CN107710890A - Manufacture method, surface treatment copper foil, laminate, printing distributing board, semiconductor packages and the e-machine of printing distributing board - Google Patents

Manufacture method, surface treatment copper foil, laminate, printing distributing board, semiconductor packages and the e-machine of printing distributing board Download PDF

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Publication number
CN107710890A
CN107710890A CN201680038794.8A CN201680038794A CN107710890A CN 107710890 A CN107710890 A CN 107710890A CN 201680038794 A CN201680038794 A CN 201680038794A CN 107710890 A CN107710890 A CN 107710890A
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CN
China
Prior art keywords
copper foil
base material
resin base
surface treatment
release layer
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.)
Pending
Application number
CN201680038794.8A
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Chinese (zh)
Inventor
高森雅之
石井雅史
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by JX Nippon Mining and Metals Corp filed Critical JX Nippon Mining and Metals Corp
Priority claimed from PCT/JP2016/072848 external-priority patent/WO2017022807A1/en
Publication of CN107710890A publication Critical patent/CN107710890A/en
Pending legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
    • 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
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Laminated Bodies (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)

Abstract

The present invention provides a kind of by setting release layer physically to peel off resin base material when the copper foil is being fitted in into resin base material in copper foil, so as in the step of removing copper foil from resin base material, lossless be needed on the profile of the copper foil surface on the surface of resin base material and the manufacture method and surface treatment copper foil of the printing distributing board of copper foil are removed with good cost.A kind of manufacture method of printing distributing board, possesses following steps：The step of surface treatment copper foil of release layer is bonded resin base material from release layer side is provided with surface；By removing surface treatment copper foil from resin base material, and obtain resin base material of the release surface transferred with the surface profile of copper foil the step of；And the resin base material transferred with surface profile stripping surface side formed plating pattern the step of.

Description

The manufacture method of printing distributing board, surface treatment copper foil, laminate, printing distributing board, Semiconductor packages and e-machine
Technical field
The present invention relates to a kind of manufacture method of printing distributing board, surface treatment copper foil, laminate, printing distributing board, half Conductor encapsulates and e-machine.
Background technology
In the circuit forming method of printed wiring board and conductor package substrate, subtractive process is main flow, but because in recent years Further fine distribution, M-SAP (Modified Semi-Additive Process, improves semi-additive process), or makes The new method such as the semi-additive process with the surface profile of copper foil is being risen.
Among these new circuit forming methods, one as the semi-additive process of the surface profile using copper foil of the latter is real Example is applied, can be listed below.I.e., first, whole facet etch is carried out to copper foil of the lamination in resin base material, using laser etc. to transferred with The etching substrate surface of copper foil surface profile carries out perforate, implements to turn on the electroless copper layer of aperture portion, is coated to using dry film Electroless copper surface, by the exposed and developed dry films for removing circuit forming portion of UV, to the electroless plating copper face being coated to without dry film Implement electrolytic copper plating, and peel off dry film, finally utilize the etching solution etc. containing sulfuric acid, hydrogen peroxide to be etched electroless copper layer (dodging erosion, fast-etching), is consequently formed fine circuit (patent document 1, patent document 2).
[patent document 1] Japanese Patent Laid-Open 2006-196863 publications
[patent document 2] Japanese Patent Laid-Open 2007-242975 publications.
The content of the invention
However, in the previous semi-additive process using the profile of copper foil surface, it is good for the profile of lossless copper foil surface The surface of resin base material is needed on well and the copper foil is removed with good cost, the leeway for still having research.
The present inventor carries out effort research, as a result finds, by setting release layer to be fitted in by the copper foil in copper foil Resin base material can be physically peeled off during resin base material, so as in the step of removing copper foil from resin base material, lossless transfer Copper foil is removed with good cost in the profile of the copper foil surface on the surface of resin base material.
The present invention completed based on opinion above is a kind of manufacture method of printing distributing board on the one hand, and it has Standby following steps：The step of surface treatment copper foil of release layer is bonded resin base material from above-mentioned release layer side is provided with surface； By removing above-mentioned surface treatment copper foil from above-mentioned resin base material, and obtain the surface profile in release surface transferred with above-mentioned copper foil Resin base material the step of；And form plating pattern in the above-mentioned stripping surface side of the resin base material transferred with above-mentioned surface profile Step.
The present invention is a kind of manufacture method of printing distributing board, it possesses following steps on the other hand：Set on surface The step of surface treatment copper foil for having release layer is bonded resin base material from above-mentioned release layer side；By being removed from above-mentioned resin base material Above-mentioned surface treatment copper foil, and obtain resin base material of the release surface transferred with the surface profile of above-mentioned copper foil the step of；And Transferred with above-mentioned surface profile resin base material above-mentioned stripping surface side formed printed patterns the step of.
The present invention so that on the other hand, be a kind of manufacture method of printing distributing board, it possesses following steps：On surface It is provided with the step of surface treatment copper foil of release layer is bonded resin base material from above-mentioned release layer side；By from above-mentioned resin base material Remove above-mentioned surface treatment copper foil, and obtain resin base material of the release surface transferred with the surface profile of above-mentioned copper foil the step of； And the resin base material transferred with above-mentioned surface profile above-mentioned stripping surface side set increasing layer the step of.
The manufacture method of the printing distributing board of the present invention in one embodiment, fitting form above-mentioned increasing layer resin and on Intensity when stating the untreatment surface of resin base material each other and stretching and peel off is 500g/cm2Below.
In another embodiment, the resin for forming above-mentioned increasing layer includes liquid to the manufacture method of the printing distributing board of the present invention Crystalline polymer or polytetrafluoroethylene (PTFE).
The present invention printing distributing board manufacture method so that another embodiment in, above-mentioned release layer is by following formula：
[chemical formula 1]
(R1)m-M-(R2)n
(in formula, R1For alkoxy or halogen atom, R2It is the hydrocarbon in the group being made up of alkyl, cycloalkyl and aryl Base, or their any alkyl that more than one hydrogen atom is substituted with halogen atoms, any one of M Al, Ti, Zr, n For the integer below 0 or 1 or valence mumber that 2, m are more than 1 and M, R1It is at least one be alkoxy；Furthermore m+n is M valence mumber, It is 3 i.e. in Al situation, aluminic acid ester compounds, titanate compound, the zirconic acid esterification in Ti, Zr situation 4) to represent Compound, their hydrolysate, the condensation body of the hydrolysate are used alone or combine a variety of uses and form.
The present invention printing distributing board manufacture method so that another embodiment in, above-mentioned release layer is by following formula：
[chemical formula 2]
(in formula, R1For alkoxy or halogen atom, R2It is the hydrocarbon in the group being made up of alkyl, cycloalkyl and aryl Base, or their any alkyl that more than one hydrogen atom is substituted with halogen atoms, R3And R4It is separately former for halogen Son, or alkoxy, or the alkyl in the group being made up of alkyl, cycloalkyl and aryl, or more than one hydrogen atom is by halogen Their any alkyl of plain atom substitution) silane compound, its hydrolysate, the condensation body list of the hydrolysate that represent Solely a variety of use is used or combines to form.
The present invention printing distributing board manufacture method so that another embodiment in, above-mentioned release layer is to use molecule The compound inside with the sulfydryl of less than 2 forms.
The present invention printing distributing board manufacture method so that another embodiment in, above-mentioned copper foil is in above-mentioned release layer Side surface has convex portion, on raised part, using electron microscope, makes the platform of the above-mentioned copper foil of mounting from horizontal plane The photo of the release layer side surface of above-mentioned copper foil is shot in the state of 45 °, by the receipts of the convex portion measured based on the photo obtained The height of contracting part to the front end of convex portion is set to a, the Breadth Maximum of the widest part of convex portion is set into b, by the contraction flow region of convex portion When minimum widith is set to c, meet both following formula.
In the situation of a/b≤1, (b-c)/b≤0.2 and b >=10nm
In a/b ＞ 1 situation, (b-c)/b≤0.03 and b >=10nm
The present invention printing distributing board manufacture method so that another embodiment in, in above-mentioned copper foil and the above-mentioned demoulding It is provided between layer selected from by refractory layer, antirust coat, chromic acid processing (chromate treatment) layer and silane coupling processing The layer of one or more of the group of layer composition.
The present invention printing distributing board manufacture method so that another embodiment in, it is above-mentioned be selected from by refractory layer, The surface of the layer of one or more of the group of antirust coat, chromic acid process layer and silane coupling process layer composition is provided with resin bed.
The present invention printing distributing board manufacture method so that another embodiment in, in above-mentioned surface treatment copper foil Release layer side surface is provided with resin bed.
The present invention printing distributing board manufacture method so that another embodiment in, above-mentioned resin bed for then with tree The resin of fat, priming paint or semi-hardened state.
The present invention printing distributing board manufacture method so that another embodiment in, the thickness of above-mentioned surface treatment copper foil Spend for 9~70 μm.
The present invention so that be on the other hand a kind of surface treatment copper foil, it is with copper foil and being arranged on above-mentioned copper foil table The release layer person in face, above-mentioned copper foil have convex portion in above-mentioned release layer side surface, on raised part, using electron microscope, Make the platform of the above-mentioned copper foil of mounting shot from the state of 45 ° of horizontal plane above-mentioned copper foil release layer side surface photograph Piece, and the height of the front end of the constriction of the convex portion measured based on the photo obtained to convex portion is set to a, by convex portion most The Breadth Maximum in wide portion is set to b, when the minimum widith of the contraction flow region of convex portion is set into c, meets both following formula.
In the situation of a/b≤1, (b-c)/b≤0.2 and b >=10nm
In a/b ＞ 1 situation, (b-c)/b≤0.03 and b >=10nm
In one embodiment, above-mentioned copper foil is in above-mentioned release layer side surface without thick for the surface treatment copper foil of the present invention Change particle.
In another embodiment, above-mentioned release layer is by following formula to the surface treatment copper foil of the present invention：
[chemical formula 3]
(R1)m-M-(R2)n
(in formula, R1For alkoxy or halogen atom, R2It is the hydrocarbon in the group being made up of alkyl, cycloalkyl and aryl Base, or their any alkyl that more than one hydrogen atom is substituted with halogen atoms, any one of M Al, Ti, Zr, n For the integer below 0 or 1 or valence mumber that 2, m are more than 1 and M, R1It is at least one be alkoxy；Furthermore m+n is M valence mumber, It is 3 i.e. in Al situation, aluminic acid ester compounds, titanate compound, the zirconic acid esterification in Ti, Zr situation 4) to represent Compound, their hydrolysate, the condensation body of the hydrolysate are used alone or combine a variety of uses and form.
The present invention surface treatment copper foil so that another embodiment in, above-mentioned release layer is by following formula：
[chemical formula 4]
(in formula, R1For alkoxy or halogen atom, R2It is the hydrocarbon in the group being made up of alkyl, cycloalkyl and aryl Base, or their any alkyl that more than one hydrogen atom is substituted with halogen atoms, R3And R4It is separately former for halogen Son, or alkoxy, or the alkyl in the group being made up of alkyl, cycloalkyl and aryl, or more than one hydrogen atom is by halogen Their any alkyl of plain atom substitution) silane compound, its hydrolysate, the condensation body list of the hydrolysate that represent Solely a variety of use is used or combines to form.
The present invention surface treatment copper foil so that another embodiment in, above-mentioned release layer be using intramolecular have 2 The compound of individual following sulfydryl forms.
The present invention surface treatment copper foil so that another embodiment in, set between above-mentioned copper foil and above-mentioned release layer It is equipped with the layer selected from one or more of the group being made up of refractory layer, antirust coat, chromic acid process layer and silane coupling process layer.
The present invention surface treatment copper foil so that another embodiment in, it is above-mentioned be selected from by refractory layer, antirust coat, chromium The surface of the layer of one or more of the group of acid treatment layer and silane coupling process layer composition is provided with resin bed.
The present invention surface treatment copper foil so that another embodiment in, above-mentioned release layer side surface is provided with resin Layer.
The present invention surface treatment copper foil so that another embodiment in, above-mentioned resin bed for then with resin, priming paint Or the resin of semi-hardened state.
The present invention surface treatment copper foil so that another embodiment in, thickness be 9~70 μm.
The present invention so that on the other hand be a kind of laminate, it possess the present invention surface treatment copper foil and be arranged on State the resin base material of the release layer side of surface treatment copper foil.
In one embodiment, above-mentioned resin base material is prepreg to the laminate of the present invention, or contains thermosetting resin.
The present invention so that on the other hand be a kind of printing distributing board, it possess the present invention surface treatment copper foil.
The present invention so that on the other hand be a kind of printing distributing board, its be using the present invention surface treatment copper foil and make Make.
The present invention so that on the other hand be a kind of semiconductor packages, it possess the present invention printing distributing board.
The present invention so that on the other hand be a kind of e-machine, it possess the present invention printing distributing board or the present invention Semiconductor packages.
