CN101492814B - Process for producing double-layer flexible cover copper plate - Google Patents
Process for producing double-layer flexible cover copper plate Download PDFInfo
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- CN101492814B CN101492814B CN2009100466621A CN200910046662A CN101492814B CN 101492814 B CN101492814 B CN 101492814B CN 2009100466621 A CN2009100466621 A CN 2009100466621A CN 200910046662 A CN200910046662 A CN 200910046662A CN 101492814 B CN101492814 B CN 101492814B
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Abstract
The invention belongs to the field of micronano-electronic material, and relates to a method for preparing a two-layer flexible copper-clad lamination. The preparation method obtains the two-layer flexible copper-clad lamination through modifying surface of a flexible polyester substrate and self-assembling a chemical copper plating, and comprises the following steps: hydroxylating and sulfhydrylating surface of the flexible polyester substrate, and self assembling the chemical copper plating to obtain the flexible copper-clad lamination. A copper film and the substrate are connected through a chemical bond, and are generated in situ, so the prepared copper-clad lamination has the advantages of lightness and thinness, high tractility, high bonding strength, high conductivity, high flatness, acid resistance, alkali resistance, organic solvent resistance and the like, and can be widely applied to flexible circuit boards and flexible electronic devices, such as a flexible field effect transistor, a flexible solar cell, a flexible light emitting diode and the like.
Description
Technical field
The invention belongs to the micro-nano technical field of electronic materials, be specifically related to a kind of preparation method of double-layer flexible cover copper plate.
Background technology
(Flexible Copper Clad Lamination FCCL) is the basic material of producing flexible printed circuit board to flexible copper-clad plate, so the production technique of flexible copper-clad plate has greatly influence to the performance and the outward appearance of electronic product.Traditional FCCL adopts tackiness agent that insulated substrate and metal copper foil are bonded, and therefore is called three stratotype flexible copper-clad plates (3L-FCCL).But this flexible copper-clad plate thermotolerance is low, and dimensional stability is relatively poor, and base material thickness is bigger.And double-layer flexible cover copper plate is thinner, has premium propertiess such as higher flexibility, thermotolerance, can satisfy the requirement of high-density wiring to FCCL, therefore obtains high speed development.
The preparation method of double-layer flexible cover copper plate mainly contains: sputter electrochemical plating (Sputtering), laminating (Lamination), precasting cover (.CN101340774 such as Jin Hao such as method of being coated with (Casting); CN1579754 such as Xia Dengfeng; Model and equality .CN101157077), owing to cancelled Copper Foil and substrate intermediary tackiness agent, double-layer flexible cover copper plate is thinner about 12 microns than three layer flexible cover copper plates, this for adopt FCCL produce multi-layer flexible printed circuit board (Multilayer Flexible Printed Circuit Board) be very favourable (Yang Peifa etc. insulating material, 2006,39 (3), 27.).
At present, the fatal problem of double-layer flexible cover copper plate is that Copper Foil comes off from substrate easily.Trace it to its cause, it is physical adsorption that sputter electrochemical plating, laminating, precasting cover between the Copper Foil of ordinary method such as Tu Fa preparation and the substrate, i.e. Van der Waals force effect, in case expand with heat and contract with cold, the copper-clad plate internal stress is excessive, will cause that Copper Foil comes off or breaks, thereby influence the performance of flexible PCB.
The ordinary method that addresses this problem is as follows: with the substrate surface alligatoring, increase surface-area, further strengthen the riveted power of Copper Foil and substrate.This method can promote the binding property of Copper Foil and substrate to a certain extent, but directly consequence is that substrate surface is uneven, and the surface finish that causes copper-clad plate is tens to the hundreds of micron; The microelectronic integrated circuit live width has reached 100 nanometers and following level at present, and the copper-clad plate of method for preparing obviously can not be suitable for.
