CN107699930A - The carrier extra thin copper foil of a kind of composite multi-component Nanoalloy as peel ply and preparation method thereof - Google Patents
The carrier extra thin copper foil of a kind of composite multi-component Nanoalloy as peel ply and preparation method thereof Download PDFInfo
- Publication number
- CN107699930A CN107699930A CN201710842236.3A CN201710842236A CN107699930A CN 107699930 A CN107699930 A CN 107699930A CN 201710842236 A CN201710842236 A CN 201710842236A CN 107699930 A CN107699930 A CN 107699930A
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- China
- Prior art keywords
- copper foil
- peel ply
- thin copper
- layer
- carrier
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
Abstract
The invention discloses the carrier extra thin copper foil of a kind of composite multi-component Nanoalloy as peel ply and preparation method thereof, it is made up of carrier copper foil layer, peel ply, extra thin copper foil layer, described peel ply is made up of organic layer and polynary nanometer alloy-layer；Organic layer is made up of metal organic framework compound and high molecular polymer, and polynary nanometer alloy-layer is made up of two or more the metal in zinc, copper, aluminium, nickel, tin.
Description
Technical field
The present invention relates to carrier extra thin copper foil technical field, more particularly to a kind of composite multi-component Nanoalloy is as peel ply
Carrier extra thin copper foil and preparation method thereof.
Background technology
Extra thin copper foil refers to thickness at 9 μm and its following copper foil used for printed circuit board（Again by title ultrathin copper foil）.Due to
Difficulty of the extra thin copper foil on taking, therefore typically it is all compounded with carrier as support.The species of carrier has metal foil (copper
Paper tinsel, aluminium foil), organic film etc..Because its current product form significant portion is all with the thin copper foil with carrier, therefore the text having
Offer the middle copper foil being referred to as it with carrier（Carrier copper foil）.PCB extra thin copper foils are usually by being electrolysed or rolling the manufacturing
Go out, and to use the copper foil kind that electrolytic method produces as the overwhelming majority.Either ultrathin electrolytic copper foil, or ultra-thin calendering
Copper foil belongs to the electronics copper foil of high-performance, high added value.
Electrolytic copper foil of the peelable type with carrier foils is again to peel off carrier after being laminated with base material by hot pressing processing mostly,
Used using extra thin copper foil as copper clad laminate, if peeled off at the combination interface of carrier foils and copper foil unstable situation or
Electrolytic copper foil is just peeled off when processing or can not be completely exfoliated after follow-up hot pressing processing, it will directly reduces circuit board
Combination property.In order to solve these problems, researchers are more using one centre of formation between carrier foils and extra thin copper foil layer
Peel ply so that there is certain peel strength, peel ply is broadly divided into inorganic release layer, organic between carrier foils and extra thin copper foil
Peel ply and the class of compound peel ply three, inorganic release layer are mainly metal level or alloy-layer；Organic peel ply be nitrogen-containing compound,
Sulfur-containing compound and carboxylic acid etc., often from BTA and carboxyl benzotriazole etc., and organic peel ply often poorly conductive,
Cause to occur organic matter absorption to be difficult to peel off less, adsorb the drawbacks of more electric conductivity are bad；Compound peel ply often selects organic layer
With alloy-layer together as peel ply, rare earth metal is wherein contained in alloy-layer, price is higher.
The content of the invention
A kind of the defects of present invention is in order to make up prior art, there is provided carrier of composite multi-component Nanoalloy as peel ply
Extra thin copper foil and preparation method thereof.
The present invention is achieved by the following technical solutions：
Carrier extra thin copper foil of a kind of composite multi-component Nanoalloy as peel ply, by carrier copper foil layer, peel ply, extra thin copper foil
Layer composition, described peel ply are made up of organic layer and polynary nanometer alloy-layer；Organic layer is by metal organic framework chemical combination
Thing forms with high molecular polymer, and polynary nanometer alloy-layer is by two or more the metal in zinc, copper, aluminium, nickel, tin
Composition.
Described carrier copper foil thickness degree is 30-35 μm.
Described metal organic framework compound is in ZIF-7, ZIF-8, UiO-66, UiO-67, MIL-100, MIL-125
One kind.
