact area of bulbous protrusion thing and Copper Foil is much smaller than the diameter of (spherical) thrust with circularity.
For fear of this " powder falls " phenomenon, after above-mentioned roughened, on thrust, form thin copper coating, to prevent peel off (the referenced patent document 1) of thrust.This technology has the effect that prevents " powder falls ", but exists operation to increase and prevent the copper facing different problems of effect because of approaching of " powder falls ".
In addition, the tectal technology of nodosity (patent documentation 2) of the needle-like that constitutes of the known alloy that on Copper Foil, forms by copper and mickel.This nodosity cover layer is a needle-like; Therefore think and compare with said patent documentation 1 disclosed (spherical) thrust with circularity; Increase with the adhesive strength of resin; But its be composition with as the different copper-nickel alloy of the Copper Foil of base material, when the etching that is used to form copper circuit, have different etching rates.Therefore, there is the problem that is not suitable for carrying out stable circuit design.
When forming printed wiring board-use copper-clad, form heat-resisting/antirust processing layer usually.As the example of the metal or alloy that is used to form heat-resisting processing layer, the tectal multiple Copper Foil that is formed with Zn, Cu-Ni, Cu-Co and Cu-Zn etc. has been realized practical application (for example, the referenced patent document 3).
Wherein, The Copper Foil that is formed with the heat-resisting processing layer that is made up of Cu-Zn (brass) extensively is used in industry; This is because it has following good characteristic: the stain that does not have resin bed in the time of on being laminated to the printed circuit board (PCB) that is made up of epoxy resin etc.; And the deterioration of peel strength is few after the heat, etc.
About forming the method for this heat-resisting processing layer that constitutes by brass, in patent documentation 4 and patent documentation 5, write up is arranged.
Next this Copper Foil that is formed with the heat-resisting processing layer that is made up of brass carries out etch processes in order to form printed circuit.Recently, in the formation of printed circuit, using hydrochloric acid just more and more is etching solution.
But using hydrochloric acid is etching solution (for example, CuCl
2, FeCl
3Deng) printed circuit board (PCB) that use is formed with the Copper Foil of the heat-resisting processing layer that is made up of brass carries out etch processes; And when not the needing part of the Copper Foil except that removing the printed circuit part and formation electroconductive circuit; Can cause erosion (circuit erosion) phenomenon of so-called circuit end (edge part) in the both sides of circuit pattern, thus the problem of the peel strength deterioration of generation and resin base material.
This circuit erosion; Be meant: from the gluing boundary layer of the Copper Foil of the circuit that forms through above-mentioned etch processes and resin base material, promptly constitute the etching side that heat-resisting/antirust processing layer exposes by brass; Corroded by said etching solution; And because washing afterwards is insufficient, and the feasible both sides that present yellow (because being made up of brass) usually are etched and present redness, and the phenomenon of the remarkable deterioration of peel strength of this part.And if this phenomenon produces on the entire circuit pattern, then circuit pattern can be peeled off from base material, thereby causes problem.
The technology that proposes in view of such problem is: carry out the antirust processing and chromate processing of roughened, zinc or kirsite on the surface of Copper Foil after, the silane coupler that absorption contains the small additions of chromium ion on the surface after chromate is handled is to improve salt tolerant acid (referenced patent document 7).
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 8-236930 communique
Patent documentation 2: No. 3459964 communique of Japan Patent
Patent documentation 3: the special public clear 51-35711 communique of Japan
Patent documentation 4: the special public clear 54-6701 communique of Japan
Patent documentation 5: No. 3306404 communique of Japan Patent
Patent documentation 6: Japan special hope 2002-170827 communique
Patent documentation 7: japanese kokai publication hei 3-122298 communique
Summary of the invention
Problem of the present invention is: the conductor package substrate of developing the circuit erosion of under the situation of all other deterioration in characteristics that do not make Copper Foil, avoiding above-mentioned is used Copper Foil.Problem of the present invention particularly in: the roughened that can improve Copper Foil layer is provided, and can improves the printed wiring board-use copper-clad and the manufacturing approach thereof of the adhesive strength of Copper Foil and resin.
In order to solve above-mentioned problem, the inventor has carried out research extensively and profoundly, and the result provides following printed wiring board-use copper-clad and manufacturing approach thereof.
1) a kind of printed wiring board-use copper-clad is characterized in that, at least one face of Copper Foil, has the roughened layer, and it is that 0.1～2.0 μ m and aspect ratio are the fine copper coarse particles of the needle-like more than 1.5 that said roughened layer comprises diameter.
2) a kind of printed wiring board-use copper-clad is characterized in that, at least one face of Copper Foil, has the roughened layer, and it is that 0.1～2.0 μ m and aspect ratio are the fine copper coarse particles of the needle-like more than 3.0 that said roughened layer comprises diameter.
3) as above-mentioned 1) or 2) described printed wiring board-use copper-clad, it is characterized in that the quantity of needle-like coarse particles is in the circuit width of 10 μ m, to exist more than 5.
4) as above-mentioned 1) or 2) described printed wiring board-use copper-clad, it is characterized in that the quantity of needle-like coarse particles is in the circuit width of 10 μ m, to exist more than 10.
5) each described printed wiring board-use copper-clad above-mentioned 1)～4); It is characterized in that; On said roughened layer, has the heat-resisting/antirust coat that contains at least a above element that is selected from zinc, nickel, copper, phosphorus; On this heat-resisting/antirust coat, have chromate, and have silane coupling agent layer on by rete at this chromate by rete.