The present invention is directed to the shortcoming of traditional technology, a kind of preparation method of double-layer flexible cover copper plate of high-flatness is proposed, substrate surface is carried out modification, under the prerequisite of failure surface planeness not, introduce active group---sulfydryl, by the self-assembly electroless plating, make Copper Foil be connected by the Cu-S chemical bond with substrate; Generate because Copper Foil is an original position, and and substrate between be chemical b ` power, make the stripping strength of Copper Foil greatly improve; The stripping strength of the copper-clad plate of the present invention preparation is greater than 80N/mm, and conventional copper-clad plate only be about 2N/mm (Hu Futian etc. glass reinforced plastic/matrix material, 2008,2,83.).
Summary of the invention
The objective of the invention is to propose a kind of preparation method of double-layer flexible cover copper plate.
The preparation method of the double-layer flexible cover copper plate that the present invention proposes, its concrete steps are:
(1) clean substrate: with flexible polyester substrate cleaning, oven dry;
(2) substrate surface hydroxylation: the substrate after will cleaning placed amino substituted silane solution 0.5～2.5 hour, took out and cleaned, and oven dry makes the substrate surface hydroxylation;
(3) substrate surface sulfhydrylation: substrate was placed sulfydryl substituted silane solution 3～6 hours again, take out and clean, oven dry makes the substrate surface sulfhydrylation;
(4) electroless copper: at last the polyester substrate behind the sulfhydrylation is placed the copper chemical plating fluid,, takes out and clean in 20～80 ℃ of electroless platings 0.5～6 hour, oven dry, flexible copper-clad plate.
Among the present invention, its material of used polyester substrate be in polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate, poly terephthalic acid pentadiol ester, PEN or the poly terephthalic acid glycerine ester any one.
Among the present invention, the solute of used amino substituted silane solution is any one in γ-aminoethyl aminopropyl trimethoxysilane, γ-aminoethyl aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane or the 3-aminopropyl triethoxysilane; Solvent is any one in methyl alcohol, ethanol, Virahol, propyl carbinol, ethylene glycol, acetone, butanone, pimelinketone or the tetrahydrofuran (THF); The mass concentration of amino substituted silane solution is 0.1%～5%.
Among the present invention, the solute of used sulfydryl substituted silane solution is any one in 2-mercaptoethyl Trimethoxy silane, 2-mercaptoethyl triethoxyl silane, 3-sulfydryl propyl trimethoxy silicane or the 3-sulfydryl propyl-triethoxysilicane; Solvent is any one in acetone, butanone, pimelinketone, tetrahydrofuran (THF) or the ethyl acetate; The mass concentration of sulfydryl substituted silane solution is 0.1%～5%.
Among the present invention, the prescription of used copper chemical plating fluid is as follows: solvent is a deionized water, and solute is a copper sulfate (concentration: 4～8g/L), sodium-potassium tartrate (concentration: 5～10g/L), Trisodium Citrate (concentration: 8～12g/L), disodium ethylene diamine tetraacetate (concentration: 4～8g/L), dimethylamine borane (concentration: 4～8g/L), sodium hydroxide (concentration: 1～2g/L).
The present invention is by the flexible polyester surface modified substrate, and the self-assembly electroless copper gets double-layer flexible cover copper plate again; Because copper film is connected by chemical bond with substrate, and original position generates, the copper-clad plate of preparation has advantages such as frivolous, high ductibility, high bond strength, high conductivity, high-flatness and acidproof, alkaline-resisting, organic solvent-resistant, can be widely used in flexible PCB, flexible electronic device is as flexible field-effect transistor, flexible solar battery, flexible photodiode etc.
Description of drawings
Fig. 1 is the stereoscan photograph of double-layer flexible cover copper plate coating.
Embodiment
The invention is further illustrated by the following examples
Embodiment 1
With thickness is that 50 microns, area are that the polyethylene terephthalate substrate of 30 centimetres of 20 cm x is cleaned with deionized water, oven dry, placing concentration is the ethanolic soln of γ-aminoethyl aminopropyl trimethoxysilane of 0.1%, soaked 1 hour, take out, use ethanol drip washing, dry, get the polyethylene terephthalate substrate of surface hydroxylation.
