WO2017050272A1 - 薄膜涂层组合物与涂覆方法 - Google Patents

薄膜涂层组合物与涂覆方法 Download PDF

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WO2017050272A1
WO2017050272A1 PCT/CN2016/099874 CN2016099874W WO2017050272A1 WO 2017050272 A1 WO2017050272 A1 WO 2017050272A1 CN 2016099874 W CN2016099874 W CN 2016099874W WO 2017050272 A1 WO2017050272 A1 WO 2017050272A1
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Prior art keywords
coating
composition
film
substrate
poly
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PCT/CN2016/099874
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English (en)
French (fr)
Inventor
杨军
胡明俊
张腾元
郭秋泉
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杨军
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Priority to CN201680055011.7A priority Critical patent/CN108463519B/zh
Priority to CA2999372A priority patent/CA2999372A1/en
Publication of WO2017050272A1 publication Critical patent/WO2017050272A1/zh
Priority to US15/928,527 priority patent/US20180208792A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
    • C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C09D139/08—Homopolymers or copolymers of vinyl-pyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
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    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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    • C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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    • 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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    • 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
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/01—Tools for processing; Objects used during processing
    • H05K2203/0104—Tools for processing; Objects used during processing for patterning or coating
    • H05K2203/013—Inkjet printing, e.g. for printing insulating material or resist
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/072—Electroless plating, e.g. finish plating or initial plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
    • H05K2203/0783—Using solvent, e.g. for cleaning; Regulating solvent content of pastes or coatings for adjusting the viscosity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/12—Using specific substances
    • H05K2203/125—Inorganic compounds, e.g. silver salt
    • 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
    • H05K3/181—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 by electroless plating

Definitions

  • the invention relates to the field of solution-based film coating materials, such as polyester fiber film, polyimide film, polyvinyl chloride film, semi-embossed film, polyvinyl chloride film analog, etc., in particular, special It relates to coating materials based on SU-8 and poly(4-vinylpyridine) (P4VP).
  • solution-based film coating materials such as polyester fiber film, polyimide film, polyvinyl chloride film, semi-embossed film, polyvinyl chloride film analog, etc.
  • P4VP poly(4-vinylpyridine)
  • Electroless metal deposition provides a good solution to the aforementioned problem of metallization of the printed pattern by depositing a thin layer of metal onto the pre-loaded substrate via an autocatalytic redox reaction.
  • the active catalyst can be configured to a designated area on a flexible substrate and then obtained by electroless deposition to obtain the desired pattern of metal patterns.
  • untreated flexible plastics do not capture the catalyst components well due to the lack of binding sites, whereas pure physical adsorption typically causes the catalyst to diffuse into the ELD solution, causing the metal to be deposited.
  • the bonding of the substrate is not strong, resulting in poor coating quality, forming metal layer peeling or metal bumps, which is particularly prominent when the metal layer is thick. Therefore, it is necessary to change the surface properties of the flexible substrate to more efficiently take up the catalyst component and increase the degree of bonding of the metal to be deposited and the substrate.
  • Surface modification refers to changing the roughness of the surface or generating an active functional group by in situ oxidation reaction on the original surface, such as chemical etching or oxygen plasma treatment.
  • Surface addition refers to the addition of an additional active layer to the original plastic surface.
  • Typical surface additions include polymer grafting (A. Garcia, J. Polesel-Maris, P. Learn, S. Palacin, T .Berthelot, Adv. Funct. Mater. 2011, 21, 2096–2102.; A. Garcia, T. Berthelot, P. Learn, P. Jégou, S. Palacin, ChemPhysChem 2011, 12, 2973–2978.), surface Silanization (S. Sawada, Y. Masuda, P. Zhu, K. Koumoto, Langmuir 2006, 22, 332-337.; Y. Chang, C.