6) a kind of manufacturing approach of printed wiring board-use copper-clad; It is characterized in that; Use contains at least a above material that is selected from alkyl sodium sulfate ester salt, tungsten ion, arsenic ion and the electrobath that comprises sulfuric acid/copper sulphate; On at least one face of Copper Foil, form the roughened layer, it is that 0.1～2.0 μ m and aspect ratio are the fine copper coarse particles of the needle-like more than 1.5 that said roughened layer comprises diameter.
7) as above-mentioned 6) manufacturing approach of described printed wiring board-use copper-clad; It is characterized in that; On said roughened layer, form the heat-resisting/antirust coat that contains at least a above element that is selected from zinc, nickel, copper, phosphorus; On this heat-resisting/antirust coat, form chromate then by rete, form silane coupling agent layer at this chromate on by rete again.
The invention effect
As implied above, in the printed wiring board-use copper-clad of the present invention, be not that (spherical) thrust with circularity that is used for roughened was preferably thought in formation in the past, but at least one face of Copper Foil, form the fine coarse particles of needle-like.Thus; Has following remarkable result: the adhesive strength that can improve Copper Foil self and resin can be provided; For base plate for packaging,, and can carry out meticulous etched Copper Foil and manufacturing approach thereof even the chemical treatments when forming fine pattern also can improve peel strength.
In recent years in the fine patterning and high frequency propelling of printed circuit, the present invention pastes with Copper Foil and semiconductor-sealing-purpose resin and the semiconductor-sealing-purpose substrate made is extremely effective as copper foil for printed circuit (conductor package substrate is used Copper Foil) and with conductor package substrate.
Description of drawings
Fig. 1 is the SEM photo of the roughened layer of embodiment 1.
Fig. 2 is the SEM photo of the roughened layer of embodiment 2.
Fig. 3 is the SEM photo of the roughened layer of embodiment 3.
Fig. 4 is the SEM photo of embodiment 4.
Fig. 5 is the SEM photo of the roughened layer of embodiment 5.
Fig. 6 is the SEM photo of embodiment 6.
Fig. 7 is the SEM photo of the roughened layer of embodiment 7.
Fig. 8 is the SEM photo of the roughened layer of comparative example 1.
Fig. 9 is the SEM photo of the roughened layer of comparative example 2.
Embodiment
Below, in order to understand the present invention easily, the present invention is carried out concrete, detailed explanation.The Copper Foil that uses among the present invention can be in electrolytic copper foil or the rolled copper foil any one.
As stated, in the printed wiring board-use copper-clad of the present invention, be not that (spherical) thrust with circularity that is used for roughened was preferably thought in formation in the past, but at least one face of Copper Foil, form the fine copper coarse particles of needle-like.Its shape is that diameter is 0.1～2.0 μ m and vertical (length) and the ratio of horizontal (diameter) is the roughened layer more than 1.5.
Further, expect for diameter 0.1～2.0 μ m and aspect ratio to be the fine copper coarse particles, promptly microscler of the needle-like more than 3.0.
The shape of this copper coarse particles roughly has the shape of scouring rush (っ く), as after shown in the microphotograph stated, majority has convexity up.Minimum diameter is about 1: 1～about 1: 1.2 with the ratio of maximum gauge.This is than the principal element for adhesive tension is further improved, if the spicule of said numerical value then can be realized the purpose that the application invents fully.
In addition; In the fine copper coarse particles of this needle-like; The ratio that departs from diameter and be 0.1～2.0 μ m and vertical (length) and horizontal (diameter) is that the particle of the numerical value 1.5 or more, the particle that for example length is lacked, the situation with particle of dissimilar shape are not exist; If but its amount then can not impact the adhesive strength of Copper Foil self and resin in all 5%.
When forming circuit, expect that the quantity of said copper needle-like coarse particles exists more than 5 in the circuit width of 10 μ m through etch printing wiring board-use copper-clad.Thus, can significantly improve the adhesive strength of Copper Foil and resin.Especially, the quantity of expectation copper needle-like coarse particles exists more than 10 in the circuit width of 10 μ m.
The roughened layer that comprises the fine copper coarse particles of needle-like can use the electrobath that contains at least a above material that is selected from alkyl sodium sulfate ester salt, tungsten ion, arsenic ion and comprise sulfuric acid/copper sulphate to make.
In order to prevent the falling stop powder and improve peel strength that the roughened layer that expectation comprises the fine copper coarse particles of needle-like carries out the clad type plating with the electrobath that comprises sulfuric acid/copper sulphate.
Concrete treatment conditions are described below.
(liquid forms 1)
CuSO
4·5H
2O：39.3～118g/L
Cu：10～30g/L
H
2SO
4：10～150g/L
Na
2WO
4·2H
2O：0～90mg/L
W：0～50mg/L
Lauryl sodium sulfate: 0～50mg
H
3AsO
3(60% aqueous solution): 0～6315mg/L
As：0～2000mg/L
(plating condition 1)
Temperature: 30～70 ℃
(current condition 1)
Current density: 25～110A/dm
2
Roughening coulomb amount: 50～500As/dm
2
The plating time: 0.5～20 second
(liquid forms 2)
CuSO
4·5H
2O：78～314g/L
Cu：20～80g/L
H
2SO
4：50～200g/L
(plating condition 2)
Temperature: 30～70 ℃
(current condition 2)
Current density: 5～50A/dm
2
Roughening coulomb amount: 50～300As/dm
2
The plating time: 1～60 second
In addition; On above-mentioned roughened layer, further form the heat-resisting/antirust coat that contains at least a above element that is selected from zinc, nickel, copper, phosphorus; On this heat-resisting/antirust coat, further form chromate by rete; And formed silane coupling agent layer by an enterprising step of rete, thereby can obtain printed wiring board-use copper-clad at this chromate.