[The effect of invention]
The present invention provides a kind of by can physics when copper foil sets release layer the copper foil is being fitted in into resin base material Property peel off resin base material, so as to which the surface of resin base material in the step of removing copper foil from resin base material, lossless can be needed on Copper foil surface profile and the manufacture method and surface treatment copper foil of the printing distributing board of copper foil are removed with good cost.
Brief description of the drawings
Fig. 1 is that the section of the copper foil with convex portion (when during the situation in ungauged regions portion with the situation of contraction flow region be present) is illustrated Figure.
Fig. 2 is the diagrammatic cross-section of the copper foil with roughening particle (tuberculosis).
Fig. 3 is the diagrammatic cross-section for the state that Fig. 2 copper foil is fitted in resin base material from roughening particle side surface.
Fig. 4 be in figure 3 remove copper foil after resin base material surface formed plating pattern state diagrammatic cross-section.
Fig. 5 is the diagrammatic cross-section for the state that plating pattern is formed on the resin base material formed in the present invention.
Fig. 6 represents the outline embodiment of the semi-additive process of the profile using copper foil.
Fig. 7 is the micro- sem observation photo of the release layer side surface of sample No.58 surface treatment copper foil.
Fig. 8 is the micro- sem observation photo of the release layer side surface of sample No.55 surface treatment copper foil.
Fig. 9 is the sample (copper foil) of the evaluation method of the convex portion for the release layer side surface for representing face processing copper foil and put down The schematic diagram of platform.
Embodiment
(manufacture method of printing distributing board)
The manufacture method of the printing distributing board of the present invention possesses following steps on the one hand：Surface is provided with release layer The step of surface treatment copper foil is bonded resin base material from above-mentioned release layer side；By being removed from above-mentioned resin base material at above-mentioned surface Copper foil is managed, and is obtained resin base material of the release surface transferred with the surface profile of above-mentioned copper foil the step of；And transferred with above-mentioned The above-mentioned stripping surface side of the resin base material of surface profile forms the step of plating pattern.By such a composition, set in copper foil de- Mold layer and resin base material can be physically peeled off when the copper foil is fitted in into resin base material, from resin base material removal of copper paper tinsel The step of in, lossless can be needed on the profile of the copper foil surface on the surface of resin base material and copper foil is removed with good cost. In the manufacture method, it can form required circuit after plating pattern is formed using the plating pattern and make printing distributing board.
Also, the manufacture method of the printing distributing board of the present invention possesses following steps on the other hand：It is provided with surface de- The step of surface treatment copper foil of mold layer is bonded resin base material from above-mentioned release layer side；It is above-mentioned by being removed from above-mentioned resin base material Surface treatment copper foil, and obtain resin base material of the release surface transferred with the surface profile of above-mentioned copper foil the step of；And transferring The step of above-mentioned stripping surface side for having the resin base material of above-mentioned surface profile forms printed patterns.By such a composition, in copper foil Release layer is set and resin base material can be physically peeled off when the copper foil is fitted in into resin base material, is removed from resin base material In the step of copper foil, it lossless can be needed on the profile of the copper foil surface on the surface of resin base material and copper removal is gone with good cost Paper tinsel.In the manufacture method, for example, can be containing conductive paste etc. in using ink ink-jet and after forming printed patterns, utilize this Printed patterns form required printed circuit and make printing distributing board.
And then the manufacture method of printing distributing board of the invention so that on the other hand possess following steps：Set on surface It is equipped with the step of surface treatment copper foil of release layer is bonded resin base material from above-mentioned release layer side；By being gone from above-mentioned resin base material Except above-mentioned surface treatment copper foil, and obtain resin base material of the release surface transferred with the surface profile of above-mentioned copper foil the step of；And The step of increasing layer is set in the above-mentioned stripping surface side of the resin base material transferred with above-mentioned surface profile.By such a composition, in copper Paper tinsel sets release layer and resin base material can be physically peeled off when the copper foil is fitted in into resin base material, is gone from resin base material Except in the step of copper foil, lossless being needed on the profile of the copper foil surface on the surface of resin base material, and removed with good cost Copper foil.Herein, on the resin for the increasing layer for forming the surface for being arranged on resin base material, the resin and resin base material are not entered respectively Any processing of row and be bonded to each other (fitting form above-mentioned increasing layer resin and above-mentioned resin base material untreatment surface each other) simultaneously Intensity (tensile strength) when stretching and peeling off can be 500g/cm2Below.On forming the increasing on the surface for being arranged on resin base material The resin of layer, intensity when being bonded to each other post-tensioning not carrying out any handle to the resin and resin base material respectively and peel off (tensile strength) is even if to be low such as 500g/cm2Following value, in the situation of the profile of resin base material transfer copper foil surface, structure The adhesion of resin and resin base material into increasing layer also improves, and tensile strength is for example as 800g/cm2More than, more preferably into For 1000g/cm2More than.
Herein, so-called " increasing layer " refers to the layer with the insulator such as conductive layer, Wiring pattern or circuit and resin.The resin Shape Deng insulator can be stratiform.Also, the insulator such as above-mentioned conductive layer, Wiring pattern or circuit and resin can be with any suitable Sequence or position are configured.
Increasing layer can be led by being set in release surface transferred with the stripping surface side of the resin base material of the surface profile of above-mentioned copper foil The insulator such as electric layer, Wiring pattern or circuit and resin and make.As the forming method of conductive layer, Wiring pattern or circuit, Method known to semi-additive process, fully-additive process, subtractive process, part addition process etc. can be used.
Increasing layer can have multilayer, can also have the insulators (layer) such as plurality of conductive layers, Wiring pattern or circuit and resin.
Plurality of conductive layers, Wiring pattern or circuit can electrically be insulated by insulators such as resins.Also can be by setting After the insulators such as fat form perforation and/or blind hole using laser and/or drill bit, copper plate etc. is formed in the perforation and/or blind hole Coating is turned on, and the plurality of conductive layers electrically to insulate, Wiring pattern or circuit are electrically coupled.
Furthermore resin base can be fitted in from above-mentioned release layer side by the way that surface to be provided with to the surface treatment copper foil of release layer The two sides of material, thereafter, surface treatment copper foil is removed, the surface profile of copper foil is handled in the two sides transfer surface of resin base material, The two sides of the resin base material sets circuit, Wiring pattern or increasing layer, so as to manufacture printing distributing board.
Form the insulators such as the resin of such a increasing layer and resin described in this specification, resin bed, resin base can be used Material, and known resin, resin bed, resin base material, insulator, prepreg, the base for making glass cloth be formed containing resin pickup can be used Material etc..The insulators such as resin can contain organic/inorganic substance and/or organic matter.Can be by LCP (liquid also, forming the insulators such as the resin of increasing layer Crystalline polymer) or the material with low relative dielectric constant such as polytetrafluoroethylene (PTFE) formed.In recent years, with the expansion of high frequency product Greatly, by LCP (liquid crystal polymer) or polytetrafluoroethylene (PTFE) (Teflon：Registration mark) etc. have low relative dielectric constant material lead Enter more active to the trend in the structure of printed base plate.Now, because these materials are thermoplasticity, so when hot pressing is processed Change in shape is inevitable, and the substrate composition of LCP (liquid crystal polymer) or Teflon monomer has production yield and do not improved Basic volume production on problem.In the manufacture method of the invention described above, also for such a problem, by using epoxy resin Etc thermosetting resin be bonded as resin substrate, and with it, it is possible to provide a kind of high frequency characteristics is excellent and can prevent from applying The printing distributing board of shape distortion when hot.
(surface treatment copper foil)
As the surface treatment copper foil used in the manufacture method of the printing distributing board of the invention described above, preferably make With following surface treatment copper foil.That is, the surface treatment copper foil is that have copper foil and be arranged on the release layer of above-mentioned copper foil surface Person, and above-mentioned copper foil has convex portion in above-mentioned release layer side surface.Herein, in Fig. 1 represent have expressed " a ", " b " and The diagrammatic cross-section of the copper foil of the convex portion of " c ".On raised part, it is preferable to use electron microscope, as shown in figure 9, making The photo that the platform of above-mentioned copper foil shoots the release layer side surface of above-mentioned copper foil from the state of 45 ° of horizontal plane is loaded, will The height of front end of the constriction of convex portion based on photo (following, for example, following Fig. 8) measure obtained to convex portion is set For a, the Breadth Maximum of the widest part of convex portion is set to b, when the minimum widith of the contraction flow region of convex portion is set into c, meets following formula Both.
In the situation of a/b≤1, (b-c)/b≤0.2 and b >=10nm
In a/b ＞ 1 situation, (b-c)/b≤0.03 and b >=10nm
Furthermore when forming the situation of roughening treatment particle on the surface of copper foil, " a ", " b ", " c " of convex portion are that selection can survey Fixed convex portion and be measured.Herein, so-called above-mentioned measurable convex portion refers to the convex portion that contraction flow region can be observed.It is so-called considerable The convex portion for observing contraction flow region is the convex portion for the crest line (being illustrated in Fig. 8) that convex portion can be observed.
Also, when " contraction flow region " is set to the situation observed in the convex portion to copper foil surface in the direction of close copper foil, After width broadens once from convex portion front end, the part of narrowed width.
" width of convex portion " refers to parallel with the horizontal frame of photo on the photo obtained using sweep electron microscope It is being separated by the profile or crest line of convex portion abreast to be marked with the photo horizontal frame when ground marks the situation for the line for crossing convex portion The straight line for crossing convex portion length.Herein, when the situation of more than 3 crest lines be present in convex portion, 2 ribs of selection most nearby Line.
" the minimum widith c " of contraction flow region is set to the minimum value of the width of the convex portion of contraction flow region.For example, represent in fig. 8 The flat part (line segment) of the crest line of convex portion.In the situation in ungauged regions portion, c=b is set to.
" the height a " of the front end of the constriction of convex portion to convex portion is set to be worth as follows：Received from the front end of convex portion to measure When the line that convex portion is abreast crossed with photo horizontal frame that is being marked during the minimum widith c in contracting portion draws the situation of vertical line, received to measure The line that crosses convex portion parallel with photo horizontal frame that be being marked during the minimum widith c in contracting portion and the vertical line marked from the convex portion front end Intersection point distance (a') with 2 subduplicate product.
" front end of convex portion " refers to when observing photo, the supposition of the convex portion based on judgements such as captured concavo-convex shades For highest part (reference picture 7).
" when the Breadth Maximum b " of widest part has the situation of contraction flow region in convex portion, it is set to from convex portion front end to contraction flow region Between the straight line that crosses convex portion parallel with the horizontal frame of photo the most long length separated by the profile of convex portion.
Convex portion when electrolysis when the convex portion of above-mentioned copper foil can be copper foil formation is handled in caused concave-convex surface, also may be used For by implementation roughening treatment and convex portion that caused roughening particle is formed.
Previous using in the method for the surface profile of copper foil, such as the copper foil (figure that will there is roughening particle (tuberculosis) 2) resin base material (Fig. 3) is fitted in from roughening particle side surface, then removes copper foil, be thus needed on the profile of copper foil surface Resin base material surface, and (Fig. 4) such as plating patterns is formed in the transfer surface.
Herein, it is different according to its shape when copper foil surface has the situation of tuberculosis, remove the resin base material table after copper foil The transfer profile in face can produce space, and according to the size in the space, used plating solution can not when existing to form plating pattern The situation of entrance.Now, as shown in figure 4, as leaving space between resin base material surface and the plating pattern formed State.If such a state for leaving space, then printing distributing board etc. is being made using plating pattern forming circuit thereafter It during situation, can expand, send out near the space because of reliability test (such as 250 DEG C of ± 10 DEG C × 1 hour heat runs) The problems such as raw generation circuit is peeled off or substrate bloats.
For such a problem, according to the surface treatment copper foil of the invention described above, copper foil has convex portion in release layer side surface, Section of the convex portion when edge is cut off perpendicular to the direction of short transverse, from copper foil surface between the traveling of the widest part of section With contraction flow region, the height of convex portion is being set to a, and the section when edge is cut off perpendicular to the direction of short transverse, will The Breadth Maximum of widest part is set to b, when the minimum widith of contraction flow region is set into c, in the situation of a/b≤1, meets (b-c)/b ≤ 0.2 and b >=10nm, also, in a/b ＞ 1 situation, meet (b-c)/b≤0.03 and b >=10nm, so in resin base material Space will not be produced between surface and the plating pattern (or printed patterns or increasing layer) formed, even if or producing, plating pattern Formation when plating solution (if printed patterns formation when, then to include the ink of conductive paste etc., if the formation of increasing layer When, then it is the resin material) it can also fill up the space.Therefore, thereafter, using plating pattern (or printed patterns or increasing layer) and When making the situation of printing distributing board etc., even if progress reliability test (such as 250 DEG C of examinations of the heating of ± 10 DEG C × 1 hour Test), generation circuit can also be peeled off or substrate bulging is suppressed to good (Fig. 5).