  • surface modification of the flexible substrate serves two main purposes, namely, selective and efficient ingestion of the catalyst component, and an increase in the degree of bonding of the substrate to the metal. Therefore, the surface modification of the plastic substrate should at least consider the above two aspects.
  • the modified surface must contain functional groups capable of efficiently capturing the catalyst component; on the other hand, the modified surface should be chemically resistant to the electroless plating bath and act as a buffer between the original substrate and the metal. Layers to improve the degree of bonding between the two.
  • surface modification by different methods can improve the compatibility between metals and organic plastics, but most of them are either too complicated or not environmentally friendly, or difficult to scale production. There are still large distances for production, low cost applications.
  • silane-based modified films containing ligands are not resistant to acids and alkalis, since most metal coating baths are alkaline Therefore, the silane-modified film cannot withstand the long-term electroless metal deposition process; the grafting of the brush polymer usually involves complicated steps and severe experimental conditions; the polyelectrolyte layer-by-layer deposition requires dozens of times. Repeated coating operations are therefore time consuming and inefficient. Therefore, these methods are not suitable for surface modification of large-area flexible plastics on a large scale.
  • P4VP molecules can also be applied directly to the surface of the substrate, simple physical adsorption often results in poor bonding of the modified layer. Therefore, it is necessary to develop a more cost-effective method to increase the degree of binding of P4VP molecules to substrates.
  • pyridine molecules can be used to cure epoxy resins (Xue, G.; Ishida, H.; Konig, JLM Akromol. Chem., Rapid Commun. 7 (1986) 37; Idem., Angew. Makromol. Chem. 142 (1986) 17), and subsequently P4VP shows the ability to crosslink epoxy resins (Meng, F.; Zhang, W.; Zheng, SJ Mater. Sci.
  • epoxy resin has strong reactivity and can form good chemical and mechanical bonds with polymer substrates; on the other hand, epoxy resin molecules can react with each other and with P4VP molecules. A strong crosslinked polymer network is formed on the substrate.
  • Another object of the present invention is to provide an effective coating to ensure that a deposited copper layer having a thickness of more than 7 microns can be conveniently fabricated on the surface of a flexible substrate without spalling, which is difficult to achieve on other modified surfaces.
  • the present invention achieves this goal by increasing the degree of bonding during dip coating to form a thicker decorative layer.
  • the coating allows the formation of a reticle by laser printing, ink jet printing, screen printing, gravure printing, and the like or direct deposition of a functional catalyst onto the surface of the film to promote the formation of a pattern of metal patterns.
  • SU-8 molecule and poly(4-vinylpyridine) (P4VP) as the main components of the film forming solution, wherein SU -8 as a curing agent and a binder, P4VP is used as a metal ligand, and then the solution is dip-coated on the surface of the plastic substrate and then cured.
  • P4VP poly(4-vinylpyridine)
  • a desirable film coating composition comprises one or more of the following components: poly(4-vinylpyridine), SU-8, 1,4-dioxane, 2-propanol and ethanol.
  • a method of coating a film substrate such as a polyester fiber film, a polyimide film, a polyvinyl chloride film, a semi-embossed film, and a polyvinyl chloride film analog, includes the following steps: 1) poly(4-vinylpyridine), 2) SU-8 is dissolved in a mixture of 1,4-dioxane and 2-propanol to form a uniform coating solution; a sufficient amount of the coating solution is passed through the dip Coating, spin coating, knife coating, inkjet printing, screen printing, and the like are applied to the surface of the substrate to form a uniform film coating on the substrate; the film coating on the substrate is baked in a furnace .
  • coating solutions containing poly(4-vinylpyridine), SU-8, 1,4-dioxane and 2-propanol An optional but more desirable solution is to incorporate one or more of the following components into the coating solution: glycerin, ethanol, polyvinylpyrrolidone, polyethylene glycol, surfactants, and the like.
  • Poly(4-vinylpyridine) (P4VP) is an excellent surface modifier for the uptake of transition metal ions due to its good alcohol solubility, chelating power and coordination metal loading capacity.