As heat-resisting/antirust coat, not special restriction can be used heat-resisting/antirust coat in the past.For example, can use the brass cover layer that in the past conductor package substrate was used with Copper Foil.
In addition, on this heat-resisting/antirust coat, form chromate by rete and silane coupling agent layer, thus obtain Copper Foil at least with the gluing surface of resin.To have range upon range of being glued on the resin of tectal Copper Foil that is constituted by rete and silane coupling agent layer by these chromate; On this Copper Foil, form the printed circuit of elching resistant again; Then through the Copper Foil of etching except that removing the printed circuit part do not need part, form electroconductive circuit thus.
As heat-resisting/antirust coat, can use existing processing, particularly, for example can use following processing.
(liquid composition)
NaOH：40～200g/L
NaCN：70～250g/L
CuCN：50～200g/L
Zn(CN)
2：2～100g/L
As
2O
3：0.01～1g/L
(liquid temperature)
40～90℃
(current condition)
Current density: 1～50A/dm
2
The plating time: 1～20 second
Said chromate by rete can use electrolytic chromate by rete or the dipping chromate by rete.Expect that this chromate is 25-150 μ g/dm by the Cr of rete amount
2
The Cr amount is lower than 25 μ g/dm
2The time, no antirust coat effect.In addition, the Cr amount surpasses 150 μ g/dm
2The time, effect is saturated so cause waste.Therefore, the Cr amount preferably is adjusted to 25-150 μ g/dm
2
Below enumerate and be used to form said chromate by the example of the condition of rete.But, as previously mentioned, be not necessarily limited to this condition, can use known any one chromate to handle.This antirust processing is one of acid proof factor of influence, handles through chromate and further improves acid resistance.
(a) the dipping chromate is handled
K
2Cr
2O
7: 1～5g/L, pH:2.5～4.5, temperature: 40～60 ℃, time: 0.5～8 second
(b) electrolytic chromate is handled (chromium-zinc is handled (alkaline bath))
K
2Cr
2O
7: 0.2～20g/L, acid: phosphoric acid, sulfuric acid, organic acid, pH:1.0～3.5, temperature: 20～40 ℃, current density: 0.1～5A/dm
2, the time: 0.5～8 second
(c) electrolysis chromium-zinc is handled (alkaline bath)
K
2Cr
2O
7(Na
2Cr
2O
7Or CrO
3) 2～10g/L, NaOH or KOH:10～50g/L, ZnOH or ZnSO
47H
2O:0.05～10g/L, pH:7～13, bath temperature: 20～80 ℃, current density: 0.05～5A/dm
2, the time: 5～30 seconds
(d) electrolytic chromate is handled (chromium-zinc is handled (acid bath))
K
2Cr
2O
7: 2～10g/L, Zn:0～0.5g/L, Na
2SO
4: 5～20g/L, pH:3.5～5.0, bath temperature: 20～40 ℃, current density: 0.1～3.0A/dm
2, the time: 1～30 second
With the silane coupling agent layer that uses in the Copper Foil, can use the silane coupler that in Copper Foil, uses usually as conductor package substrate of the present invention, not special restriction.For example, the actual conditions of silane treatment is described below.
0.2% epoxy radicals silicone hydride/0.4%TEOS, PH5
Also can use and contain tetraalkoxysilane and possess more than one the silane coupler that has with the alkoxy silane of reactive functional group of resin.Much less, the selection of this silane coupling agent layer also is arbitrarily, but expectation is being considered to select with the adhesivity of resin.
Embodiment
Below, embodiment and comparative example are described.In addition, what present embodiment was enumerated is a preferred example, therefore the invention is not restricted to these embodiment.Therefore, the distortion that comprises in the technological thought of the present invention, other embodiment or mode all comprise in the present invention.
In addition, in order to compare, comparative example is provided with the present invention.
(embodiment 1)
The electrolytic copper foil of used thickness 12 μ m is at matsurface (the delustring face: carry out roughening plating as follows the M face) of this Copper Foil.Treatment conditions below are shown.
(liquid forms 1)
CuSO
4·5H
2O：58.9g/L
Cu：15g/L
H
2SO
4：100g/L
As addition: 1000ppm: use H
3AsO
3(60% aqueous solution)
(electroplating temperature 1) 50 ℃
(current condition 1)
Current density: 90A/dm
2
Roughening coulomb amount: 200As/dm
2
After this roughened, carry out normal plating as follows.Treatment conditions below are shown.
(liquid forms 2)
CuSO
4·5H
2O：156g/L
Cu：40g/L
H
2SO
4：100g/L
(electroplating temperature 1) 40 ℃
(current condition 1)
Current density: 30A/dm
2
Roughening coulomb amount: 150As/dm
2
The SEM photo of the roughened layer of embodiment 1 is as shown in Figure 1.The multiple of the SEM photo in the left side shown in Fig. 1 is that the multiple of the SEM photo on (* 3000), right side is (* 30000).Shown in Figure 1 like this, can find out the shape of particle that forms needle-like.Average particle diameter is that 0.57 μ m, particle length are that 1.56 μ m, aspect ratio are 2.7, satisfies the condition of the application's invention.
Then, on the roughened face of above-mentioned copper, form heat-resisting/antirust coat.Its condition can be used known heat-resisting/antirust coat, and present embodiment is implemented under following condition.