On above-mentioned formula, in the situation of a/b≤1, more preferably (b-c)/b≤0.15, and then more preferably (b- c)/b≤0.10.Also, in a/b ＞ 1 situation, more preferably (b-c)/b≤0.25, and then more preferably (b-c)/b≤ 0.20.Also, copper foil is preferably not have roughening particle in release layer side surface.
Release layer has the function that can peel off the resin base material in copper foil fitting resin base material lateral from release layer.Again Person, release layer may be provided at the two sides of copper foil.Also, fitting can be crimped and is bonded.
Copper foil (being also known as foil) is formed by electrolytic copper foil, and the thickness of copper foil is not particularly limited, such as can be set to 5 ~105 μm.Also, being easy for from for the aspect of resin base material stripping, the thickness of surface treatment copper foil is preferably 9~70 μm, more Preferably 12~35 μm, and then more preferably 18~35 μm.
As the manufacture method of copper foil (foil), it is not particularly limited, such as electricity can be made by following electrolytic conditions Solve copper foil.
It is electrolysed the electrolytic condition of foil：
Cu：30~190g/L
H2SO4：100~400g/L
Chloride ion (Cl-)：10~200 mass ppm
Electrolyte temperature：25~80 DEG C
Electrolysis time：10~300 seconds (being adjusted according to the copper thickness, the current density that are separated out)
Current density：50~150A/dm2
Electrolyte linear velocity：1.5~5m/sec
Furthermore by the copper concentration for improving electrolyte, it is possible to increase above-mentioned a, b value.It is also, dense by the copper for reducing electrolyte Degree, above-mentioned a, b value can be reduced.Also, the temperature by improving electrolyte, it is possible to increase above-mentioned a, b value.Also, by reducing electricity The temperature of liquid is solved, above-mentioned a, b, c value can be reduced.Also, by improving chloride ion concentration, it is possible to increase above-mentioned a, b value.Again Person, by improving chloride ion concentration, there is the degree of value increase of the degree of a value increase more than b.Also, pass through Chloride ion concentration is reduced, above-mentioned a, b value can be reduced.Furthermore by reducing chloride ion concentration, the value for having a reduces Degree more than b value reduce degree tendency.By extending plating time, it is possible to increase above-mentioned a, b, c value.Pass through shortening Plating time, above-mentioned a, b, c value can be reduced.
Removing copper foil from resin base material in the present invention refers to the chemical treatment by using progress such as etchings from resin base Material removes copper foil, or physically peels off resin base material from copper foil by stripping etc..By resin base material as described above with the present invention Surface treatment copper foil fitting after when removing, resin base material separates with surface treatment copper foil in release layer.Now in resin base material Release surface, can remain peel ply, the roughening particle of following copper foils, refractory layer, antirust coat, chromic acid process layer, at silane coupling A part for layer etc. is managed, but is preferably that residue is not present.
The surface treatment copper foil of the present invention is when from release layer lateral copper foil fitting resin base material, when peeling off resin base material Peel strength is preferably below 200gf/cm.It is controlled if so, then the physics of resin base material, which is peeled off, becomes easy, copper foil table The profile in face is needed on resin base material better.The peel strength is more preferably below 150gf/cm, and then more preferably Below 100gf/cm, and then more preferably below 50gf/cm, typically 1~200gf/cm, are more typically 1~150gf/ cm。
Secondly, workable release layer in the present invention is illustrated.
(1) silane compound
By by the silane compound with the structure shown in following formula, or its hydrolysate, or the condensation of the hydrolysate Body (hreinafter referred to as silane compound) is used alone or mixed a variety of uses and forms release layer, so as at coating surface When managing copper foil with resin base material, adhesion can be moderately reduced, peel strength is adjusted to above range.
Formula：
[chemical formula 5]
(in formula, R1For alkoxy or halogen atom, R2It is the hydrocarbon in the group being made up of alkyl, cycloalkyl and aryl Base, or their any alkyl that more than one hydrogen atom is substituted with halogen atoms, R3And R4It is separately former for halogen Son, or alkoxy, or the alkyl in the group being made up of alkyl, cycloalkyl and aryl, or more than one hydrogen atom is by halogen Their any alkyl of plain atom substitution.)
The silane compound must have at least one alkoxy.In the absence of alkoxy and only by selected from by alkyl, ring Alkyl in the group of alkyl and aryl composition, or their any alkyl that more than one hydrogen atom is substituted with halogen atoms When forming the situation of substituent, the adhesion for having the tendency of resin base material and copper foil excessively reduces.Also, the silane compound is necessary With at least one alkyl in the group being made up of alkyl, cycloalkyl and aryl, or more than one hydrogen atom is by halogen Their any alkyl of atom substitution.The reason is that when in the absence of the situation of the alkyl, there are resin base material and copper foil Adhesion rise tendency.Furthermore alkoxy also includes the alkoxy that more than one hydrogen atom is substituted by halogen atom.
For in terms of adjusting the peel strength of resin base material and copper foil to above range, the silane compound is preferred For with three alkoxies, and with an above-mentioned alkyl (including the hydrocarbon that more than one hydrogen atom is substituted with halogen atoms Base).If the situation, R are illustrated by above formula3And R4Both turn into alkoxy.
As alkoxy, and it is not limited, can enumerates：Methoxyl group, ethyoxyl, just or isopropoxy, just, the fourth oxygen of XOR the 3rd Base, just, XOR neopentyl oxygen, positive hexyloxy, cyclohexyloxy, straight-chain, the branched such as positive epoxide in heptan and n-octyloxy, or ring The alkoxy of the carbon number 1~20 (being preferably carbon number 1~10, more preferably carbon number 1~5) of shape.
As halogen atom, can enumerate：Fluorine atom, chlorine atom, bromine atoms and iodine atom.
As alkyl, and it is not limited, can enumerates：Methyl, ethyl, just or isopropyl, just, XOR tributyl, just, XOR The carbon number 1~20 of the straight-chains such as neopentyl, n-hexyl, n-octyl, positive decyl or branched (is preferably carbon number 1~10, more preferably For carbon number 1~5) alkyl.
As cycloalkyl, and it is not limited, can enumerates：Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl Deng the cycloalkyl of carbon number 3~10 (being preferably carbon number 5~7).
As aryl, can enumerate：Phenyl, through alkyl-substituted phenyl (example：Tolyl, xylyl), 1- or 2- naphthalenes The aryl of the carbon numbers such as base, anthryl 6~20 (being preferably 6~14).
On the alkyl, more than one hydrogen atom can be substituted by halogen atom, for example, can be substituted by fluorine atom, Chlorine atom, or bromine atoms.
As the example of preferable silane compound, can enumerate：MTMS, ethyl trimethoxy silane, just Or isopropyltri-methoxysilane, just, XOR tributyl trimethoxy silane, just, XOR neopentyl trimethoxy silane, oneself Base trimethoxy silane, octyl group trimethoxy silane, decyl trimethoxy silane, phenyltrimethoxysila,e；Substitute through alkyl Phenyltrimethoxysila,e (such as to (methyl) phenyltrimethoxysila,e), MTES, the ethoxy of ethyl three Base silane, just or isopro-pyltriethoxysilane, just, XOR tributyl triethoxysilane, amyl triethoxysilane, oneself Ethyl triethoxy silicane alkane, octyltri-ethoxysilane, decyl triethoxysilane, phenyl triethoxysilane, substitute through alkyl Phenyl triethoxysilane (such as to (methyl) phenyl triethoxysilane), (3,3,3- trifluoro propyls) trimethoxy silicon Alkane and tridecafluoro-n-octyltriethoxysilane, methyl trichlorosilane, dimethyldichlorosilane, trim,ethylchlorosilane, phenyl trichlorine Silane, Trimethlyfluorosilane, the bromo-silicane of dimethyl two, dibromodiphenyl silane, their hydrolysate and these hydrolysates Condensation body etc..Among these, for the viewpoint of the easiness obtained, preferably propyl trimethoxy silicane, the second of methyl three TMOS, hexyl trimethoxy silane, phenyl triethoxysilane, decyl trimethoxy silane.
In the forming step of release layer, silane compound can be used in the form of the aqueous solution.In order to improve in water Dissolubility, can also add the alcohol such as methanol or ethanol.The addition of alcohol especially when using hydrophobicity higher silane compound compared with To be effective.The aqueous solution of silane compound promotes the hydrolysis of alkoxy by being stirred, if mixing time is longer, promotees Enter the condensation of hydrolysate.Generally, there is tree using the silane compound for by enough mixings time hydrolyze and be condensed The tendency that the peel strength of aliphatic radical material and copper foil reduces.Therefore, by adjusting mixing time, it can adjust peel strength.As making Silane compound is dissolved in the mixing time after water, such as can be set to 1~100 hour, can typically be set to 1~30 hour, but And it is not limited.Certainly, the method for not stirring and using also be present.
Concentration the higher person of silane compound in the aqueous solution of silane compound has the stripping of metal foil and plate-shaped support The tendency of intensity decreases, by adjusting the concentration of silane compound, it can adjust peel strength.Silane compound is in aqueous Concentration can be set to 0.01~10.0 volume %, can typically be set to 0.1~5.0 volume %, but and be not limited.
There is no particular restriction by the pH of the aqueous solution of silane compound, can be utilized in acidic side, can also be utilized in alkaline side.Example If used with the pH of 3.0~10.0 scope.For the viewpoint without special pH adjustment, preferably it is set to as in The pH of 5.0~9.0 scope near property, more preferably it is set to the pH of 7.0~9.0 scope.
(2) compound of the intramolecular with the sulfydryl of less than 2
Release layer is formed using compound of the intramolecular with the sulfydryl of less than 2, by being pasted via the release layer Resin base material and copper foil, adhesion also can be moderately reduced, adjust peel strength.
Wherein, make compound or its salt of the intramolecular with the sulfydryl of more than 3 be situated between to exist between resin base material and copper foil And during the situation of fitting, be not suitable for the purpose that peel strength reduces.Think the reason is that if intramolecular excessively has mercapto Base, then in the presence of following situation：Or sulfydryl and the chemical reaction of metal foil and mistake by sulfydryl each other, or sulfydryl and plate-shaped support, Amount ground generation sulfide linkage, cystine linkage or polysulfide bond, form firm 3-dimensional cross-linked structure, therefore shell between resin base material and copper foil Rise from intensity.Such a example is disclosed in Japanese Patent Laid-Open 2000-196207 publications.
As compound of the intramolecular with the sulfydryl of less than 2, can enumerate：Mercaptan, two mercaptan, thiocarboxylic acid or its Salt, carbodithioic acid or its salt, thiosulfonic acid or its salt and two thiosulfonic acids or its salt, it can be used in these at least It is a kind of.
Mercaptan system intramolecular has a sulfydryl person, such as is represented by R-SH.Herein, R represents that hydroxyl or amido can be contained Fatty family or fragrant family alkyl or heterocyclic radical.
Two mercaptan system intramoleculars have two sulfydryl persons, such as by R (SH)2Represent.R is represented containing hydroxyl or amido Fatty family or fragrant family alkyl or heterocyclic radical.Also, two sulfydryls can be bonded to identical carbon respectively, can also be bonded to mutually Different carbon or nitrogen.
The hydroxyl of thiocarboxylic acid system organic carboxyl acid is substituted by sulfydryl person, such as represented by R-CO-SH.R represents to contain There are the fatty family or fragrant family alkyl or heterocyclic radical of hydroxyl or amido.Also, thiocarboxylic acid can also be used in the form of salt. Furthermore the compound with two thiocarboxylic acid bases also can be used.
2 oxygen atoms in the carboxyl of carbodithioic acid system organic carboxyl acid are substituted by sulphur atom person, such as by R- (CS)-SH is represented.R represents the fatty family containing hydroxyl or amido or fragrant family alkyl or heterocyclic radical.Also, two is thio Carboxylic acid can also be used in the form of salt.Furthermore the compound with two carbodithioic acid bases also can be used.
The hydroxyl of thiosulfonic acid system organic sulfonic acid is substituted by sulfydryl person, such as by R (SO2)-SH expressions.R represents to contain There are the fatty family or fragrant family alkyl or heterocyclic radical of hydroxyl or amido.Also, thiosulfonic acid can also be used in the form of salt.
Two hydroxyls of two thiosulfonic acid system organic-disulfonates are substituted by sulfydryl respectively person, such as by R- ((SO2)- SH)2Represent.R represents the fatty family containing hydroxyl or amido or fragrant family alkyl or heterocyclic radical.Also, two thio sulphurs Acidic group can be bonded to identical carbon respectively, can also be bonded to mutually different carbon.Also, two thiosulfonic acids also can be in the form of salt Use.
Herein, as the suitably fatty family alkyl as R, alkyl, cycloalkyl can be enumerated, the alkyl can contain hydroxyl With amido either or both.