  • 4-vinylpyridine, as a reactive monomer can be initiated in situ by ultraviolet light or plasma, and thus can be used for surface modification of substrates.
  • SU-8 acts as a bridging agent to anchor the P4VP molecule to the surface of the substrate.
  • the coating adheres well to the substrate due to the strong covalent bonding.
  • the carbon-oxygen bond will become the main bonding type.
  • the oxycarbon ether linkage is more alkali resistant than the silicone-bonded and oxy-bonded groups of other polymers. This is for subsequent alkaline plating Electroless copper plating in liquid is very beneficial.
  • poly(4-vinylpyridine) is dissolved in 2-propanol to form a homogeneous solution, preferably at a concentration of from 1 w/v% to 8 w/v%, preferably from 3 w/v% to 6 w/ v%.
  • SU-8 is dissolved in 1,4-dioxane to form a homogeneous solution, preferably at a concentration of from 0.1 w/v% to 2 w/v%, preferably from 0.3 w/v% to 1 w/v. %.
  • the above two solutions are mixed to form a clear coating solution.
  • An ideal coating solution contains from 0.5 w/v% to 4 w/v% of P4VP and from 0.05 w/v% to 1 w/v% of SU-8, preferably from 1.5 w/v% to 3 w/v% of P4VP and 0.15 w/v% to 0.5 w/v% of SU-8.
  • the concentration of each component in the coating composition of the present invention is as follows, in terms of mass/volume:
  • Figure 1a is a schematic flow diagram of coating a PET film using a mixture of P4VP and SU-8;
  • Figure 1b is a thin transparent PET film
  • Figure 1c is a PET film modified with P4VP and SU-8;
  • Figure 1d shows a PET film coated with a copper layer after 1 h of electroless copper plating.
  • Figure 2a shows the FT-IR of P4VP, P4VP and SU-8 composite coatings, P4VP and SU-8 composite coatings without NaOH treatment, and P4VP and SU-8 composite coatings cured by 1M NaOH for 1 hour. Spectrum;
  • Figure 2b is a contact angle diagram of water and a pure PET film
  • Figure 2c is a schematic view showing the contact angle of water and a modified PET film
  • 2d is a schematic view showing the contact angle of the modified PET film after the curing of water and sodium hydroxide
  • Figure 3a is a schematic view showing the use of a laser printer to print a toner reticle on the surface of a modified substrate to produce a flexible circuit;
  • Figures 3b and 3c are two circuit patterns on two different sides of the same PET film, respectively.
  • 4a and 4b are SEM images of the surface of a copper layer plated with copper for 10 minutes;
  • 4c and 4d are SEM images of the surface of the copper layer after copper plating for 30 min and 1 h, respectively;
  • 4e and 4f are SEM images of a cross section of a copper layer deposited by 1 h and 12 h, respectively.
  • Figure 5 is a graph showing the surface resistivity of the copper layer and the thickness of the copper layer as a function of plating time.
  • Figure 6 is an SEM image of a cross section of a different thickness copper layer as a function of plating time.
  • the above two solutions were then mixed in a 1:1 ratio to give a clear solution.
  • the final solution contained 2 w/v% P4 VP and 0.2 w/v% SU-8.
  • the transparent PET film was washed with a 1:1 mixed solution of ethanol and acetone, and then dip-coated with an oxygen plasma treatment or directly immersed in a film-forming solution without using an oxygen plasma treatment. After 30 seconds, the film was slowly withdrawn from the solution and dried in air. Next, the dip-coated film was placed in a furnace at 120 ° C for 20 minutes to cause an in-situ crosslinking reaction of P4VP and SU-8.
  • the thickness of the coating can be controlled by adjusting the concentration of P4VP and SU-8 in a mixed solvent of 2-propanol and 1,4-dioxane.