(liquid composition)
NaOH：72g/L
NaCN：112g/L
CuCN：91.6g/L(Cu：65g/L)
Zn(CN)
2：8.1g/L(Zn：4.5g/L)
As
2O
3：0.125g/L(As：95ppm)
(liquid temperature) 76.5 ℃
(current condition)
Current density: 6.7A/dm
2
Electric current: 4.0A
The plating time: 5 seconds
Then, on heat-resisting/antirust coat, carrying out electrolytic chromate handles.
Electrolytic chromate is handled (chromium-zinc is handled (acid bath))
Cr
2O
3：0.73g/L
ZnSO
4·7H
2O：2.46g/L
Na
2SO
4：18g/L
H
3PO
3：0.53g/L
PH:4.6, bath temperature: 37 ℃
Current density: 2.06A/dm
2
Time: 1～30 second
(pH regulates through sulfuric acid or potassium hydroxide and implements)
Then, implement silane treatment (carrying out) at this chromate on by rete through coating.
The condition of silane treatment is described below.
0.2% epoxy radicals silicone hydride/0.4%TEOS, PH5
Such copper foil manufactured laminated stickiness to glass cloth base material BT (BMI-triazine) resin plate, is measured or analyzed following project.
(1) the fall observation of powder
Do not observe powder.The result is as shown in table 1.
(2) normality peel strength
The normality peel strength is 0.79kg/cm, has good peel strength.The result is as shown in table 1.
(3) salt tolerant Suan Shi test
Acid for salt tolerant, on the 0.4mm circuit, use 12 weight % hydrochloric acid, will represent with % in loss (Loss) amount of 60 ℃ of dippings after 90 minutes.Below same.Loss (Loss) amount is 5%, loss (Loss) amount than after the comparative example stated lack the demonstration good properties.The result is as shown in table 1.
(4) result of the test of anti-dioxysulfate water-based (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ℃)
On the 0.4mm circuit, implement.At this moment, examine or check for the situation of etching 2 μ m.Loss (Loss) amount is represented with %.Below same.The result is as shown in table 1.
Can find out obviously that from table 1 the Loss amount is low to moderate 6.6%, anti-dioxysulfate water-based is good.
(embodiment 2)
The electrolytic copper foil of used thickness 12 μ m is at the matsurface of this Copper Foil (delustring face: the M face) go up and implement roughening plating as follows and the normal plating same with embodiment 1.Roughening plating treatment conditions below are shown.
(liquid forms 1)
CuSO
4·5H
2O：58.9g/L
Cu：15g/L
H
2SO
4：100g/L
Na
2WO
4·2H
2O：5.4mg/L
W addition: 3ppm
(electroplating temperature 1) 50 ℃
(current condition 1)
Current density: 40A/dm
2
Roughening coulomb amount: 300As/dm
2
The SEM photo of the roughened layer of embodiment 2 is as shown in Figure 2.The multiple of the SEM photo in the left side shown in Fig. 2 is that the multiple of the SEM photo on (* 3000), right side is (* 30000).Shown in Figure 2 like this, can find out the shape of particle that forms needle-like.Average particle diameter is that 0.67 μ m, particle length are that 1.78 μ m, aspect ratio are 2.7, satisfies the condition of the application's invention.
Then, on the roughened face of above-mentioned copper, form the heat-resisting/antirust coat same, on this heat-resisting/antirust coat, carry out electrolytic chromate and handle, implement silane treatment (carrying out) at this chromate on by rete again through coating with embodiment 1.
Such copper foil manufactured laminated stickiness to glass cloth base material BT (BMI-triazine) resin plate, is measured or analyzed following project.
(1) the fall observation of powder
Do not observe powder.The result is as shown in table 1.
(2) normality peel strength
The normality peel strength is 0.83kg/cm, has good peel strength.The result is as shown in table 1.
(3) salt tolerant Suan Shi test
Acid for salt tolerant, on the 0.4mm circuit, use 12 weight % hydrochloric acid, will represent with % in loss (Loss) amount of 60 ℃ of dippings after 90 minutes.Below same.Loss (Loss) amount is 2.3%, loss (Loss) amount than after the comparative example stated lack the demonstration good properties.The result is as shown in table 1.
(4) result of the test of anti-dioxysulfate water-based (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ℃)
On the 0.4mm circuit, implement.At this moment, the situation of etching 2 μ m is examined or check.Loss (Loss) amount is represented with %.Below same.The result is as shown in table 1.
Can find out obviously that from table 1 the Loss amount is low to moderate 4.4%, anti-dioxysulfate water-based is good.
(embodiment 3)
The electrolytic copper foil of used thickness 12 μ m is at the matsurface of this Copper Foil (delustring face: carry out roughening plating as follows and the normal plating same with embodiment 1 the M face).Roughening plating treatment conditions below are shown.
(liquid forms 1)
CuSO
4·5H
2O：58.9g/L
Cu：15g/L
H
2SO
4：100g/L
Lauryl sodium sulfate addition: 10ppm
(electroplating temperature 1) 50 ℃
(current condition 1)
Current density: 100A/dm
2
Roughening coulomb amount: 200As/dm
2
The SEM photo of the roughened layer of embodiment 3 is as shown in Figure 3.The multiple of the SEM photo in the left side shown in Fig. 3 is that the multiple of the SEM photo on (* 3000), right side is (* 30000).Shown in Figure 3 like this, though can find out slightly, keep the shape of particle of needle-like near spherical.Average particle diameter is that 0.6 μ m, particle length are that 1.5 μ m, aspect ratio are 2.5, satisfies the condition of the application's invention.