Described high molecular polymer is dimethyl silicone polymer, polyether amide block copolymer, polymethyl-benzene base silica
One kind in alkane.
A kind of preparation method of the described composite multi-component Nanoalloy as the carrier extra thin copper foil of peel ply, including it is following
Step：
(1) foil carriers are prepared by electrolysis or the tape casting, table then is carried out to it with 17 fluorine decyl trimethoxy silanes
Face is modified；
（2）High molecular polymer is put into hexamethylene, stirring is completely dissolved it, solution concentration control 5-20%, then adds
Metal organic framework compound, addition are the 1-15% of high molecular polymer, the processing of system sonic oscillation, are made dispersed
Treatment fluid, be subsequently added into crosslinking agent tetraethyl orthosilicate and catalyst dibutyl tin dilaurate, stir 20-24h, obtain organic layer
Standby into film liquid, wherein high molecular polymer, crosslinking agent, the weight ratio of catalyst three are 1：（0.05-0.15）：（0.01-
0.015）；
（3）Foil carriers after surface modification are immersed into organic layer into film liquid, processing time 10-25s, form organic layer；
（4）By organic layer, electro-deposition forms alloy-layer in polynary nanometer aluminium alloy is placed in, in polynary nanometer aluminium alloy metal from
Sub- concentration range is 5-100g/L, and complexing agent concentration 10-50g/L, electrodeposition temperature is 45-50 DEG C, 1.5-3A/dm2, processing
Time 5-10s；
(5) extra thin copper foil that a layer thickness is 1-9 μm is electroplated on alloyed layer, produces described carrier extra thin copper foil.
Described polynary nanometer aluminium alloy be prepared by complexing agent, polynary nanometer alloyed oxide and diluted acid or diluted alkaline and
Into pH value 4-10, temperature is 35-40 DEG C.
Described polynary nanometer alloyed oxide is that two or more element is selected from zinc, copper, aluminium, nickel, tin
Metal powder mixture is formed, then the metal powder mixture is put into vacuum smelting furnace and is smelted into multicomponent alloy liquid, is led to
Cross pure oxygen in high pressure to be atomized aluminium alloy, obtained in combustion tower after direct combustion oxidation.
Carrier extra thin copper foil advantage prepared by the present invention is：
（1）Surface modification is carried out to carrier copper foil with 17 fluorine decyl trimethoxy silanes, improves its bonding energy with organic layer
Power, improve the rippability after carrier copper foil is heated；
（2）Peel ply, profit are used as using the high molecular polymer of doping metals organic framework compounds and polynary nanometer alloy layer
The interface bond strength of carrier copper foil and peel ply is added with the unique performance of metallic framework compound, while is also had good
Good electric conductivity, and the electroplating deposition effect of follow-up alloy-layer is improved, the multicomponent alloy layer of formation is more fine and close smooth, peels off
Intensity controlled, it is easy to completely strip after heated, the copper foil interface hydrophobicity after stripping is good, and anti-corrosion capability is strong, effective to improve
The performance of follow-up printed circuit board.
Embodiment
Carrier extra thin copper foil of a kind of composite multi-component Nanoalloy as peel ply, by carrier copper foil layer, peel ply, ultra-thin
Copper foil layer is formed, and described peel ply is made up of organic layer and the Nanoalloy layer formed by zinc, copper compound；Wherein organic layer
It is made up of ZIF-7 and dimethyl silicone polymer.
Described carrier copper foil thickness degree is 30 μm.