Also, as alkyl, and be not limited, it can enumerate：Methyl, ethyl, just or isopropyl, just, XOR tributyl, just, The carbon number 1~20 of the straight-chains such as XOR neopentyl, n-hexyl, n-octyl, positive decyl or branched (is preferably carbon number 1~10, more Preferably carbon number 1~5) alkyl.
Also, as cycloalkyl, and be not limited, it can enumerate：Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, ring are pungent The cycloalkyl of the carbon numbers such as base 3~10 (being preferably carbon number 5~7).
Also, as the suitably aromatic hydrocarbyl as R, can enumerate：Phenyl, through alkyl-substituted phenyl (example：Tolyl, Xylyl), 1- or 2- naphthyls, the aryl of the carbon number 6~20 such as anthryl (being preferably 6~14), these alkyl can contain hydroxyl With amido either or both.
Also, as the suitably heterocyclic radical as R, can enumerate：Imidazoles, triazole, tetrazolium, benzimidazole, BTA, thiophene Azoles, benzothiazole, contain either or both of hydroxyl and amido.
As the preferred of compound of the intramolecular with the sulfydryl of less than 2, can enumerate：3- sulfydryls -1,2- the third two Alcohol, 2 mercapto ethanol, 1,2- dithioglycols, 6- sulfydryl -1- hexanols, 1- spicy thioalcohols, 1- dodecyl mercaptans, 10- hydroxyls Base -1- dodecyl mercaptans, 10- carboxyl -1- dodecyl mercaptans, 10- amido -1- dodecyl mercaptans, 1- dodecane sulphur Alcohol sodium sulfonate, benzenethiol, thiobenzoate, 4- amidos-benzenethiol, toluene-ω-thiol, 2,4- thiophenol dimethyl benzenes, 3- mercaptos Base -1,2,4- triazoles, 2- Mercapto-benzothiazoles.Among these, with regard to the viewpoint in terms of water-soluble and offal treatment Speech, preferably 3- sulfydryls -1,2-PD.
In the forming step of release layer, compound of the intramolecular with the sulfydryl of less than 2 can be with the shape of the aqueous solution State uses.In order to improve the dissolubility in water, the alcohol such as methanol or ethanol can be also added.The addition of alcohol is especially using hydrophobicity It is more effective during compound of the higher intramolecular with the sulfydryl of less than 2.
The concentration the higher person of compound of the intramolecular with the sulfydryl of less than 2 in aqueous has resin base material and copper foil The tendency that reduces of peel strength, by adjusting the concentration of compound of the intramolecular with the sulfydryl of less than 2, can adjust and peel off Intensity.The concentration of compound of the intramolecular with the sulfydryl of less than 2 in aqueous can be set to 0.01~10.0 weight %, allusion quotation 0.1~5.0 weight % can be set to type, but and is not limited.
There is no particular restriction by the pH of the aqueous solution of compound of the intramolecular with the sulfydryl of less than 2, can be in acidic side profit With can also be utilized in alkaline side.Such as it can be used with the pH of 3.0~10.0 scope.The just sight without special pH adjustment For point, the pH of 5.0~9.0 scope as near neutral is preferably set to, is more preferably set to 7.0~9.0 scope PH.
(3) metal alkoxide
Aluminic acid ester compounds, titanate compound, zirconic acid ester compounds with the structure shown in following formula, or its hydrolysis production Thing, or the hydrolysate condensation body (hreinafter referred to as metal alkoxide) can be separately formed release layer or mixing it is a variety of and Form release layer.By being bonded resin base material and copper foil via the release layer, adhesion can be moderately reduced, regulation is peeled off strong Degree.
[chemical formula 6]
(R1)m-M-(R2)n
In formula, R1For alkoxy or halogen atom, R2It is the alkyl in the group being made up of alkyl, cycloalkyl and aryl, Or their any alkyl that more than one hydrogen atom is substituted with halogen atoms, any one of M Al, Ti, Zr, n 0 1 or 2, m be more than 1 and M valence mumber below integer, R1It is at least one be alkoxy.Furthermore m+n is M valence mumber, i.e., It is 3 in Al situation, is 4 in Ti, Zr situation.
The metal alkoxide must have at least one alkoxy.In the absence of alkoxy and only by selected from by alkyl, Alkyl in the group of cycloalkyl and aryl composition, or their any hydrocarbon that more than one hydrogen atom is substituted with halogen atoms When base forms the situation of substituent, the adhesion for having the tendency of resin base material and copper foil excessively reduces.Also, the metal alkoxide There must be 0~2 alkyl in the group being made up of alkyl, cycloalkyl and aryl, or more than one hydrogen atom is by halogen Their any alkyl of plain atom substitution.The reason is that in the situation with more than 3 alkyl, there is resin base The tendency that the adhesion of material and copper foil excessively reduces.Furthermore alkoxy is also substituted by halogen including more than one hydrogen atom The alkoxy of atom.For in terms of the peel strength of resin base material and copper foil is adjusted to above range, the metal alcoxyl Compound is preferably have a two or more alkoxy, and has one or two above-mentioned alkyl (including more than one hydrogen atom quilt The alkyl of halogen atom substitution).
Also, as alkyl, and be not limited, it can enumerate：Methyl, ethyl, just or isopropyl, just, XOR tributyl, just, The carbon number 1~20 of the straight-chains such as XOR neopentyl, n-hexyl, n-octyl, positive decyl or branched (is preferably carbon number 1~10, more Preferably carbon number 1~5) alkyl.
Also, as cycloalkyl, and be not limited, it can enumerate：Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, ring are pungent The cycloalkyl of the carbon numbers such as base 3~10 (being preferably carbon number 5~7).
Also, as being suitably used as R2Aromatic hydrocarbyl, can enumerate：Phenyl, through alkyl-substituted phenyl (example：Tolyl, Xylyl), 1- or 2- naphthyls, the aryl of the carbon number 6~20 such as anthryl (being preferably 6~14), these alkyl can contain hydroxyl With amido either or both.On these alkyl, more than one hydrogen atom can be substituted by halogen atom, such as can quilt It is substituted by fluorine atom, chlorine atom, or bromine atoms.
As the example of preferable aluminic acid ester compounds, can enumerate：Aluminium methoxide, methyl dimethoxy epoxide aluminium, ethyl diformazan Epoxide aluminium, just or isopropyl dimethoxy aluminium, just, XOR tributyl dimethoxy aluminium, just, XOR neopentyl dimethoxy Aluminium, hexyl dimethoxy aluminium, octyl group dimethoxy aluminium, decyl dimethyl epoxide aluminium, phenyl dimethoxy aluminium；Through alkyl-substituted benzene Base dimethoxy aluminium (such as to (methyl) phenyl dimethoxy aluminium), dimethyl aluminum methoxide, aluminium ethoxide, methyl diethoxy Base aluminium, ethyl diethoxy aluminium, just or isopropyl diethoxy aluminium, just, XOR tributyl diethoxy aluminium, amyl group diethoxy Base aluminium, hexyl diethoxy aluminium, octyl group diethoxy aluminium, decyl diethoxy aluminium, diethylamino phenyl epoxide aluminium, through alkyl-substituted Diethylamino phenyl epoxide aluminium (such as to (methyl) diethylamino phenyl epoxide aluminium), dimethyl aluminum ethoxide, aluminium isopropoxide, methyl two Aluminum isopropoxide, ethyl diisopropoxy aluminium, just or isopropyl diethoxy aluminium, just, XOR tributyl diisopropoxy aluminium, Amyl group diisopropoxy aluminium, hexyl diisopropoxy aluminium, octyl group diisopropoxy aluminium, decyl diisopropoxy aluminium, phenyl two are different It is propoxyl group aluminium, different through alkyl-substituted phenyl diisopropoxy aluminium (such as to (methyl) phenyl diisopropoxy aluminium), dimethyl Propoxyl group aluminium, (3,3,3- trifluoro propyls) dimethoxy aluminium and ten trifluoro octyl group diethoxy aluminium, methylaluminum dichloride, diformazan Base aluminium chloride, phenyl dichloro aluminium, dimethylaluminum fluoride, dimethyl aluminium bromide, diphenyl aluminium bromide, they hydrolysate, And condensation body of their hydrolysate etc..Among these, for the viewpoint of the easiness obtained, preferably trimethoxy Aluminium, aluminium ethoxide, aluminium isopropoxide.
As the example of preferable titanate compound, can enumerate：Titanium tetramethoxide, methyl trimethoxy epoxide titanium, ethyl front three Epoxide titanium, just or isopropyl trimethoxy titanium, just, XOR tributyl trimethoxy titanium, just, XOR neopentyl trimethoxy Titanium, hexyl trimethoxy titanium, octyl group trimethoxy titanium, decyl trimethoxy titanium, phenyl trimethoxy titanium；Through alkyl-substituted benzene Base trimethoxy titanium (such as to (methyl) phenyl trimethoxy titanium), dimethylformamide dimethyl epoxide titanium, purity titanium tetraethoxide, the second of methyl three Epoxide titanium, ethyl triethoxy titanium, just or isopropyl triethoxy titanium, just, XOR tributyl triethoxy titanium, the second of amyl group three Epoxide titanium, hexyl triethoxy titanium, octyl group triethoxy titanium, decyl triethoxy titanium, phenyl triethoxy titanium, substitute through alkyl Phenyl triethoxy titanium (such as to (methyl) phenyl triethoxy titanium), dimethyl diethoxy titanium, tetraisopropoxy titanium, first The titanium isopropoxide of base three, the titanium isopropoxide of ethyl three, just or isopropyl triethoxy titanium, just, the isopropyl oxygen of XOR tributyl three Base titanium, the titanium isopropoxide of amyl group three, the titanium isopropoxide of hexyl three, the titanium isopropoxide of octyl group three, the titanium isopropoxide of decyl three, phenyl Three titanium isopropoxides, through the alkyl-substituted titanium isopropoxide of phenyl three (such as to the titanium isopropoxide of (methyl) phenyl three), diformazan Base diisopropoxy titanium, (3,3,3- trifluoro propyls) trimethoxy titanium and ten trifluoro octyl group triethoxy titaniums, methyl tri-chlorination Titanium, dimethyl titanium chloride, trimethyl ammonia chloride titanium, phenyl titanium trichloride, dimethyl bifluoride titanium, dimethyl dibrominated titanium, two Condensation body of phenyl dibrominated titanium, their hydrolysate and their hydrolysate etc..Among these, what is just obtained is easy For the viewpoint of property, preferably titanium tetramethoxide, purity titanium tetraethoxide, tetraisopropoxy titanium.
As the example of preferable zirconic acid ester compounds, can enumerate：Tetramethoxy zirconium, methyl trimethoxy epoxide zirconium, ethyl front three Epoxide zirconium, just or isopropyl trimethoxy zirconium, just, XOR tributyl trimethoxy zirconium, just, XOR neopentyl trimethoxy Zirconium, hexyl trimethoxy zirconium, octyl group trimethoxy zirconium, decyl trimethoxy zirconium, phenyl trimethoxy zirconium；Through alkyl-substituted benzene Base trimethoxy zirconium (such as to (methyl) phenyl trimethoxy zirconium), dimethylformamide dimethyl epoxide zirconium, tetraethoxy zirconium, the second of methyl three Epoxide zirconium, ethyl triethoxy zirconium, just or isopropyl triethoxy zirconium, just, XOR tributyl triethoxy zirconium, the second of amyl group three Epoxide zirconium, hexyl triethoxy zirconium, octyl group triethoxy zirconium, decyl triethoxy zirconium, phenyl triethoxy zirconium, substitute through alkyl Phenyl triethoxy zirconium (such as to (methyl) phenyl triethoxy zirconium), dimethyl diethoxy zirconium, zirconium tetraisopropoxide, first The isopropoxy zirconium of base three, the isopropoxy zirconium of ethyl three, just or isopropyl triethoxy zirconium, just, the isopropyl oxygen of XOR tributyl three Base zirconium, the isopropoxy zirconium of amyl group three, the isopropoxy zirconium of hexyl three, the isopropoxy zirconium of octyl group three, the isopropoxy zirconium of decyl three, phenyl Three isopropoxy zirconiums, through the alkyl-substituted isopropoxy zirconium of phenyl three (such as to the isopropoxy zirconium of (methyl) phenyl three), diformazan Base diisopropoxy zirconium, (3,3,3- trifluoro propyls) trimethoxy zirconium and ten trifluoro octyl group triethoxy zirconiums, methyl tri-chlorination Zirconium, dimethyl zirconium dichloride, trimethyl ammonia chloride zirconium, phenyl tri-chlorination zirconium, dimethyl zirconium difluoride, dimethyl dibrominated zirconium, two Condensation body of phenyl dibrominated zirconium, their hydrolysate and their hydrolysate etc..Among these, what is just obtained is easy For the viewpoint of property, preferably tetramethoxy zirconium, tetraethoxy zirconium, zirconium tetraisopropoxide.