It is the acetone soln of 1% 2-mercaptoethyl Trimethoxy silane that the polyethylene terephthalate substrate of surface hydroxylation is placed concentration, soaks 3 hours, takes out, and use acetone drip washing, oven dry, polyethylene terephthalate substrate that must surperficial sulfhydrylation.
4g copper sulfate, 10g sodium-potassium tartrate, 8g Trisodium Citrate, 6g disodium ethylene diamine tetraacetate, 6g dimethylamine borane, 1.5g sodium hydroxide are dissolved in the 500mL deionized water, and dissolving finishes, and adds deionized water, to liquor capacity be 1L, the copper chemical plating fluid.
The polyethylene terephthalate substrate of surperficial sulfhydrylation is placed above-mentioned plating bath,, takes out, wash with 50 ℃ of electroless platings 3 hours, oven dry, the copper-clad plate of polyethylene terephthalate base, copper thickness is 2 microns, stripping strength is greater than 80N/mm.
Embodiment 2
With thickness is that 50 microns, area are that the Poly(Trimethylene Terephthalate) substrate of 30 centimetres of 20 cm x is cleaned with deionized water, oven dry, placing concentration is the methanol solution of 0.5% 3-aminopropyl trimethoxysilane, soaked 1.5 hours, take out, use ethanol drip washing, dry, get the Poly(Trimethylene Terephthalate) substrate of surface hydroxylation.
It is the butanone solution of 0.1% 2-mercaptoethyl triethoxyl silane that the Poly(Trimethylene Terephthalate) substrate of surface hydroxylation is placed concentration, soaked 6 hours, and took out, use butanone drip washing, dry, get the Poly(Trimethylene Terephthalate) substrate of surperficial sulfhydrylation.
8g copper sulfate, 5g sodium-potassium tartrate, 12g Trisodium Citrate, 4g disodium ethylene diamine tetraacetate, 8g dimethylamine borane, 2g sodium hydroxide are dissolved in the 500mL deionized water, and dissolving finishes, and adds deionized water, to liquor capacity be 1L, the copper chemical plating fluid.
The Poly(Trimethylene Terephthalate) substrate of surperficial sulfhydrylation is placed above-mentioned plating bath,, takes out, wash with 20 ℃ of electroless platings 6 hours, oven dry, the copper-clad plate of Poly(Trimethylene Terephthalate) base, copper thickness is 0.5 micron, stripping strength is greater than 80N/mm.
Embodiment 3
With thickness is that 50 microns, area are that the polybutylene terephthalate substrate of 30 centimetres of 20 cm x is cleaned with deionized water, oven dry, placing concentration is the acetone soln of γ-aminoethyl aminopropyl triethoxysilane of 1%, soaked 2 hours, take out, use acetone drip washing, dry, get the polybutylene terephthalate substrate of surface hydroxylation.
It is the tetrahydrofuran solution of 5% 3-sulfydryl propyl trimethoxy silicane that the polybutylene terephthalate substrate of surface hydroxylation is placed concentration, soaked 4.5 hours, and took out, use tetrahydrofuran (THF) drip washing, dry, get the polybutylene terephthalate substrate of surperficial sulfhydrylation.
6g copper sulfate, 7.5g sodium-potassium tartrate, 10g Trisodium Citrate, 8g disodium ethylene diamine tetraacetate, 6g dimethylamine borane, 1g sodium hydroxide are dissolved in the 500mL deionized water, and dissolving finishes, and adds deionized water, to liquor capacity be 1L, the copper chemical plating fluid.
The polybutylene terephthalate substrate of surperficial sulfhydrylation is placed above-mentioned plating bath,, takes out, wash with 80 ℃ of electroless platings 0.5 hour, oven dry, the copper-clad plate of polybutylene terephthalate base, copper thickness is 3 microns, stripping strength is greater than 80N/mm.
Embodiment 4
With thickness is that 50 microns, area are that the poly terephthalic acid pentadiol ester substrate of 30 centimetres of 20 cm x is cleaned with deionized water, oven dry, placing concentration is the ethylene glycol solution of γ-aminoethyl aminopropyl trimethoxysilane of 2%, soaked 2.5 hours, take out, spent glycol drip washing is dried, and gets the poly terephthalic acid pentadiol ester substrate of surface hydroxylation.