A kind of composite multi-component Nanoalloy of the embodiment includes as the preparation method of the carrier extra thin copper foil of peel ply
Following steps：
(1) foil carriers are prepared by electrolysis or the tape casting, table then is carried out to it with 17 fluorine decyl trimethoxy silanes
Face is modified；
（2）Dimethyl silicone polymer is put into hexamethylene, stirring is completely dissolved it, solution concentration control 5%, then adds
ZIF-7, addition are the 1% of dimethyl silicone polymer, the processing of system sonic oscillation, dispersed treatment fluid are made, then adds
Enter crosslinking agent tetraethyl orthosilicate and catalyst dibutyl tin dilaurate, stir 20h, it is standby into film liquid to obtain organic layer, wherein poly-
Dimethyl siloxane, crosslinking agent, the weight ratio of catalyst three are 1：0.05：0.01；
（3）Foil carriers after surface modification are immersed into organic layer into film liquid, processing time 10s, form organic layer；
（4）By organic layer, electro-deposition forms alloy-layer in zinc-copper Nanoalloy liquid is placed in, zinc ion in polynary nanometer aluminium alloy
Concentration be 20 g/L, the concentration of copper ion is 15 g/L, and complexing agent concentration 10g/L, electrodeposition temperature is 45 DEG C, 1.5A/
Dm2, processing time 5s；
（5）The extra thin copper foil that a layer thickness is 1 μm is electroplated on alloyed layer, produces described carrier extra thin copper foil.
Described zinc-copper Nanoalloy liquid is formulated by complexing agent, zinc-copper Nanoalloy oxide and dilute sulfuric acid,
PH value is 4, and temperature is 35 DEG C.
Wherein zinc-copper Nanoalloy oxide is that the metal powder mixture of zinc, copper composition is put into vacuum smelting furnace
Multicomponent alloy liquid is smelted into, is atomized aluminium alloy by pure oxygen in high pressure, is obtained in combustion tower after direct combustion oxidation.
Claims (7)
- A kind of 1. carrier extra thin copper foil of composite multi-component Nanoalloy as peel ply, by carrier copper foil layer, peel ply, ultra-thin copper Layers of foil is formed, it is characterised in that described peel ply is made up of organic layer and polynary nanometer alloy-layer；Organic layer is by metal Organic framework compounds form with high molecular polymer, and polynary nanometer alloy-layer is by two kinds or two in zinc, copper, aluminium, nickel, tin The metal composition of the kind above.
- 2. carrier extra thin copper foil of a kind of composite multi-component Nanoalloy as peel ply as claimed in claim 1, its feature exist In described carrier copper foil thickness degree is 30-35 μm.
- 3. carrier extra thin copper foil of a kind of composite multi-component Nanoalloy as peel ply as claimed in claim 1, its feature exist In described metal organic framework compound is one in ZIF-7, ZIF-8, UiO-66, UiO-67, MIL-100, MIL-125 Kind.
- 4. carrier extra thin copper foil of a kind of composite multi-component Nanoalloy as peel ply as claimed in claim 1, its feature exist In described high molecular polymer is in dimethyl silicone polymer, polyether amide block copolymer, PSI It is a kind of.
- A kind of 5. preparation side of composite multi-component Nanoalloy as the carrier extra thin copper foil of peel ply as described in claim 1-4 Method, it is characterised in that comprise the following steps：(1) foil carriers are prepared by electrolysis or the tape casting, table then is carried out to it with 17 fluorine decyl trimethoxy silanes Face is modified；（2）High molecular polymer is put into hexamethylene, stirring is completely dissolved it, solution concentration control 5-20%, then adds Metal organic framework compound, addition are the 1-15% of high molecular polymer, the processing of system sonic oscillation, are made dispersed Treatment fluid, be subsequently added into crosslinking agent tetraethyl orthosilicate and catalyst dibutyl tin dilaurate, stir 20-24h, obtain organic layer Standby into film liquid, wherein high molecular polymer, crosslinking agent, the weight ratio of catalyst three are 1：（0.05-0.15）：（0.01- 0.015）；（3）Foil carriers after surface modification are immersed into organic layer into film liquid, processing time 10-25s, form organic layer；（4）By organic layer, electro-deposition forms alloy-layer in polynary nanometer aluminium alloy is placed in, in polynary nanometer aluminium alloy metal from Sub- concentration range is 5-100g/L, and complexing agent concentration 10-50g/L, electrodeposition temperature is 45-50 DEG C, 1.5-3A/dm2, processing Time 5-10s；(5) extra thin copper foil that a layer thickness is 1-9 μm is electroplated on alloyed layer, produces described carrier extra thin copper foil.