In the forming step of release layer, metal alkoxide can be used in the form of the aqueous solution.In order to improve in water In dissolubility, can also add the alcohol such as methanol or ethanol.The addition of alcohol is especially using the higher metal alkoxide of hydrophobicity When it is more effective.
The concentration the higher person of metal alkoxide in aqueous has inclining for the peel strength of resin base material and copper foil reduction To, by adjusting metal alkoxide concentration, adjustable peel strength.The concentration of metal alkoxide in aqueous can be set to 0.001~1.0mol/L, 0.005~0.2mol/L can be typically set to, but and be not limited.
There is no particular restriction by the pH of the aqueous solution of metal alkoxide, can be utilized in acidic side, can also be utilized in alkaline side. Such as it can be used with the pH of 3.0~10.0 scope.For the viewpoint without special pH adjustment, conduct is preferably set to The pH of 5.0~9.0 scope of near neutral, more preferably it is set to the pH of 7.0~9.0 scope.
(4) other
Material with release property known to the releasing agent of silicon systems, resin coating with release property etc. can be used for release layer.
The present invention surface treatment copper foil can be set between copper foil and release layer be selected from by roughening treatment layer, refractory layer, More than a kind of layer in the group of antirust coat, chromic acid process layer and silane coupling process layer composition.Herein, so-called chromic acid process layer Refer to carry out handling the layer formed using the liquid comprising chromic anhybride, chromic acid, dichromic acid, chromate or bichromate.At chromic acid Manage layer can contain the element such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic and titanium (can be metal, alloy, oxide, Any forms such as nitride, sulfide).As the concrete example of chromic acid process layer, can enumerate：Utilize chromic anhybride or potassium bichromate water Solution carries out the chromic acid process layer that forms of processing, or handled using the treatment fluid comprising chromic anhybride or potassium bichromate and zinc and Into chromic acid process layer etc..
Roughening treatment layer can for example be formed by following processing.Furthermore by improving used in roughening treatment Copper concentration in plating solution, it is possible to increase above-mentioned a, b value.Also, by reducing the copper in the plating solution used in roughening treatment Concentration, above-mentioned a, b value can be reduced.Also, by improving the metal beyond the copper in the plating solution used in roughening treatment Concentration, above-mentioned a, b value can be reduced.Also, the temperature by improving plating solution, it is possible to increase above-mentioned a, b value.Also, pass through reduction The temperature of plating solution, above-mentioned a, b, c value can be reduced.By extending plating time, it is possible to increase above-mentioned a, b, c value.Pass through contracting Short plating time, above-mentioned a, b, c value can be reduced.
[spherical roughening]
Using by Cu, H2SO4, the following described copper roughening plating bath that is formed of As and form spherical roughening particle.
Liquid composition 1
CuSO4·5H278~196g/L of O
20~50g/L of Cu
H2SO450~200g/L
0.7~3.0g/L of arsenic
30~76 DEG C of (electroplating temperature 1)
35~105A/dm of (current condition 1) current density2(more than the limiting current density of bath)
(plating time 1) 1~240 second
Then, in order to prevent coming off and raising peel strength for roughening particle, the copper being made up of sulfuric acid, copper sulphate is utilized Electrobath carries out covering plating.Covering plating condition is recorded in following.
Liquid composition 2
CuSO4·5H288~352g/L of O
22~90g/L of Cu
H2SO450~200g/L
25~80 DEG C of (electroplating temperature 2)
(current condition 2) current density：15~32A/dm2(not up to the limiting current density of bath)
(plating time 1) 1~240 second
[fine roughening (1 type)]
First, roughening treatment is carried out under the following conditions.It is roughened current density and the limit during formation of (processing) particle The ratio between current density is that (current density/carrying current during=roughening (processing) particle formation is close for relative limit current density ratio Degree) it is set to 2.10~2.90.
Liquid composition 1
CuSO4·5H229.5~118g/L of O
7.5~30g/L of Cu
H2SO450~200g/L
Na2WO4·2H22.7~10.8mg/L of O
5~20ppm of lauryl sodium sulfate addition
20~70 DEG C of (electroplating temperature 1)
34~74A/dm of (current condition 1) current density2
(plating time 1) 1~180 second
Then, it is following it is shown under conditions of carry out normal plating.
Liquid composition 2
CuSO4·5H288~352g/L of O
40~90g/L of Cu
H2SO450~200g/L
30~65 DEG C of (electroplating temperature 2)
21~45A/dm of (current condition 2) current density2
(plating time 2) 1~180 second
[fine roughening (2 type)]
First, Cu-Co-Ni ternary alloy layers are formed under following liquid composition 1 and plating conditions 1, thereafter, On the ternary alloy layer cobalt-nickel alloy coating is formed under following liquid composition 2 and plating conditions 2.
Liquid composition 1
10~20g/L of Cu
1~10g/L of Co
1~10g/L of Ni
PH 1~4
30~50 DEG C of (electroplating temperature 1)
25~45A/dm of (current condition 1) current density2
(plating time 1) 1~60 second
Liquid composition 2
1~30g/L of Co
1~30g/L of Ni
PH 1.0~3.5
30~80 DEG C of (electroplating temperature 2)
3~10A/dm of (current condition 2) current density2
(plating time 2) 1~60 second
Also, as refractory layer, antirust coat, known refractory layer, antirust coat can be used.For example, refractory layer and/or antirust coat Can be comprising selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum family element, iron, tantalum group in More than a kind of element layer, also can be by selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, Platinum family element, iron, tantalum group in more than a kind of the element metal level or alloy-layer that are formed.Also, refractory layer and/or antirust Layer contains comprising selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum family element, iron, tantalum Oxide, nitride, the silicide of more than a kind of element in group.Also, refractory layer and/or antirust coat also can be comprising nickel- The layer of kirsite.Also, refractory layer and/or antirust coat can be nickel-zinc alloy-layer.Above-mentioned nickel-zinc alloy-layer can be except can not keep away Beyond the impurity exempted from, contain nickel 50wt%~99wt%, zinc 50wt%~1wt% person.The zinc and nickel of above-mentioned nickel-zinc alloy-layer Total adhesion amount can be 5~1000mg/m2, preferably 10~500mg/m2, preferably 20~100mg/m2.Also, it is preferably to wrap Ratio (the attachment of=nickel of the adhesion amount of the nickel of layer or above-mentioned nickel-zinc alloy-layer containing above-mentioned nickel-zinc alloy and the adhesion amount of zinc The adhesion amount of amount/zinc) it is 1.5~10.Also, the attachment of the nickel of the layer comprising above-mentioned nickel-zinc alloy or above-mentioned nickel-zinc alloy-layer Amount is preferably 0.5mg/m2~500mg/m2, more preferably 1mg/m2~50mg/m2。
Such as refractory layer and/or antirust coat can be that sequentially lamination adhesion amount is 1mg/m2~100mg/m2(it is preferably 5mg/m2 ~50mg/m2) nickel or nickel alloy layer and adhesion amount be 1mg/m2~80mg/m2(it is preferably 5mg/m2~40mg/m2) tin layers And winner, above-mentioned nickel alloy layer can be made up of nickel-molybdenum, nickel-zinc, any of nickel-molybdenum-cobalt.Also, refractory layer and/or In antirust coat, nickel or total adhesion amount of nickel alloy and tin are preferably 2mg/m2~150mg/m2, more preferably 10mg/m2~ 70mg/m2.Also, refractory layer and/or antirust coat preferably [the nickel adhesion amount in nickel or nickel alloy]/[tin adhesion amount]=0.25~ 10, more preferably 0.33~3.
Furthermore known silane coupling agent can be used in the silane coupling agent used in silane coupling processing, such as can make With amido system silane coupling agent or epoxy silane coupling agent, sulfydryl system silane coupling agent.Also, second also can be used in silane coupling agent Alkenyl trimethoxy silane, ethenylphenyl trimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, 4- glycidyls butyl trimethoxy silane, γ-aminocarbonyl propyl three Ethoxysilane, N- β-(amido ethyl)-γ-aminocarbonyl propyl trimethoxy silane, the N-3- (4- (oxygen of 3- amidos third Base) butoxy) propyl group -3- aminocarbonyl propyl trimethoxy silanes, imidizole silane, triazine silane, γ-mercaptopropyi trimethoxy Base silane etc..
Epoxy silane, amido system silane, methacryloxy system silane, mercapto can be used in above-mentioned silane coupling process layer Silane coupling agents such as base system silane etc. and formed.Furthermore such a silane coupling agent can mix two or more uses.Wherein, preferably Formed using amido system silane coupling agent or epoxy silane coupling agent.
The amido system silane coupling agent of so-called meaning herein, can be selected from by N- (2- amidos ethyl) -3- amidos third Base trimethoxy silane, 3- (N- styrylmethyl -2- amido ethyls amido) propyl trimethoxy silicane, 3- amidos Propyl-triethoxysilicane, double (2- hydroxyethyls) -3- aminocarbonyl propyl triethoxysilanes, aminocarbonyl propyl trimethoxy silicon Alkane, N- methylaminos propyl trimethoxy silicane, N- phenyl aminocarbonyl propyl trimethoxy silane, N- (3- acryloyl-oxies Base -2- hydroxypropyls) -3- aminocarbonyl propyl triethoxysilanes, 4- amido butyl triethoxysilane, (amido ethylamine Ylmethyl) phenethyl trimethoxy silane, N- (2- amido ethyl -3- aminocarbonyl propyls) trimethoxy silane, N- (2- amine Base ethyl -3- aminocarbonyl propyls) three (2- ethyl hexyl oxies) silane, 6- (aminohexyl aminocarbonyl propyl) trimethoxy silane, Aminocarbonyl phenyl trimethoxy silane, 3- (1- amidos propoxyl group) -3,3- dimethyl -1- acrylic trimethoxy silanes, 3- aminocarbonyl propyls three (methoxyethoxyethoxy) silane, 3- aminocarbonyl propyl triethoxysilanes, 3- aminocarbonyl propyl front threes TMOS, ω-amido undecyltrimethoxysilane, 3- (2-N- benzylamino ethyls aminocarbonyl propyl) trimethoxy Silane, double (2- hydroxyethyls) -3- aminocarbonyl propyl triethoxysilanes, (N, N- diethyl -3- aminocarbonyl propyls) front three TMOS, (N, N- dimethyl -3- aminocarbonyl propyls) trimethoxy silane, N- methylaminos propyl trimethoxy silicane, N- phenyl aminocarbonyl propyl trimethoxy silane, 3- (N- styrylmethyl -2- amido ethyls amido) propyl trimethoxy Silane, γ-aminocarbonyl propyl triethoxysilane, N- β-(amido ethyl)-γ-aminocarbonyl propyl trimethoxy silane, N- Person in the group of 3- (4- (3- amidos propoxyl group) butoxy) propyl group -3- aminocarbonyl propyl trimethoxy silanes composition.
More satisfactory silane coupling process layer is to be calculated as 0.05mg/m with silicon atom conversion2~200mg/m2(it is preferably 0.15mg/m2~20mg/m2, preferably 0.3mg/m2~2.0mg/m2) in the range of set., can in the situation of above range Further improve the adhesion of resin base material and copper foil.
Also, in copper foil, roughening particle layer, refractory layer, antirust coat, silane coupling process layer, chromic acid process layer or release layer Surface, International Publication numbering WO2008/053878, Japanese Patent Laid-Open 2008-111169, Japanese Patent No. can be carried out No. 5024930, International Publication numbering WO2006/028207, Japanese Patent No. 4828427, International Publication numbering WO2006/ 134868th, Japanese Patent No. 5046927, International Publication numbering WO2007/105635, Japanese Patent No. 5180815, Japan Described surface treatment in open patent 2013-19056.
Resin bed can be set on the surface of the surface treatment copper foil of the present invention.Resin bed is normally located on release layer.
The resin bed on above-mentioned surface treatment copper foil surface can be then to use resin, i.e. solid, can be priming paint, also can be to connect The insulating resin layer for the semi-hardened state (B-stage state).So-called semi-hardened state (B-stage state) is even if including with hand Its surface of abutment is also felt without adhering, and the insulating resin layer can overlap and take care of, and then can be produced firmly if heated processing Change the state of reaction.The resin bed on above-mentioned surface treatment copper foil surface shows appropriate stripping when being preferably and being contacted with release layer The resin bed of intensity (such as 2gf/cm~200gf/cm).Again, it is preferable to use follow the bumps of copper foil surface, being not likely to produce can Cause the space of bulging or the mixed resin of bubble.For example, when copper foil surface sets the resin bed, it is preferable to use resin Viscosity for 10000mPas (25 DEG C) below, more preferably the viscosity of resin is 5000mPas (25 DEG C) such as the following viscosity Relatively low resin and resin bed is set.By being set between insulated substrate and surface treatment copper foil of the lamination in surface treatment copper foil Above-mentioned resin bed is put, even if when using being not easy to follow the situation of the concavo-convex insulated substrate of copper foil surface, resin bed is also followed In copper foil surface, so space or bubble can be made to be not likely to produce between surface treatment copper foil and insulated substrate, so it is more effective.