It is the ethyl acetate solution of 2% 3-sulfydryl propyl-triethoxysilicane that the poly terephthalic acid pentadiol ester substrate of surface hydroxylation is placed concentration, soaked 3 hours, and took out, use ethyl acetate drip washing, dry, get the poly terephthalic acid pentadiol ester substrate of surperficial sulfhydrylation.
4g copper sulfate, 5g sodium-potassium tartrate, 8g Trisodium Citrate, 4g disodium ethylene diamine tetraacetate, 4g dimethylamine borane, 1g sodium hydroxide are dissolved in the 500mL deionized water, and dissolving finishes, and adds deionized water, to liquor capacity be 1L, the copper chemical plating fluid.
The poly terephthalic acid pentadiol ester substrate of surperficial sulfhydrylation is placed above-mentioned plating bath,, takes out, wash with 60 ℃ of electroless platings 2 hours, oven dry, the copper-clad plate of poly terephthalic acid pentanediol ester group, copper thickness is 2 microns, stripping strength is greater than 80N/mm.
Embodiment 5
With thickness is that 50 microns, area are that the PEN substrate of 30 centimetres of 20 cm x is cleaned with deionized water, oven dry, placing concentration is the tetrahydrofuran solution of 5% 3-aminopropyl trimethoxysilane, soaked 0.5 hour, take out, use tetrahydrofuran (THF) drip washing, dry, get the PEN substrate of surface hydroxylation.
It is the pimelinketone solution of 1% 3-sulfydryl propyl trimethoxy silicane that the PEN substrate of surface hydroxylation is placed concentration, soaks 5 hours, takes out, and use pimelinketone drip washing, oven dry, PEN substrate that must surperficial sulfhydrylation.
8g copper sulfate, 8g sodium-potassium tartrate, 8g Trisodium Citrate, 8g disodium ethylene diamine tetraacetate, 8g dimethylamine borane, 2g sodium hydroxide are dissolved in the 500mL deionized water, and dissolving finishes, and adds deionized water, to liquor capacity be 1L, the copper chemical plating fluid.
The PEN substrate of surperficial sulfhydrylation is placed above-mentioned plating bath,, takes out, wash with 60 ℃ of electroless platings 6 hours, oven dry, the copper-clad plate of PEN base, copper thickness is 10 microns, stripping strength is greater than 80N/mm.
Embodiment 6
With thickness is that 50 microns, area are that the poly terephthalic acid glycerine ester substrate of 30 centimetres of 20 cm x is cleaned with deionized water, oven dry, placing concentration is the butanone solution of 0.5% 3-aminopropyl triethoxysilane, soaked 1.5 hours, take out, use butanone drip washing, dry, get the poly terephthalic acid glycerine ester substrate of surface hydroxylation.
It is the acetone soln of 0.5% 2-mercaptoethyl triethoxyl silane that the poly terephthalic acid glycerine ester substrate of surface hydroxylation is placed concentration, soaked 4 hours, and took out, use acetone drip washing, dry, get the poly terephthalic acid glycerine ester substrate of surperficial sulfhydrylation.
5g copper sulfate, 5g sodium-potassium tartrate, 10g Trisodium Citrate, 4g disodium ethylene diamine tetraacetate, 5g dimethylamine borane, 1g sodium hydroxide are dissolved in the 500mL deionized water, and dissolving finishes, and adds deionized water, to liquor capacity be 1L, the copper chemical plating fluid.
The poly terephthalic acid glycerine ester substrate of surperficial sulfhydrylation is placed above-mentioned plating bath,, takes out, wash with 40 ℃ of electroless platings 4 hours, oven dry, the copper-clad plate of poly terephthalic acid glycerol ester group, copper thickness is 2.5 microns, stripping strength is greater than 80N/mm.