- A kind of 6. preparation side of composite multi-component Nanoalloy as the carrier extra thin copper foil of peel ply as claimed in claim 5 Method, it is characterised in that described polynary nanometer aluminium alloy is matched somebody with somebody by complexing agent, polynary nanometer alloyed oxide and diluted acid or diluted alkaline System forms, pH value 4-10, and temperature is 35-40 DEG C.
- A kind of 7. preparation side of composite multi-component Nanoalloy as the carrier extra thin copper foil of peel ply as claimed in claim 6 Method, it is characterised in that described polynary nanometer alloyed oxide is to select two or more from zinc, copper, aluminium, nickel, tin Element composition metal powder mixture, then the metal powder mixture is put into vacuum smelting furnace and is smelted into multicomponent alloy Liquid, aluminium alloy is atomized by pure oxygen in high pressure, obtained in combustion tower after direct combustion oxidation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710842236.3A CN107699930A (en) | 2017-09-18 | 2017-09-18 | The carrier extra thin copper foil of a kind of composite multi-component Nanoalloy as peel ply and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710842236.3A CN107699930A (en) | 2017-09-18 | 2017-09-18 | The carrier extra thin copper foil of a kind of composite multi-component Nanoalloy as peel ply and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN107699930A true CN107699930A (en) | 2018-02-16 |
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|---|---|---|---|
| CN201710842236.3A Pending CN107699930A (en) | 2017-09-18 | 2017-09-18 | The carrier extra thin copper foil of a kind of composite multi-component Nanoalloy as peel ply and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112853408A (en) * | 2020-12-31 | 2021-05-28 | 江西理工大学 | Preparation method of ultrathin carrier-attached copper foil easy to peel and pure in interface |
| CN113881980A (en) * | 2021-11-12 | 2022-01-04 | 山东金宝电子股份有限公司 | Stripping layer treatment liquid and preparation method of strippable carrier-attached ultrathin copper foil |
| CN114672855A (en) * | 2022-03-29 | 2022-06-28 | 电子科技大学 | Preparation method of ultrathin copper foil |
| CN115058711A (en) * | 2022-06-17 | 2022-09-16 | 山东大学 | Preparation method of easy-to-peel ultrathin carrier copper foil |
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| JP2002292788A (en) * | 2001-03-30 | 2002-10-09 | Nippon Denkai Kk | Composite copper foil and method for manufacturing the same |
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| CN102784562A (en) * | 2012-08-09 | 2012-11-21 | 大连理工大学 | Method for preparing metal organic framework film |
| US20140141274A1 (en) * | 2012-11-16 | 2014-05-22 | Nan Ya Plastics Corporation | Copper foil structure having blackened ultra-thin foil and manufacturing method thereof |
| CN106498467A (en) * | 2016-11-16 | 2017-03-15 | 山东金宝电子股份有限公司 | A kind of preparation method of the ultra-thin carrier copper foil that stably can be peeled off |
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2017
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Patent Citations (6)
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| JP2002292788A (en) * | 2001-03-30 | 2002-10-09 | Nippon Denkai Kk | Composite copper foil and method for manufacturing the same |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112853408A (en) * | 2020-12-31 | 2021-05-28 | 江西理工大学 | Preparation method of ultrathin carrier-attached copper foil easy to peel and pure in interface |
| CN112853408B (en) * | 2020-12-31 | 2021-11-16 | 江西理工大学 | Preparation method of ultrathin carrier-attached copper foil easy to peel and pure in interface |
| CN113881980A (en) * | 2021-11-12 | 2022-01-04 | 山东金宝电子股份有限公司 | Stripping layer treatment liquid and preparation method of strippable carrier-attached ultrathin copper foil |
| CN114672855A (en) * | 2022-03-29 | 2022-06-28 | 电子科技大学 | Preparation method of ultrathin copper foil |
| CN114672855B (en) * | 2022-03-29 | 2023-09-26 | 电子科技大学 | Preparation method of ultrathin copper foil |
| CN115058711A (en) * | 2022-06-17 | 2022-09-16 | 山东大学 | Preparation method of easy-to-peel ultrathin carrier copper foil |
| CN115058711B (en) * | 2022-06-17 | 2022-12-27 | 山东大学 | Preparation method of easily-stripped ultrathin carrier copper foil |
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Application publication date: 20180216 |