Then, on the roughened face of above-mentioned copper, form the heat-resisting/antirust coat same, on this heat-resisting/antirust coat, carry out electrolytic chromate and handle, implement silane treatment (carrying out) at this chromate on by rete again through coating with embodiment 1.
Such copper foil manufactured laminated stickiness to glass cloth base material BT (BMI-triazine) resin plate, is measured or analyzed following project.
(1) the fall observation of powder
Do not observe powder.The result is as shown in table 1.
(2) normality peel strength
The normality peel strength is 0.75kg/cm, has good peel strength.The result is as shown in table 1.
(3) salt tolerant Suan Shi test
Acid for salt tolerant, on the 0.4mm circuit, use 12 weight % hydrochloric acid, will represent with % in loss (Loss) amount of 60 ℃ of dippings after 90 minutes.Below same.Loss (Loss) amount is 7.8%, loss (Loss) amount than after the comparative example stated lack the demonstration good properties.The result is as shown in table 1.
(4) result of the test of anti-dioxysulfate water-based (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ℃)
On the 0.4mm circuit, implement.At this moment, the situation of etching 2 μ m is examined or check.Loss (Loss) amount is represented with %.Below same.The result is as shown in table 1.
Can find out obviously that from table 1 the Loss amount is low to moderate 8.7%, anti-dioxysulfate water-based is good.
(embodiment 4)
The electrolytic copper foil of used thickness 12 μ m is at the matsurface of this Copper Foil (delustring face: carry out roughening plating as follows and the normal plating same with embodiment 1 the M face).Roughening plating treatment conditions below are shown.
(liquid forms 1)
CuSO
4·5H
2O：58.9g/L
Cu：15g/L
H
2SO
4：100g/L
Na
2WO
4·2H
2O：5.4mg/L
W：3ppm
As:150ppm (uses H
3AsO
3(60% aqueous solution))
(electroplating temperature 1) 50 ℃
(current condition 1)
Current density: 90A/dm
2
Roughening coulomb amount: 200As/dm
2
The SEM photo of the roughened layer of embodiment 4 is as shown in Figure 4.The multiple of the SEM photo in the left side shown in Fig. 4 is that the multiple of the SEM photo on (* 3000), right side is (* 30000).Shown in Figure 4 like this, can find out the shape of particle that forms needle-like.Average particle diameter is that 0.59 μ m, particle length are that 1.9 μ m, aspect ratio are 3.2, satisfies the condition of the application's invention.
Then, on the roughened face of above-mentioned copper, form the heat-resisting/antirust coat same, on this heat-resisting/antirust coat, carry out electrolytic chromate and handle, implement silane treatment (carrying out) at this chromate on by rete again through coating with embodiment 1.
Such copper foil manufactured laminated stickiness to glass cloth base material BT (BMI-triazine) resin plate, is measured or analyzed following project.
(1) the fall observation of powder
Do not observe powder.The result is as shown in table 1.
(2) normality peel strength
The normality peel strength is 0.82kg/cm, has good peel strength.The result is as shown in table 1.
(3) salt tolerant Suan Shi test
Acid for salt tolerant, on the 0.4mm circuit, use 12 weight % hydrochloric acid, will represent with % in loss (Loss) amount of 60 ℃ of dippings after 90 minutes.Below same.Loss (Loss) amount is 4.3%, loss (Loss) amount than after the comparative example stated lack the demonstration good properties.The result is as shown in table 1.
(4) result of the test of anti-dioxysulfate water-based (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ℃)
On the 0.4mm circuit, implement.At this moment, the situation of etching 2 μ m is examined or check.Loss (Loss) amount is represented with %.Below same.The result is as shown in table 1.
Can find out obviously that from table 1 the Loss amount is low to moderate 6.8%, anti-dioxysulfate water-based is good.
(embodiment 5)
The electrolytic copper foil of used thickness 12 μ m is at the matsurface of this Copper Foil (delustring face: carry out roughening plating as follows and the normal plating same with embodiment 1 the M face).Roughening plating treatment conditions below are shown.
(liquid composition)
CuSO
4·5H
2O：58.9g/L
Cu：15g/L
H
2SO
4：100g/L
Lauryl sodium sulfate addition: 10ppm
As addition: 1000ppm: use H
3AsO
3(60% aqueous solution)
(electroplating temperature) 50 ℃
(current condition)
Current density: 40A/dm
2
Roughening coulomb amount: 240As/dm
2
The SEM photo of the roughened layer of embodiment 5 is as shown in Figure 5.The multiple of the SEM photo in the left side shown in Fig. 5 is that the multiple of the SEM photo on (* 3000), right side is (* 30000).Shown in Figure 5 like this, can find out the shape of particle that forms needle-like.Average particle diameter is that 0.72 μ m, particle length are that 1.93 μ m, aspect ratio are 2.7, satisfies the condition of the application's invention.
Then, on the roughened face of above-mentioned copper, form the heat-resisting/antirust coat same, on this heat-resisting/antirust coat, carry out electrolytic chromate and handle, implement silane treatment (carrying out) at this chromate on by rete again through coating with embodiment 1.
Such copper foil manufactured laminated stickiness to glass cloth base material BT (BMI-triazine) resin plate, is measured or analyzed following project.
(1) the fall observation of powder
Do not observe powder.The result is as shown in table 1.
(2) normality peel strength
The normality peel strength is 0.83kg/cm, has good peel strength.The result is as shown in table 1.
(3) salt tolerant Suan Shi test
Acid for salt tolerant, on the 0.4mm circuit, use 12 weight % hydrochloric acid, will represent with % in loss (Loss) amount of 60 ℃ of dippings after 90 minutes.Below same.Loss (Loss) amount is 4.6%, loss (Loss) amount than after the comparative example stated lack the demonstration good properties.The result is as shown in table 1.