Also, the resin bed on above-mentioned surface treatment copper foil surface can contain thermosetting resin, also can be thermoplastic resin. Also, the resin bed on above-mentioned surface treatment copper foil surface can contain thermoplastic resin.The resin bed on above-mentioned surface treatment copper foil surface Can contain known resin, hardening of resin agent, compound, hardening accelerator, dielectric substance, reaction catalyst, crosslinking agent, polymer, Prepreg, skeleton material etc..Also, International Publication numbering WO2008/ for example can be used in the resin bed on above-mentioned surface treatment copper foil surface 004399th, International Publication numbering WO2008/053878, International Publication numbering WO2009/084533, Japanese Patent Laid-Open 11- No. 5828, Japanese Patent Laid-Open 11-140281, Japanese Patent No. 3184485, International Publication numbering WO97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open 2000-43188, Japanese Patent No. 3612594, Japan Patent are special Open No. 2002-179772, Japanese Patent Laid-Open 2002-359444, Japanese Patent Laid-Open 2003-304068, Japan specially Profit the 3992225th, Japanese Patent Laid-Open 2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open 2004-349654, Japanese Patent No. No. 4286060, Japanese Patent Laid-Open 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open 2005- No. 53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication numbering WO2004/005588, day This patent JP 2006-257153, Japanese Patent Laid-Open 2007-326923, Japanese Patent Laid-Open 2008-111169 Number, Japanese Patent No. 5024930, International Publication numbering WO2006/028207, Japanese Patent No. 4828427, Japan Patent JP 2009-67029, International Publication numbering WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication numbering WO2007/105635, Japanese Patent No. 5180815, International Publication numbering WO2008/114858, International Publication numbering WO2009/008471, Japanese Patent Laid-Open 2011-14727, International Publication are compiled Number WO2009/001850, International Publication numbering WO2009/145179, International Publication numbering WO2011/068157, Japan Patent Described material (resin, hardening of resin agent, compound, hardening accelerator, dielectric substance, reaction in JP 2013-19056 Catalyst, crosslinking agent, polymer, prepreg, skeleton material etc.) and/or resin bed forming method, forming apparatus and formed.
(laminate, semiconductor packages, e-machine)
Resin base material can be set in the release layer side of the surface treatment copper foil of the present invention and make laminate.The laminate can By paper base material phenol resin, paper base material epoxy resin, synthetic fibers cloth base material epoxy resin, glass cloth-paper composite base material asphalt mixtures modified by epoxy resin Fat, glass cloth-glass adhesive-bonded fabric composite base material epoxy resin and glass cloth base material epoxy resin etc. and form resin base material.Tree Aliphatic radical material can be prepreg, can also contain thermosetting resin.Also, electricity is formed by the surface treatment copper foil in the laminate Road, printing distributing board can be made.And then by the way that in printing distributing board electronic component mounting class, printed circuit board (PCB) can be made.At this In invention, " printing distributing board " also includes the printing distributing board for being so equipped with electronic component class and printed circuit board (PCB) and printing base Plate.Also, the printing distributing board can be used and make e-machine, can be used the printed circuit board (PCB) that is equipped with the electronic component class and E-machine is made, also be can be used and be equipped with the printed base plate of the electronic component class and make e-machine.Also, above-mentioned " printing Circuit board " also includes semiconductor-sealing-purpose circuit forming board.And then electricity can be carried in semiconductor-sealing-purpose circuit forming board Sub- part class and make semiconductor packages.And then the semiconductor packages can be used and make e-machine.
The copper foil of the present invention can be used to form fine circuits by semi-additive process.The profile using copper foil is represented in Fig. 6 Semi-additive process outline example.In the semi-additive process, the surface profile of copper foil is used.Specifically, first, in resin base material Laminate is made from the surface treatment copper foil of the release layer side lamination present invention.Secondly, removed using etching, or peel off laminate Copper foil (surface treatment copper foil).Secondly, the surface of the resin base material transferred with copper foil surface profile is cleaned using dilute sulfuric acid etc. Afterwards, electroless copper is implemented.Then, using the part for not forming circuit of the coated with resin base material such as dry film, to not being coated to by dry film The surface of electroless copper layer implement electric (electrolysis) copper facing.Thereafter, after dry film is removed, remove formation and or not the portion of circuit The electroless copper layer divided, is consequently formed fine circuit.Fine circuits formed in the present invention by with transferred with the present invention Copper foil surface profile resin base material release surface contiguity, so its touch power (peel strength) become good.
Also, the another embodiment of semi-additive process is as described below.
So-called semi-additive process refers to carry out relatively thin electroless plating on resin base material or copper foil, after forming pattern, uses The method that plating and etching form conductive pattern.Therefore, in the manufacturer of the printing distributing board of the invention using semi-additive process In one embodiment of method, comprise the following steps：The step of preparing the surface treatment copper foil and resin base material of the present invention；
Above-mentioned surface treatment copper foil is from release layer side laminated resin base material the step of；
After the above-mentioned surface treatment copper foil of lamination and resin base material, removed using etching, or peel off above-mentioned surface treatment copper The step of paper tinsel；
Peel off above-mentioned surface treatment copper foil and the release surface of caused resin base material perforation and/or blind hole are set the step of；
The step of removing glue Slag treatment is carried out to the region comprising above-mentioned perforation and/or blind hole；
To utilizing the eluted resin base material tables such as dilute sulfuric acid comprising above-mentioned resin base material and the region of above-mentioned perforation and/or blind hole Face, and the step of electroless plating (such as electroless copper layer) is set；
The step of plating resist is set on above-mentioned electroless plating；
Above-mentioned plating resist is exposed, thereafter, remove form circuit region plating resist the step of；
In the region for eliminating the above-mentioned formation circuit of above-mentioned plating resist, electro deposition (such as electrolytic copper plated layer) is set The step of；
The step of removing above-mentioned plating resist；And
The step of electroless plating in the region being located at by dodging the removals such as erosion beyond the region of above-mentioned formation circuit.
In the another embodiment using the manufacture method of the printing distributing board of the invention of semi-additive process, including it is as follows Step：The step of preparing the surface treatment copper foil and resin base material of the present invention；
Above-mentioned surface treatment copper foil is from release layer side laminated resin base material the step of；
After the above-mentioned surface treatment copper foil of lamination and resin base material, removed using etching, or peel off above-mentioned surface treatment copper The step of paper tinsel；
To the above-mentioned surface treatment copper foil of stripping, the release surface of caused resin base material utilizes the eluted resin bases such as dilute sulfuric acid Material surface, and the step of electroless plating (such as electroless copper layer) is set；
The step of plating resist is set on above-mentioned electroless plating；
Above-mentioned plating resist is exposed, thereafter, remove form circuit region plating resist the step of；
In the region for eliminating the above-mentioned formation circuit of above-mentioned plating resist, electro deposition (such as electrolytic copper plated layer) is set The step of；
The step of removing above-mentioned plating resist；And
The step of electroless plating in the region being located at by dodging the removals such as erosion beyond the region of above-mentioned formation circuit.
Can in the above described manner the resin base material after surface treatment copper foil is peeled off release surface formed circuit, and make printing Circuit forming board, semiconductor-sealing-purpose circuit forming board.And then the circuit forming board can be used, and make printed wiring Plate, semiconductor packages.And then can be used the printing distributing board, semiconductor packages and make e-machine.
On the other hand, using fully-additive process printing distributing board of the invention manufacture method another embodiment In, comprise the following steps：The step of preparing the surface treatment copper foil and resin base material of the present invention；
Above-mentioned surface treatment copper foil is from release layer side laminated resin base material the step of；
After the above-mentioned surface treatment copper foil of lamination and resin base material, removed using etching, or peel off above-mentioned surface treatment copper The step of paper tinsel；
Release surface to peeling off above-mentioned surface treatment copper foil and caused resin base material, utilizes the eluted resin base such as dilute sulfuric acid The step of material surface；
The step of plating resist is set on above-mentioned clean resin base material surface；
Above-mentioned plating resist is exposed, thereafter, remove form circuit region plating resist the step of；
It (such as can be electroless copper to set electroless plating in the region for eliminating the above-mentioned formation circuit of above-mentioned plating resist Layer, the electroless plating thickened) the step of；And
The step of removing above-mentioned plating resist.
Furthermore in semi-additive process and fully-additive process, have by cleaning above-mentioned resin base material surface and with easily setting The situation of the effect of electroless plating.Especially when release layer residues in the situation on resin base material surface, cleaned by this, release layer Part or all by from resin base material surface remove, so have by above-mentioned resin base material surface clean, have more hold The situation of the effect of electroless plating is easily set.Method of cleaning known to the clean usable utilization (species of used liquid, The coating method etc. of temperature, liquid) cleaning of carrying out.Again, it is preferable to use can remove the present invention release layer a part or Whole method of cleaning.
Can in the above described manner, by fully-additive process, the release surface of the resin base material after surface treatment copper foil is peeled off is formed Circuit, and make printed circuit and form substrate, semiconductor-sealing-purpose circuit forming board.And then the circuit can be used to form base Plate, and make printing distributing board, semiconductor packages.And then can be used the printing distributing board, semiconductor packages and make e-machine.
Furthermore the surface of copper foil or surface treatment copper foil is utilized and possesses XPS (x-ray photoelectron light-dividing device), EPMA The machines such as (electron beam microanalyzer), EDX (energy dispersion-type X-ray analysis) SEM are measured, if Si is detected, then can speculate silane compound be present on the surface of copper foil or surface treatment copper foil.Also, surface treatment copper foil with When the peel strength of resin substrate is below 200gf/cm situation, it can speculate using workable in the release layer for having the present invention Above-mentioned silane compound.
It is also, (electric using possessing XPS (x-ray photoelectron light-dividing device), EPMA to the surface of copper foil or surface treatment copper foil Beamlet microanalyzer), the machine such as EDX (energy dispersion-type X-ray analysis) SEM be measured, detecting To S, and when the peel strength of surface treatment copper foil and resin substrate is below 200gf/cm situation, can speculate in copper foil or The surface of surface treatment copper foil, workable above-mentioned intramolecular in the release layer of the present invention be present with the sulfydryl of less than 2 Compound.
It is also, (electric using possessing XPS (x-ray photoelectron light-dividing device), EPMA to the surface of copper foil or surface treatment copper foil Beamlet microanalyzer), the machine such as EDX (energy dispersion-type X-ray analysis) SEM be measured, detecting To Al, Ti, Zr, and when the peel strength of surface treatment copper foil and resin substrate is below 200gf/cm situation, can speculate On the surface of copper foil or surface treatment copper foil, workable above-mentioned metal alkoxide in the release layer of the present invention be present.
[embodiment]
For experimental example described below as embodiments of the invention and comparative example, the embodiment is to more fully understand this Invention and its advantage and provide, and the intention of unlimited invention.
The manufacture of foil (copper foil before surface treatment)
Under following electrolytic condition, the electrolysis foil of thickness described in table 1 is made.
(electrolyte composition)
Cu 120g/L
H2SO4 100g/L
Chloride ion (Cl-)70ppm
60 DEG C of electrolyte temperature
Current density 70A/dm2
Electrolyte linear velocity 2m/sec
Surface treatment
Secondly, as surface treatment, to the M faces (frosted face) of foil, it is as follows it is each under the conditions of, be roughened Processing, barrier processing (resistance to heat treatment), antirust treatment, silane coupling processing, resin bed form any of processing, or will everywhere Reason is combined and carried out.Then, release layer is formed in the processing side surface of copper foil under conditions of as follows.Furthermore simultaneously During not specifically mentioned situation, each processing is carried out according to record order.Also, in table 1, it is described in the column throughout managed "None" person represents that these processing are not carried out.
(1) roughening treatment
[spherical roughening]
Using by Cu, H2SO4, the copper roughening plating bath as described below that is formed of As and form spherical roughening particle.
Liquid composition 1
CuSO4·5H278~118g/L of O
20~30g/L of Cu
H2SO4 12g/L
1.0~3.0g/L of arsenic
25~33 DEG C of (electroplating temperature 1)
(current condition 1) current density 78A/dm2(more than the limiting current density of bath)
(plating time 1) 1~45 second
Then, in order to prevent coming off and raising peel strength for roughening particle, the copper being made up of sulfuric acid, copper sulphate is utilized Electrobath carries out covering plating.Covering plating condition is recorded in following.
Liquid composition 2
CuSO4·5H2O 156g/L
Cu 40g/L
H2SO4 120g/L
40 DEG C of (electroplating temperature 2)
(current condition 2) current density：20A/dm2(not up to the limiting current density of bath)
(plating time 2) 1~60 second
[fine roughening (1 type)]
First, roughening treatment is carried out under the following conditions.Relative limit current density ratio during roughening particle formation is set For 2.70.