  • the PET film exhibited a smooth surface with good surface uniformity.
  • the film coating on the PET substrate has good long-lasting uniformity, low tack and excellent adhesion.
  • AgNO 3 was dissolved in deionized water to prepare a 1 w/v% AgNO 3 solution, and the coated PET film was immersed in the above AgNO 3 solution for 10 seconds to take up silver ions. The film was then washed several times with water to remove free silver ions that were not bound to the pyridine ligand. The film is dried and placed in an electroless copper plating bath for a different period of time.
  • the electroless copper plating bath contains CuSO4 ⁇ 5H 2 O (14 g/L), NaOH (12 g/L), sodium potassium tartrate (16 g/L), EDTA ⁇ 2Na (20 g/L), HCHO (16.5 mL/L), 2,2'-bipyridyl (20 mg/L) and potassium ferrocyanide (10 mg/L).
  • Figure 1a shows a schematic flow diagram of coating a PET film using a mixture of P4VP and SU-8.
  • Oxygen plasma is used to introduce oxygen-containing groups and free radicals on the surface to activate the surface. In theory, these reactive groups excited by oxygen plasma can react with the epoxy groups of SU-8 to form covalent bonds.
  • Figures 1b and 1c show a digital photograph of a neat clear PET film and a P4VP and SU-8 modified PET film, respectively. It can be seen that even with a layer of P4VP and SU-8 composite, the film is flexible and highly transparent. The addition of P4VP and SU-8 thin layer composites did not significantly affect the appearance and mechanical properties of the PET film.
  • FT-IR Fourier Transform Infrared Spectroscopy
  • Figure 2a shows the FT-IR spectrum of P4VP coated on a substrate and its composites.
  • the different spectra differ somewhat in the position and intensity of the peaks.
  • the peak at 871 cm -1 corresponds well to the absorption peak of the benzene ring, indicating that SU-8 was successfully introduced into the composite coating.
  • the vibration absorption of the amide group at 1664 cm -1 is enhanced, further indicating that a crosslinking reaction occurs between the pyridyl group and the epoxy group and a new product containing an amide group is formed, which is related to other research reports. Consistent. In addition, for all coatings, between 1500 cm -1 and 1600 cm -1 , there are two strong absorption peaks belonging to the P4VP molecular pyridine ring. Before and after curing, there was no significant change in the position and strength of these two peaks, indicating that only a small amount of pyridine ligand was consumed by the epoxy group during the curing process, which was due to the relatively high content of P4VP in the composite material.
  • Figure 2a also shows the FT-IR spectrum of the P4VP and SU-8 composite coatings cured after 1 hour of treatment with 1 M NaOH. This spectrum is almost identical to the spectrum of the sample that has not been treated with NaOH, indicating that the initial coating remains well on the surface of the substrate and is somewhat resistant to corrosion by alkaline solutions.
  • Figure 2b shows that the contact angle of water with the neat PET film is approximately 46 degrees. The contact angle after surface modification increased to about 77 degrees, probably due to the introduction of hydrophobic SU-8. After treatment with NaOH, the contact angle was slightly reduced but still significantly larger than the contact angle of the pure PET film.
  • the coating of the present invention alters the surface energy of PET and makes PET more hydrophobic. Perhaps enhanced hydrophobicity is not conducive to the wettability of the film, but can prevent excessive diffusion of the aqueous ink. When the modified film is used as a substrate for inkjet printing, this will also help to improve the printing ink on the substrate. Resolution.
  • the coating composition and coating method were identical to those of Example 1.
  • the coated PET film was activated by dipping in a 1 w/v% AgNO 3 solution for 10 seconds and then dried for printing.
  • the commercial HP laser printer HP6700 is used to print toner masks. After printing, the film was placed in a furnace at 90 ° C for 1 min to stabilize the toner reticle and then immersed in an electroless copper plating bath for various times. The exposed areas will be plated with a copper layer and, at the same time, the copper layer will not form due to catalyst deactivation of the reticle coverage area. After obtaining a copper pattern of a certain thickness, the reticle layer can be ultrasonically eluted in acetone or directly eluted with dichloromethane or tetrahydrofuran.