(4) result of the test of anti-dioxysulfate water-based (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ℃)
On the 0.4mm circuit, implement.At this moment, the situation of etching 2 μ m is examined or check.Loss (Loss) amount is represented with %.Below same.The result is as shown in table 1.
Can find out obviously that from table 1 the Loss amount is low to moderate 7.5%, anti-dioxysulfate water-based is good.
(embodiment 6)
The electrolytic copper foil of used thickness 12 μ m is at the matsurface of this Copper Foil (delustring face: carry out roughening plating as follows and the normal plating same with embodiment 1 the M face).Roughening plating treatment conditions below are shown.
(liquid forms 1)
CuSO
4·5H
2O：58.9g/L
Cu：15g/L
H
2SO
4：100g/L
Na
2WO
4·2H
2O：5.4mg/L
W：3ppm
Lauryl sodium sulfate addition: 10ppm
(electroplating temperature 1) 50 ℃
(current condition 1)
Current density: 100A/dm
2
Roughening coulomb amount: 200As/dm
2
The SEM photo of the roughened layer of embodiment 6 is as shown in Figure 6.The multiple of the SEM photo in the left side shown in Fig. 6 is that the multiple of the SEM photo on (* 3000), right side is (* 30000).Shown in Figure 6 like this, can find out the shape of particle that forms needle-like.Average particle diameter is that 0.48 μ m, particle length are that 1.6 μ m, aspect ratio are 3.3, satisfies the condition of the application's invention.
Then, on the roughened face of above-mentioned copper, form the heat-resisting/antirust coat same, on this heat-resisting/antirust coat, carry out electrolytic chromate and handle, implement silane treatment (carrying out) at this chromate on by rete again through coating with embodiment 1.
Such copper foil manufactured laminated stickiness to glass cloth base material BT (BMI-triazine) resin plate, is measured or analyzed following project.
(1) the fall observation of powder
Do not observe powder.The result is as shown in table 1.
(2) normality peel strength
The normality peel strength is 0.83kg/cm, has good peel strength.The result is as shown in table 1.
(3) salt tolerant Suan Shi test
Acid for salt tolerant, on the 0.4mm circuit, use 12 weight % hydrochloric acid, will represent with % in loss (Loss) amount of 60 ℃ of dippings after 90 minutes.Below same.Loss (Loss) amount is 3.9%, loss (Loss) amount than after the comparative example stated lack the demonstration good properties.The result is as shown in table 1.
(4) result of the test of anti-dioxysulfate water-based (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ℃)
On the 0.4mm circuit, implement.At this moment, the situation of etching 2 μ m is examined or check.Loss (Loss) amount is represented with %.Below same.The result is as shown in table 1.
Can find out obviously that from table 1 the Loss amount is low to moderate 5.2%, anti-dioxysulfate water-based is good.
(embodiment 7)
The electrolytic copper foil of used thickness 12 μ m is at the matsurface of this Copper Foil (delustring face: carry out roughening plating as follows and the normal plating same with embodiment 1 the M face).Roughening plating treatment conditions below are shown.
(liquid forms 1)
CuSO
4·5H
2O：58.9g/L
Cu：15g/L
H
2SO
4：100g/L
Na
2WO
4·2H
2O：5.4mg/L
W：3ppm
Lauryl sodium sulfate addition: 10ppm
As addition: 150ppm: use H
3AsO
3(60% aqueous solution)
(electroplating temperature 1) 50 ℃
(current condition 1)
Current density: 80A/dm
2
Roughening coulomb amount: 280As/dm
2
The SEM photo of the roughened layer of embodiment 7 is as shown in Figure 7.The multiple of the SEM photo in the left side shown in Fig. 7 is that the multiple of the SEM photo on (* 3000), right side is (* 30000).Shown in Figure 7 like this, can find out the shape of particle that forms needle-like.Average particle diameter is that 0.55 μ m, particle length are that 1.7 μ m, aspect ratio are 3.1, satisfies the condition of the application's invention.
Then, on the roughened face of above-mentioned copper, form the heat-resisting/antirust coat same, on this heat-resisting/antirust coat, carry out electrolytic chromate and handle, implement silane treatment (carrying out) at this chromate on by rete again through coating with embodiment 1.
Such copper foil manufactured laminated stickiness to glass cloth base material BT (BMI-triazine) resin plate, is measured or analyzed following project.
(1) the fall observation of powder
Do not observe powder.The result is as shown in table 1.
(2) normality peel strength
The normality peel strength is 0.85kg/cm, has good peel strength.The result is as shown in table 1.
(3) salt tolerant Suan Shi test
Acid for salt tolerant, on the 0.4mm circuit, use 12 weight % hydrochloric acid, will represent with % in loss (Loss) amount of 60 ℃ of dippings after 90 minutes.Below same.Loss (Loss) amount is 1.6%, loss (Loss) amount than after the comparative example stated lack the demonstration good properties.The result is as shown in table 1.
(4) result of the test of anti-dioxysulfate water-based (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ℃)
On the 0.4mm circuit, implement.At this moment, the situation of etching 2 μ m is examined or check.Loss (Loss) amount is represented with %.Below same.The result is as shown in table 1.
Can find out obviously that from table 1 the Loss amount is low to moderate 4.5%, anti-dioxysulfate water-based is good.