Liquid composition 1
CuSO4·5H219.6~58.9g/L of O
5~15g/L of Cu
H2SO4 120g/L
Na2WO4·2H26.0~10.4mg/L of O
Lauryl sodium sulfate addition 10ppm
20~35 DEG C of (electroplating temperature 1)
(current condition 1) current density 57A/dm2
(plating time 1) 1~25 second
Then, it is following it is shown under conditions of carry out normal plating.
Liquid composition 2
CuSO4·5H2O 156g/L
Cu 40g/L
H2SO4 120g/L
30~40 DEG C of (electroplating temperature 2)
(current condition 2) current density 38A/dm2
(plating time 2) 1~45 second
[fine roughening (2 type)]
First, after forming Cu-Co-Ni ternary alloy layers under following liquid composition 1 and plating conditions 1, at this On ternary alloy layer cobalt coating is formed under following liquid composition 2 and plating conditions 2.
Liquid composition 1
8~18g/L of Cu
1~10g/L of Co
1~10g/L of Ni
PH 1~4
30~40 DEG C of (electroplating temperature 1)
(current condition 1) current density 30A/dm2
(plating time 1) 1~30 second
Liquid composition 2
1~30g/L of Co
1~30g/L of Ni
PH 1.0~3.5
20~70 DEG C of (electroplating temperature 2)
1~4A/dm of (current condition 2) current density2
(plating time 2) 1~25 second
(2) barrier processing (resistance to heat treatment)
For sample No.9,11,12,27,29,30,45,47,48, (heat-resisting) processing is obstructed under the following conditions, And form brass coating.
(liquid composition)
Cu 70g/L
Zn 5g/L
NaOH 70g/L
NaCN 20g/L
(plating conditions)
Temperature 70 C
Current density 8A/dm2(multistage processing)
(3) antirust treatment
For sample No.10~12,28~30,46~48, antirust treatment (zinc chromate processing) is carried out under the following conditions, And form antirust treatment layer.
(liquid composition)
CrO3 2.5g/L
Zn 0.7g/L
Na2SO4 10g/L
pH 4.8
(zinc chromate condition)
54 DEG C of temperature
Current density 0.7As/dm2
(4) silane coupling is handled
For sample No.11~12, silane coupling agent coating process is carried out under the following conditions, and forms silane coupled layer.
(liquid composition)
Tetraethoxysilane content 0.4%
pH 7.5
Coating method solution is sprayed
(5) formation of release layer
For sample No.1~16,19~34,37~52,55~60, as shown in table 1 as form following release layer A~E's Any one.
[release layer A]
On the processing surface of copper foil, Bracewell coater silane-coating compound (n-propyl trimethoxy silane is used： After aqueous solution 4wt%), copper foil surface is set to dry 5 minutes and form release layer A in 100 DEG C of air.Make silane compound It is dissolved in water the mixing time afterwards to before being coated to be set to 30 hours, the determining alcohol in the aqueous solution is set to 0vol%, water The pH of solution is set to 3.8~4.2.
[release layer B]
Compound using 1- dodecyl mercaptans sodium sulfonate as intramolecular with the sulfydryl of less than 2, is applied using spraying Cloth machine is by the aqueous solution (the 1- dodecyl mercaptans sulfonic acid na concns of 1- dodecyl mercaptans sodium sulfonates：3wt%) it is coated on copper foil After process face, it is allowed to dry 5 minutes and make release layer B in 100 DEG C of air.The pH of the aqueous solution is set to 5~9.
[release layer C]
Using as the aluminium isopropoxide of aluminic acid ester compounds as metal alkoxide, using Bracewell coater by three The aqueous solution (the aluminium isopropoxide concentration of aluminum isopropoxide：After 0.04mol/L) being coated on the process face of copper foil, at 100 DEG C It is allowed to dry 5 minutes and make release layer C in air.Aluminic acid ester compounds are made to be dissolved in water stirring to before being coated afterwards Mixing the time is set to 2 hours, and the determining alcohol in the aqueous solution is set to 0vol%, and the pH of the aqueous solution is set to 5~9.
[release layer D]
, as metal alkoxide, applied using as the titanium isopropoxide of positive decyl-three of titanate compound using spraying Cloth machine is by the aqueous solution (the titanium isopropoxide concentration of positive decyl-three of the titanium isopropoxide of positive decyl-three：0.01mol/L) it is coated on After the process face of copper foil, it is allowed to dry 5 minutes and make release layer D in 100 DEG C of air.It is dissolved in titanate compound Mixing time after in water to before being coated is set to 24 hours, and methanol is set to 20vol%, water by the determining alcohol in the aqueous solution The pH of solution is set to 5~9.
[release layer E]
, as metal alkoxide, applied using as the n-butoxy of n-propyl-three zirconium of zirconic acid ester compounds using spraying Cloth machine is by the aqueous solution (the n-butoxy zirconium concentration of n-propyl-three of the n-butoxy zirconium of n-propyl-three：0.04mol/L) it is coated on After the process face of copper foil, it is allowed to dry 5 minutes and make release layer E in 100 DEG C of air.It is dissolved in titanate compound Mixing time after in water to before being coated is set to 12 hours, and the determining alcohol in the aqueous solution is set to 0vol%, the aqueous solution PH is set to 5~9.
(6) resin bed formation is handled
For sample No.12,30,48, it is coated with, after formation release layer in barrier processing, antirust treatment, silane coupling agent, And then the formation of resin bed is carried out under the following conditions.
(resins synthesis example)
It is mounted with to be equipped with to the separator in the anchor type stirring rod with stainless steel, nitrogen ingress pipe and stop cock In 2 liters of three-necked flasks of the reflux condenser of spherical condensation tube, 3,4,3', 4'- biphenyl tetracarboxylic dianhydrides 117.68g is added (400mmol), 1,3- double (3- amidos phenoxy group) benzene 87.7g (300mmol), gamma-valerolactone 4.0g (40mmol), pyridines 4.8g (60mmol), N- methyl -2- Pyrrolizidines ketone (being recited as NMP below) 300g, toluene 20g, heated 1 hour with 180 DEG C Afterwards, near room temperature is cooled to, it is double then to add 3,4,3', 4'- biphenyl tetracarboxylic dianhydrides 29.42g (100mmol), 2,2- { 4- (4- amidos phenoxy group) phenyl } propane 82.12g (200mmol), NMP 200g, toluene 40g, and it is small in mixed at room temperature 1 Shi Hou, heated 3 hours with 180 DEG C, and obtain the block copolymerized polyimide of solid content composition 38%.Gather on the block copolymerization Acid imide, following shown formulas (1)：Formula (2)=3：2, number average molecular weight：70000th, weight average molecular weight： 150000。
[chemical formula 7]
Using NMP and then the block copolymerized polyimide solution obtained in synthesis example is diluted, and solid content composition is made 10% block copolymerized polyimide solution., will double (4- maleimides in the block copolymerized polyimide solution Phenyl) methane (BMI-H, KI CHEMICAL INDUSTRY) is sub- with solid content Ingredients Weight ratio 35, block copolymerization polyamides (that is, double (4- maleimides phenyl) methane solids contained by resin solution of solid content Ingredients Weight ratio 65 of amine Thing Ingredients Weight：Contained block copolymerized polyimide solid content Ingredients Weight=35 in resin solution：65) it is mixed in 60 DEG C of dissolvings Close 20 minutes and resin solution is made.Thereafter, above-mentioned resin solution is applied in the release layer forming face of embodiment 12, and in nitrogen Under atmosphere, after carrying out 3 minutes with 120 DEG C, carry out drying process in 3 minutes with 160 DEG C, finally carried out with 300 DEG C at heating in 2 minutes Reason, and make the copper foil for possessing resin bed.Furthermore the thickness of resin bed is set to 2 μm.
(7) various evaluations
The evaluation of the convex portion of the release layer side surface of surface treatment copper foil
The sweep electron microscope manufactured using Japan Electronics Corporation, as shown in figure 9, making mounting surface treatment copper foil Platform shot from the state of 45 ° of horizontal plane surface treatment copper foil release layer side surface photo, based on being obtained Photo (following, for example, following Fig. 8), the convex portion of the release layer side surface of surface treatment copper foil is evaluated shown in Fig. 1 respectively " the height a " of the front end of the constriction of convex portion to convex portion, " Breadth Maximum b ", " minimum widith of contraction flow region of widest part c”.Furthermore the observation multiplying power of sweep electron microscope is set to 30,000 times~1,000,000 times.Also, the inclination of the platform of mounting sample It is to be carried out along with the vertical frame direction of photo for the direction at right angle and the rotary shaft in the direction parallel with the horizontal frame direction of photo.
Evaluation as shown in figure 1, to each convex portion measure " a ", " b ", " c " value, by " a " of the convex portion of more than 100, " b ", The value of the arithmetic mean of instantaneous value of " c " is set to " a ", " b ", the value of " c ".Furthermore form roughening treatment particle on the surface of copper foil Situation when, " a ", " b ", " c " of convex portion are the measurable convex portions of selection and are measured.Herein, above-mentioned measurable convex portion Refer to the convex portion that contraction flow region can be observed.The so-called convex portion that contraction flow region can be observed is that the crest line that convex portion can be observed (is illustrated in Convex portion Fig. 8).
Herein, " contraction flow region " is set to the convex portion for copper foil surface in the situation observed close to the direction of copper foil When, after width broadens once from convex portion front end, the part of narrowed width.
" width of convex portion " refers to parallel with the horizontal frame of photo on the photo obtained using sweep electron microscope It is being separated by the profile or crest line of convex portion abreast to be marked with the photo horizontal frame when ground marks the situation for the line for crossing convex portion The straight line for crossing convex portion length.Herein, when the situation of more than 3 crest lines be present in convex portion, 2 crest lines of selection most nearby.
" the minimum widith c " of contraction flow region is set to the minimum value of the width of the convex portion of contraction flow region.Situation in ungauged regions portion When, it is set to c=b.
" the height a " of the front end of the constriction of convex portion to convex portion is set to be worth as follows：Shunk from the front end of convex portion to measure When the line that convex portion is abreast crossed with photo horizontal frame that is being marked during the minimum widith c in portion draws the situation of vertical line, shunk to measure The line that crosses convex portion parallel with photo horizontal frame that be being marked during the minimum widith c in portion and the vertical line that is marked from the convex portion front end The distance (a') of intersection point and 2 subduplicate product.
" front end of convex portion " refers to when observing photo, the supposition of the convex portion based on judgements such as captured concavo-convex shades For highest part (reference picture 7).
" when the Breadth Maximum b " of widest part has the situation of contraction flow region in convex portion, it is set to from convex portion front end to contraction flow region Between the straight line that crosses convex portion parallel with the horizontal frame of photo the most long length separated by the profile of convex portion.
The manufacture of laminate
Any of following resin base material 1~3 is bonded in the processing side surface of each surface treatment copper foil.
Base material 1：The GHPL-830MBT of gas chemistry limited company of Mitsubishi manufacture
Base material 2：The 679-FG of chemical conversion industry limited company of Hitachi manufacture
Base material 3：The EI-6785TS-F of Sumitomo Bakelite limited company manufacture
The temperature of lamination pressurization, pressure, time are the recommendation conditions for using each base material manufacturer.
The fissility evaluation of surface treatment copper foil
For laminate, according to IPC-TM-650, determined from copper foil and peeled off using cupping machine Autograph 100 Normality peel strength during resin base material, and the fissility of surface treatment copper foil is evaluated based on following benchmark.
○：For 2~200gf/cm scope.
×：Not up to 2gf/cm or more than 200gf/cm.
The evaluation of the failure mode of resin
Using the release surface of the resin base material after the above-mentioned stripping of electron microscope observation, to the failure mode of resin (cohesion, Interface, cohesion and interface are mixed) observed.On the failure mode of resin, " interface " is represented in copper foil and resin Interface peel, " cohesion " represents that peel strength is too strong and resin destroys, and " being mixed " represents above-mentioned " interface " with " coagulating It is poly- " it is mixed.
Circuit is peeled off, the evaluation of substrate bulging
The release surface of resin base material 1~3 after above-mentioned stripping, using plating solution, [liquid forms：Cu：50g/L、H2SO4： 50g/L、Cl：60ppm) form plating copper pattern (line/gap=50 μm/50 μm) (example 1).Also, the resin base after above-mentioned stripping The release surface of material, printed patterns (line/gap=50 μm/50 μm) (example 2) are formed by ink-jet using the ink containing conductive paste. Also, the release surface of the resin base material after above-mentioned stripping, is laminated the resin bed being made up of liquid crystal polymer (it is assumed that forming increasing layer Resin) (example 3).
Secondly, it is confirmed whether to produce electricity by reliability test (250 DEG C of heat runs of ± 10 DEG C × 1 hour) respectively Road is peeled off or substrate bulging.Furthermore 250mm × the 250mm that is sized to of sample is evaluated, each sample number into spectrum is to 3 samples It is measured.