Claims (1)
1. the preparation method of a double-layer flexible cover copper plate is characterized in that concrete steps are:
(1) clean substrate: with flexible polyester substrate cleaning, oven dry;
(2) substrate surface hydroxylation: the substrate after will cleaning placed amino substituted silane solution 0.5～2.5 hour, took out and cleaned, and oven dry makes the substrate surface hydroxylation;
(3) substrate surface sulfhydrylation: substrate was placed sulfydryl substituted silane solution 3～6 hours again, take out and clean, oven dry makes the substrate surface sulfhydrylation;
(4) electroless copper: at last the polyester substrate behind the sulfhydrylation is placed the copper chemical plating fluid,, takes out and clean in 20～80 ℃ of electroless platings 0.5～6 hour, oven dry, flexible copper-clad plate;
Wherein, the prescription of copper chemical plating fluid is that solvent is a deionized water, and various solute concentrations are respectively in the solution:
Concentration of copper sulfate 4～8g/L;
Sodium tartrate potassium concn 5～10g/L;
Sodium citrate concentration 8～12g/L;
Disodium ethylene diamine tetraacetate concentration 4～8g/L;
Dimethylamine borane concentration 4～8g/L;
Naoh concentration 1～2g/L;
Above-mentioned polyester substrate material is: polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate, poly terephthalic acid pentadiol ester, any one in PEN or the poly terephthalic acid glycerine ester;
The solute of above-mentioned amino substituted silane solution is: any one in γ-aminoethyl aminopropyl trimethoxysilane, γ-aminoethyl aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane or the 3-aminopropyl triethoxysilane; Solvent is any one in methyl alcohol, ethanol, Virahol, propyl carbinol, ethylene glycol, acetone, butanone, pimelinketone or the tetrahydrofuran (THF); The mass concentration of amino substituted silane solution is 0.1%～5%;
The solute of above-mentioned sulfydryl substituted silane solution is: any one in 2-mercaptoethyl Trimethoxy silane, 2-mercaptoethyl triethoxyl silane, 3-sulfydryl propyl trimethoxy silicane or the 3-sulfydryl propyl-triethoxysilicane; Solvent is any one in acetone, butanone, pimelinketone, tetrahydrofuran (THF) or the ethyl acetate; The mass concentration of sulfydryl substituted silane solution is 0.1%～5%.
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| CN2009100466621A CN101492814B (en) | 2009-02-26 | 2009-02-26 | Process for producing double-layer flexible cover copper plate |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101892470A (en) * | 2010-07-19 | 2010-11-24 | 复旦大学 | Method for preparing flexible polyester nickel-coating electrode |
| CN101917826B (en) * | 2010-08-03 | 2013-08-21 | 东莞市仁吉电子材料有限公司 | Method for increasing bonding force between conductor and non-conductive polymer dielectric layer in substrate of printed circuit board |
| CN102121100A (en) * | 2011-01-27 | 2011-07-13 | 复旦大学 | 'Copper/straw' electromagnetic wave shield composite material and preparation method thereof |
| CN103060779A (en) * | 2012-12-04 | 2013-04-24 | 复旦大学 | Preparation method of copper/modal fiber composite material |
| CN104902689A (en) * | 2014-03-05 | 2015-09-09 | 立诚光电股份有限公司 | Method for manufacturing circuit and a ceramic substrate having circuit pattern |
| CN106884162A (en) * | 2017-01-05 | 2017-06-23 | 复旦大学 | A kind of preparation method of high corrosion-resistant high conductivity flexible copper-clad plate |
| CN110358128B (en) * | 2019-07-04 | 2021-09-14 | 苏州贝蒂克生物技术有限公司 | Method for modifying amino group on surface of polymer and characterization method of surface related performance of polymer |
| CN110408968B (en) * | 2019-09-04 | 2021-11-05 | 中国科学院深圳先进技术研究院 | Chemical plating solution and preparation method and application thereof |
| CN111826643B (en) * | 2020-07-14 | 2023-05-12 | 华东理工大学 | Method for improving binding force of plating layer by activating copper plating on surface of modified metal |
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