(comparative example 1)
The electrolytic copper foil of used thickness 12 μ m is at the matsurface of this Copper Foil (delustring face: carry out roughening plating as follows and the normal plating same with embodiment 1 the M face).Roughening plating treatment conditions below are shown.At this moment, the additive of the application's invention does not use fully.
(liquid composition)
CuSO
4·5H
2O：58.9g/L
Cu：15g/L
H
2SO
4：100g/L
(electroplating temperature) 50 ℃
(current condition)
Current density: 90A/dm
2
Roughening coulomb amount: 200As/dm
2
The SEM photo of the roughened layer of comparative example 1 is as shown in Figure 8.The multiple of the SEM photo in the left side shown in Fig. 8 is that the multiple of the SEM photo on (* 3000), right side is (* 30000).Shown in Figure 8 like this, can find out, form the shape of particle of dendritic crystalline.Average particle diameter is that 5 μ m, particle length are that 25 μ m, aspect ratio are 5.0, satisfies the condition of the application's invention.
Then, on the roughened face of above-mentioned copper, form the heat-resisting/antirust coat same, on this heat-resisting/antirust coat, carry out electrolytic chromate and handle, implement silane treatment (carrying out) at this chromate on by rete again through coating with embodiment 1.
Such copper foil manufactured laminated stickiness to glass cloth base material BT (BMI-triazine) resin plate, is measured or analyzed following project.
(1) the fall observation of powder
In this comparative example 1, observe powder.The result is as shown in table 1.
(2) normality peel strength
The normality peel strength is 0.58kg/cm, and peel strength is low.The result is as shown in table 1.
(3) salt tolerant Suan Shi test
Acid for salt tolerant, on the 0.4mm circuit, use 12 weight % hydrochloric acid, will represent with % in loss (Loss) amount of 60 ℃ of dippings after 90 minutes.Below same.Loss (Loss) amount is 32.4%, loss (Loss) amount than after the comparative example stated lack the demonstration good properties.The result is as shown in table 1.
(4) result of the test of anti-dioxysulfate water-based (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ℃)
On the 0.4mm circuit, implement.At this moment, the situation of etching 2 μ m is examined or check.Loss (Loss) amount is represented with %.The result is as shown in table 1.
Can find out obviously that from table 1 Loss measures up to 31%, anti-dioxysulfate water-based is bad.
(comparative example 2)
The electrolytic copper foil of used thickness 12 μ m is at the matsurface of this Copper Foil (delustring face: carry out roughening plating as follows and the normal plating same with embodiment 1 the M face).Roughening plating treatment conditions below are shown.
(liquid composition)
CuSO
4·5H
2O：58.9g/L
Cu：15g/L
H
2SO
4：100g/L
As addition: 150ppm: use H
3AsO
3(60% aqueous solution)
(electroplating temperature) 50 ℃
(current condition)
Current density: 40A/dm
2
Roughening coulomb amount: 240As/dm
2
The SEM photo of the roughened layer of comparative example 2 is as shown in Figure 8.The multiple of the SEM photo in the left side shown in Fig. 8 is that the multiple of the SEM photo on (* 3000), right side is (* 30000).Shown in Figure 8 like this, can find out to form spherical shape of particle.Average particle diameter is that 1.3 μ m, particle length are that 1.8 μ m, aspect ratio are 1.4, the condition of discontented unabridged version application invention.
Then, on the roughened face of above-mentioned copper, form the heat-resisting/antirust coat same, on this heat-resisting/antirust coat, carry out electrolytic chromate and handle, implement silane treatment (carrying out) at this chromate on by rete again through coating with embodiment 1.
Such copper foil manufactured laminated stickiness to glass cloth base material BT (BMI-triazine) resin plate, is measured or analyzed following project.
(1) the fall observation of powder
Do not observe powder.The result is as shown in table 1.
(2) normality peel strength
The normality peel strength is 0.82kg/cm, has good peel strength.The result is as shown in table 1.
(3) salt tolerant Suan Shi test
Acid for salt tolerant, use 12 weight % hydrochloric acid, will represent with % in loss (Loss) amount of 60 ℃ of dippings after 90 minutes.Below same.Loss (Loss) amount is 20%, loss (Loss) amount than after the comparative example stated lack the demonstration good properties.The result is as shown in table 1.
(4) result of the test of anti-dioxysulfate water-based (sulfuric acid 10%, hydrogen peroxide 2%, room temperature: 30 ℃)
On the 0.4mm circuit, implement.At this moment, the situation of etching 2 μ m is examined or check.Loss (Loss) amount is represented with %.Below same.The result is as shown in table 1.
Can find out obviously that from table 1 Loss measures up to 15%, anti-dioxysulfate water-based is bad.
Can find out from above content; In the printed wiring board-use copper-clad of the application's invention; Be not that formation was thought in the past and is used for (spherical) thrust with circularity of roughened or the crystal grain diameter of dendritic crystalline preferably, but at least one face of Copper Foil, form the fine coarse particles of needle-like, thus; Has following remarkable result: the adhesive strength that can improve Copper Foil self and resin can be provided; For base plate for packaging,, and can carry out meticulous etched Copper Foil and manufacturing approach thereof even the chemical treatments when forming fine pattern also can improve peel strength.
Industrial applicability
As implied above; The present invention forms the fine coarse particles of needle-like at least one face of Copper Foil; Thus, has following remarkable result: the adhesive strength that can improve Copper Foil self and resin can be provided, for base plate for packaging; Even the chemical treatments during for the formation fine pattern also can improve peel strength, and can carry out meticulous etched Copper Foil and manufacturing approach thereof.