To non-generation circuit stripping and substrate bulging person is evaluated as " ◎ ".Although will slightly generation circuit stripping or substrate drum Go out (in 1 sample for 3 under), if but Select to use position, "○" can be evaluated as article user.Also, will A large amount of generation circuits are peeled off or substrate bulging (in 1 sample more than 3 at) and "×" can not be evaluated as article user.
Each experimental condition and evaluation result are shown in table 1~4.
After the untreatment surface of the resin and resin base material that form increasing layer is bonded each other, by the resin and resin base material Intensity when stretching and peeling off
For the untreatment surface of resin base material 1~3, it will be assumed that (laughable to form the liquid crystal polymer of the resin of increasing layer The Vecstar of beautiful limited company's manufacture, model：50 μm of CT-F thickness) size 1cm square is set to, in lamination temperature 295 ± 5 DEG C, lamination pressure：1MPa, lamination time：Lamination is carried out under 30 minutes.Then, using solid by with metal wire 1cm square metallic plates are engaged in the liquid crystal polymer of institute's lamination.Furthermore metal wire is metal system, and by welding or welding and It is engaged in the central portion of 1cm square metallic plates.Then, using cupping machine Autograph 100, to passing through tensile wire And the maximum loading stretched from resin base material 1~3 when forming the resin (liquid crystal polymer) of increasing layer and peeling off is measured.To appointing Anticipate and carry out the measure at 3, the arithmetic mean of instantaneous value at 3 is set to maximum loading A (g).Furthermore the draw speed of metal wire is set to 50mm/min.Also, the direction of tensile wire is set to perpendicular to the direction on the surface of metallic plate.Also, by A (g/cm2) be set to By the untreatment surface of the resin and resin base material 1~3 that form increasing layer be bonded each other and stretch and intensity when peeling off.Measure As a result it is that on any one of resin base material 1~3, the resin (liquid crystal polymer) and resin base material 1~3 of increasing layer will be formed Intensity when untreatment surface is bonded and stretches and peel off each other turns into 500g/cm2Below.Also, will be described in table 1 After each copper foil sample lamination resin base material 1~3 described in table 1, the copper foil sample is peeled off from resin base material, and is turned It is printed on the resin base material of the concavo-convex profile of copper foil surface.Then, to the resin base in the concavo-convex profile transferred with the copper foil surface The resin (liquid crystal polymer) on the surface of material, in the same manner as described above lamination composition increasing layer, thereafter, determine stretching resin base material and structure Intensity when being peeled off into the resin of increasing layer.Its result is, in above-mentioned " circuit is peeled off, the evaluation of substrate bulging ", evaluation In experimental example for " ◎ ", stretching resin base material is with forming the resin of increasing layer and intensity when peeling off turns into 1000g/cm2More than, It is evaluated as in the experimental example of "○", stretching resin base material is with forming the resin of increasing layer and intensity when peeling off turns into 800g/cm2With On, it is evaluated as in the experimental example of "×", stretching resin base material is with forming the resin of increasing layer and intensity when peeling off turns into 600g/ cm2Below.
[table 1]
As shown in table 1~4, be provided with example No.1~16 of specific release layer, No.19~34, No.37~52,55~ 60 peel strength is suppressed, and the failure mode of resin is only interface.In this way, copper foil is removed after being bonded with resin base material When, it lossless can be needed on the profile of the copper foil surface on the surface of resin base material and remove copper foil well.
On the other hand, be not provided with release layer, or release layer to be formed and use the unsuitable example No.17 of compound~ 18th, No.35~36, No.53~54 can not form release layer, and peel strength is larger, and the failure mode of resin is cohesion and mixing It is any with interface in the presence of condensing.In this way, when removing copper foil after being bonded with resin base material, the surface of resin base material is needed on The profile of copper foil surface be damaged, and copper foil can not be removed well.
The micro- sem observation photo of the release layer side surface of the No.58 of sample surface treatment copper foil is represented in Fig. 7.
The micro- sem observation photo of the release layer side surface of the No.55 of sample surface treatment copper foil is represented in Fig. 8.

Claims (30)

1. a kind of manufacture method of printing distributing board, it possesses following steps：
The step of surface treatment copper foil of release layer is bonded resin base material from the release layer side is provided with surface；
By removing the surface treatment copper foil from the resin base material, and obtain in release surface transferred with the surface profile of the copper foil The step of resin base material；And
The step of plating pattern being formed in the stripping surface side of the resin base material transferred with the surface profile.
2. a kind of manufacture method of printing distributing board, it possesses following steps：
The step of surface treatment copper foil of release layer is bonded resin base material from the release layer side is provided with surface；
By removing the surface treatment copper foil from the resin base material, and obtain in release surface transferred with the surface profile of the copper foil The step of resin base material；And
The step of printed patterns being formed in the stripping surface side of the resin base material transferred with the surface profile.
3. a kind of manufacture method of printing distributing board, it possesses following steps：
The step of surface treatment copper foil of release layer is bonded resin base material from the release layer side is provided with surface；
By removing the surface treatment copper foil from the resin base material, and obtain in release surface transferred with the surface profile of the copper foil The step of resin base material；And
The step of increasing layer is set in the stripping surface side of the resin base material transferred with the surface profile.
4. the manufacture method of printing distributing board according to claim 3, wherein, fitting forms resin and tree of the increasing layer The untreatment surface of aliphatic radical material each other and stretches and intensity when peeling off is 500g/cm2Below.
5. the manufacture method of the printing distributing board according to claim 3 or 4, wherein, the resin for forming the increasing layer includes liquid Crystalline polymer or polytetrafluoroethylene (PTFE).
6. the manufacture method of printing distributing board according to any one of claim 1 to 5, wherein, the release layer is by under Formula：
[chemical formula 1]
(R1)m-M-(R2)n
(in formula, R1For alkoxy or halogen atom, R2It is the alkyl in the group being made up of alkyl, cycloalkyl and aryl, or Their any alkyl that more than one hydrogen atom is substituted with halogen atoms, any one of M Al, Ti, Zr, n be 0 or 1 or 2, m be more than 1 and M valence mumber below integer, R1It is at least one be alkoxy；Furthermore m+n is M valence mumber, that is, is existed It is 3 during Al situation, aluminic acid ester compounds, titanate compound, zirconic acid ester compounds in Ti, Zr situation 4) to represent And their hydrolysate, the condensation body of the hydrolysate are used alone or combine a variety of uses and form.
7. the manufacture method of printing distributing board according to any one of claim 1 to 5, wherein, the release layer is by under Formula：
[chemical formula 2]
(in formula, R1For alkoxy or halogen atom, R2It is the alkyl in the group being made up of alkyl, cycloalkyl and aryl, or Their any alkyl that more than one hydrogen atom is substituted with halogen atoms, R3And R4It is separately halogen atom, or Alkoxy, or the alkyl in the group being made up of alkyl, cycloalkyl and aryl, or more than one hydrogen atom is by halogen atom Substitution any alkyl) represent silane compound, its hydrolysate, the hydrolysate condensation body be used alone or combination A variety of uses form.
8. the manufacture method of printing distributing board according to any one of claim 1 to 5, wherein, the release layer is to use Compound of the intramolecular with the sulfydryl of less than 2 forms.
9. the manufacture method of printing distributing board according to any one of claim 1 to 8, wherein, the copper foil is in the demoulding Layer side surface has convex portion, on the convex portion, using electron microscope, makes the platform of the mounting copper foil from horizontal plane The photo of the release layer side surface of the copper foil is shot in the state of 45 °, by the contraction of the convex portion measured based on the photo obtained The height of the front end of part to convex portion is set to a, the Breadth Maximum of the widest part of convex portion is set into b, by the contraction flow region of convex portion most When small width is set to c, meet both following formula：
In the situation of a/b≤1, (b-c)/b≤0.2 and b >=10nm
In a/b ＞ 1 situation, (b-c)/b≤0.03 and b >=10nm.
10. the manufacture method of printing distributing board according to any one of claim 1 to 9, wherein, it is de- with this in the copper foil The one kind being provided between mold layer in the group being made up of refractory layer, antirust coat, chromic acid process layer and silane coupling process layer Layer above.
11. the manufacture method of printing distributing board according to claim 10, wherein, this be selected from by refractory layer, antirust coat, The surface of the layer of one or more of the group of chromic acid process layer and silane coupling process layer composition is provided with resin bed.
12. according to the manufacture method of any described printing distributing board in claim 1 to 11, wherein, in the surface treatment The release layer side surface of copper foil is provided with resin bed.
13. the manufacture method of the printing distributing board according to claim 11 or 12, wherein, the resin bed is then with tree The resin of fat, priming paint or semi-hardened state.
14. the manufacture method of the printing distributing board according to any one of claim 1 to 13, wherein, the surface treatment copper The thickness of paper tinsel is 9~70 μm.
15. a kind of surface treatment copper foil, there is copper foil and be arranged on the release layer of the copper foil surface,
The copper foil has convex portion in the release layer side surface, on the convex portion, using electron microscope, makes the mounting copper foil Platform shoots the photo of the release layer side surface of the copper foil from the state of 45 ° of horizontal plane, by based on the photo obtained The constriction of the convex portion measured to the height of the front end of convex portion is set to a, and the Breadth Maximum of the widest part of convex portion is set into b, will When the minimum widith of the contraction flow region of convex portion is set to c, meet both following formula：
In the situation of a/b≤1, (b-c)/b≤0.2 and b >=10nm
In a/b ＞ 1 situation, (b-c)/b≤0.03 and b >=10nm.
16. surface treatment copper foil according to claim 15, wherein, the copper foil is in the release layer side surface without roughening Particle.
17. the surface treatment copper foil according to claim 15 or 16, wherein, the release layer is by following formula：
[chemical formula 3]
(R1)m-M-(R2)n
(in formula, R1For alkoxy or halogen atom, R2It is the alkyl in the group being made up of alkyl, cycloalkyl and aryl, or Their any alkyl that more than one hydrogen atom is substituted with halogen atoms, any one of M Al, Ti, Zr, n be 0 or 1 or 2, m be more than 1 and M valence mumber below integer, R1It is at least one be alkoxy；Furthermore m+n is M valence mumber, that is, is existed It is 3 during Al situation, aluminic acid ester compounds, titanate compound, zirconate chemical combination in Ti, Zr situation 4) to represent Thing, their hydrolysate, the condensation body of the hydrolysate are used alone or combine a variety of uses and form.
18. the surface treatment copper foil according to claim 15 or 16, wherein, the release layer is by following formula：
[chemical formula 4]
(in formula, R1For alkoxy or halogen atom, R2It is the alkyl in the group being made up of alkyl, cycloalkyl and aryl, or Their any alkyl that more than one hydrogen atom is substituted with halogen atoms, R3And R4It is separately halogen atom, or Alkoxy, or the alkyl in the group being made up of alkyl, cycloalkyl and aryl, or more than one hydrogen atom is by halogen atom Substitution their any alkyl) represent silane compound, its hydrolysate, the hydrolysate condensation body be used alone Or a variety of uses of combination form.
19. the surface treatment copper foil according to claim 15 or 16, wherein, the release layer is that have 2 using intramolecular The compound of following sulfydryl forms.
20. the surface treatment copper foil according to any one of claim 15 to 19, wherein, the copper foil and the release layer it Between be provided with selected from by one or more of the group's that forms of refractory layer, antirust coat, chromic acid process layer and silane coupling process layer Layer.
21. surface treatment copper foil according to claim 20, wherein, it is selected from this by refractory layer, antirust coat, chromic acid processing The surface of the layer of one or more of the group of layer and silane coupling process layer composition is provided with resin bed.
22. the surface treatment copper foil according to any one of claim 15 to 21, wherein, set in the release layer side surface There is resin bed.
23. the surface treatment copper foil according to claim 21 or 22, wherein, the resin bed for then with resin, priming paint or The resin of semi-hardened state.
24. the surface treatment copper foil according to any one of claim 15 to 23, its thickness is 9~70 μm.
25. a kind of laminate, it possesses the surface treatment copper foil any one of claim 15 to 24 and is arranged on the table The resin base material of the release layer side of face processing copper foil.
26. laminate according to claim 25, wherein, the resin base material is prepreg, or contains thermosetting resin.
27. a kind of printing distributing board, it possesses the surface treatment copper foil having the right any one of requirement 15 to 24.
28. a kind of printing distributing board, it is that usage right requires the surface treatment copper foil any one of 15 to 24 and manufactured.
29. a kind of semiconductor packages, it possesses the printing distributing board described in claim 27 or 28.
30. a kind of e-machine, it possesses the printing distributing board having the right described in requirement 27 or 28, or described in claim 29 Semiconductor packages.
CN201680038794.8A 2015-08-03 2016-08-03 Manufacture method, surface treatment copper foil, laminate, printing distributing board, semiconductor packages and the e-machine of printing distributing board Pending CN107710890A (en)

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Application publication date: 20180216