  • FIG. 3 is a detailed schematic view of producing a flexible circuit by printing a toner reticle on the surface of a modified substrate by using a laser printer.
  • Figures 3b and 3c show two circuit patterns on two different sides of the same PET film. Green area For printing toner.
  • FIG. 4 shows an SEM image of a copper layer deposited as described. The surface morphology of the copper layer after 10 min of copper plating is shown in Figures 4a and 4b. Many small pits are visible on the surface of the copper layer, which may be due to the soft template effect of hydrogen bubbles generated during the electroless copper plating process.
  • the thickness of the copper layer was investigated as a function of plating time, and the corresponding images and curves are shown in FIGS. 5 and 6. The conductivity corresponding to different thicknesses is also shown. It can be seen that the copper layer continues to grow within 2 hours and has a faster growth rate in the first hour because the initial concentration and pH of copper ions in the copper plating solution are higher at this time. As the electroless copper plating process progresses, copper ions and hydroxide ions are continuously consumed, and the growth of the copper layer is gradually slowed down until all copper ions are consumed.
  • the corresponding surface resistance decreases rapidly as the thickness of the copper layer increases.
  • the surface resistance of the copper layer can reach 0.021 ⁇ /m 2 .
  • ⁇ the volume resistivity
  • Rs the surface resistivity
  • t the thickness of the metal layer
  • the volume resistivity ⁇ of the deposited copper Based on the thickness and the corresponding surface resistivity data, it can be calculated that the volume resistivity of the copper layer deposited over 10 min is about 4.8 ⁇ 10 -8 ⁇ m, which is 2.7 times the volume resistivity of ordinary copper.
  • the volume resistivity of the copper layer drops significantly and gradually approaches the volume resistivity of ordinary copper.
  • the volume resistivity of the copper layer becomes about 2.8 ⁇ 10 -8 ⁇ m, which is 1.6 times that of ordinary copper.
  • the conductivity of the copper layer can reach 70% of that of ordinary copper. Therefore, the thickened copper layer not only enhances the conduction of the copper layer, but also improves the conductivity. High conduction will significantly reduce power loss and greatly facilitate the loading of high power electronic components in flexible electronic devices.
  • Example 3-13 the components in each of the formulations were uniformly mixed to prepare a coating solution, and applied to the PET film as described in Example 1 and Example 2 to form a smooth surface.
  • the respective components of the coating composition of the present invention may also be directly added to a solvent and then mixed to form a coating solution.
  • the separately prepared solutions should be mixed in a 1:1 ratio.
  • the surface of the modified PET film carries a large amount of pyridine ligands due to the binding of a large number of P4VP molecules, and these pyridine ligands can effectively capture various transition metal ions from the solution.
  • Pd 2+ and Ag + ions are two typical catalysts for electroless copper plating. They can be attacked by lone pairs of nitrogen atoms in the pyridine ligand and form strong coordinate bonds.
  • the silver ions will be chemisorbed to the PET surface. Unlike pure physical adsorption, the chemical bonds are much stronger and the adsorbed silver ions are almost impossible to get out of the surface.
  • Figure 1d shows a PET film coated with a copper layer over 1 h of electroless copper plating. As shown, the copper layer can be well plated over the entire PET substrate with good flexibility.
  • FIGS 4c and 4d show the surface morphology of the copper layer after 30 min and 1 h copper plating, respectively. It is apparent that as the copper plating time increases, the copper grains grow and the copper layer becomes dense.
  • Figures 4e and 4f show cross sections of a copper layer deposited over 1 h and 12 h, respectively.
  • the copper layer has a thickness of about 1.3 to 1.4 ⁇ m after 1 h of copper plating.