In recent years in the fine patterning and high frequency propelling of printed circuit, the present invention pastes with Copper Foil and semiconductor-sealing-purpose resin and the semiconductor-sealing-purpose substrate made is extremely effective as copper foil for printed circuit (conductor package substrate is used Copper Foil) and with conductor package substrate.
Claims (7)
1. a printed wiring board-use copper-clad is characterized in that, at least one face of Copper Foil, has the roughened layer, and it is that 0.1～2.0 μ m and aspect ratio are the fine copper coarse particles of the needle-like more than 1.5 that said roughened layer comprises diameter.
2. a printed wiring board-use copper-clad is characterized in that, at least one face of Copper Foil, has the roughened layer, and it is that 0.1～2.0 μ m and aspect ratio are the fine copper coarse particles of the needle-like more than 3.0 that said roughened layer comprises diameter.
3. according to claim 1 or claim 2 printed wiring board-use copper-clad is characterized in that, the quantity of needle-like coarse particles is in the circuit width of 10 μ m, to exist more than 5.
4. according to claim 1 or claim 2 printed wiring board-use copper-clad is characterized in that, the quantity of needle-like coarse particles is in the circuit width of 10 μ m, to exist more than 10.
5. like each described printed wiring board-use copper-clad in the claim 1～4; It is characterized in that; On said roughened layer, has the heat-resisting/antirust coat that contains at least a above element that is selected from zinc, nickel, copper, phosphorus; On this heat-resisting/antirust coat, have chromate, and have silane coupling agent layer on by rete at this chromate by rete.
6. the manufacturing approach of a printed wiring board-use copper-clad; It is characterized in that; Use contains at least a above material that is selected from alkyl sodium sulfate ester salt, tungsten ion, arsenic ion and the electrobath that comprises sulfuric acid/copper sulphate; On at least one face of Copper Foil, form the roughened layer, it is that 0.1～2.0 μ m and aspect ratio are the fine copper coarse particles of the needle-like more than 1.5 that said roughened layer comprises diameter.
7. the manufacturing approach of printed wiring board-use copper-clad as claimed in claim 6; It is characterized in that; On said roughened layer, form the heat-resisting/antirust coat that contains at least a above element that is selected from zinc, nickel, copper, phosphorus; On this heat-resisting/antirust coat, form chromate then by rete, form silane coupling agent layer at this chromate on by rete again.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009078272 | 2009-03-27 | ||
| JP2009-078272 | 2009-03-27 | ||
| PCT/JP2010/054224 WO2010110092A1 (en) | 2009-03-27 | 2010-03-12 | Copper foil for printed wiring board and method for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102362559A true CN102362559A (en) | 2012-02-22 |
| CN102362559B CN102362559B (en) | 2014-12-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080013439.8A Active CN102362559B (en) | 2009-03-27 | 2010-03-12 | Copper foil for printed wiring board and method for producing same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5406278B2 (en) |
| KR (3) | KR102104161B1 (en) |
| CN (1) | CN102362559B (en) |
| TW (1) | TWI479958B (en) |
| WO (1) | WO2010110092A1 (en) |
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| CN103124810A (en) * | 2010-09-24 | 2013-05-29 | 吉坤日矿日石金属株式会社 | Method for manufacturing copper foil for printed circuit board and copper foil for printed circuit board |
| CN104685109A (en) * | 2012-09-28 | 2015-06-03 | Jx日矿日石金属株式会社 | Copper foil provided with carrier, and copper-clad laminate using said copper foil provided with carrier |
| CN105142897A (en) * | 2013-03-29 | 2015-12-09 | Jx日矿日石金属株式会社 | Copper foil with carrier, printed circuit board, copper clad laminated sheet, electronic device, and printed circuit board fabrication method |
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- 2010-03-12 WO PCT/JP2010/054224 patent/WO2010110092A1/en active Application Filing
- 2010-03-12 CN CN201080013439.8A patent/CN102362559B/en active Active
- 2010-03-12 KR KR1020177006093A patent/KR102104161B1/en active IP Right Grant
- 2010-03-12 KR KR1020117020739A patent/KR20110126128A/en active Application Filing
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| CN107429417B (en) * | 2015-03-31 | 2019-11-22 | 三井金属矿业株式会社 | Roughening treatment copper foil, band carrier copper foil, copper-clad laminated board and printed circuit board |
| CN108505081A (en) * | 2017-02-24 | 2018-09-07 | 南亚塑胶工业股份有限公司 | Method for manufacturing electrolytic copper foil with approximate villiform copper nodules and circuit board assembly |
| CN108505075A (en) * | 2017-02-24 | 2018-09-07 | 南亚塑胶工业股份有限公司 | Method for manufacturing electrolytic copper foil with approximately rugby-shaped copper nodules and circuit board assembly |
| US12120816B2 (en) | 2019-06-19 | 2024-10-15 | Co-Tech Development Corp. | Micro-roughened electrodeposited copper foil and copper clad laminate |
| CN114929944A (en) * | 2019-12-24 | 2022-08-19 | 日本电解株式会社 | Surface-treated copper foil and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010110092A1 (en) | 2010-09-30 |
| TWI479958B (en) | 2015-04-01 |
| CN102362559B (en) | 2014-12-10 |
| KR20170029648A (en) | 2017-03-15 |
| KR20110126128A (en) | 2011-11-22 |
| JPWO2010110092A1 (en) | 2012-09-27 |
| JP5406278B2 (en) | 2014-02-05 |
| KR20130054447A (en) | 2013-05-24 |
| KR102104161B1 (en) | 2020-04-23 |
| TW201039702A (en) | 2010-11-01 |
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