  • the copper layer was closely adhered to the substrate and no peeling was observed.
  • the scotch tape test was used to check the bond strength of the copper layer and it was found that the copper layer could be peeled off from the PET surface. Even with a thickness of 7 microns, the copper layer and the substrate still have a strong bond (Fig. 4f).
  • the copper layer is easily stripped once the copper layer becomes thicker.
  • the modified film is very suitable as a flexible substrate for flexible circuit printing.

Abstract

一种用于涂覆聚酯纤维薄膜、聚酰亚胺薄膜、聚氯乙烯薄膜、半压纹薄膜及聚氯乙烯薄膜类似物的涂层组合物，包括聚(4-乙烯基吡啶)，SU-8，溶剂如异丙醇、1,4-二氧六环；以及一种基于溶液的涂覆方法，该方法可快速地对各类材料进行表面改性，其通过提供足量的吡啶配体使过渡金属离子得以固定，形成位于基材与沉积金属之间的粘附促进层，从而催化以表面金属化为目的的化学镀铜及其它金属。

Description

[根据细则37.2由ISA制定的发明名称]　薄膜涂层组合物与涂覆方法 技术领域
本发明涉及基于溶液的薄膜涂层材料领域，所述薄膜如聚酯纤维薄膜、聚酰亚胺薄膜、聚氯乙烯薄膜、半压纹薄膜、聚氯乙烯薄膜类似物等，具体的说，特别涉及基于SU－8和聚(4-乙烯基吡啶)(P4VP)的涂层材料。
背景技术
近来，关于柔性电子器件的研究日益升温，这是由于其在许多应用领域，例如可穿戴电子设备、移动设备、医用植入体等，显露出优异的应用前景。(S.R.Forrest,Nature 2004,428,911-918.；D.H.Kim,N.S.Lu,R.Ma,Y.S.Kim,R.H.Kim,S.D.Wang,J.Wu,S.M.Won,H.Tao,A.Islam,K.J.Yu,T.I.Kim,R.Chowdhury,M.Ying,L.Z.Xu,M.Li,H.J.Chung,H.Keum,M.McCormick,P.Liu,Y.W.Zhang,F.G.Omenetto,Y.G.Huang,T.Coleman,J.A.Rogers,Science 2011,333,838.；Y.G.Sun,J.A.Rogers,Adv.Mater.2007,19,1897–1916.)柔性电路，作为柔性电子产品的“血液循环系统”，其重要性毋庸置疑。由于其灵活的数字处理模式和快速的可规模化生产的特点，现代印刷技术对于快速设计和不同样式的制作而言是一种强大的工具。将印刷技术应用于柔性电子器件的制造无疑会为柔性电路的生产打开一扇崭新的大门。由于印刷机可以高效地制作出各种图案样式，如何将印刷好的图案样式转化成导电电路自然就成了问题的关键。无电金属沉积(ELD)可通过一个自催化的氧化还原反应将薄层金属沉积于预先加载了催化剂的基材之上，为解决前述的打印图案金属化的问题提供了一个很好的方案。(R.S.Guo,Y.Yu,Z.Xie,X.Liu,X.Zhou,Yufan Gao,Z.Liu,F.Zhou,Y.Yang,Z.Zheng,Adv.；M.S.Miller,H.L.Filiatrault,G.J.E.Davidson,M.Luo,T.B.Carmichael,J.Am.Chem.Soc.2010,132,765–772.；T.Zhang,X.Wang,T.Li,Q.Guo and J.Yang,J.Mater.Chem.C,2014,2,286–294.)通过印刷技术的协助，活性催化剂可以被配置到柔性基材上的指定区域，然后通过无电沉积得到所需的金属图案样式。然而，作为一个公开的难题，未经处理的柔性塑料由于缺乏结合位点因而不能很好地抓取催化剂组分，而单纯的物理吸附则通常会导致催化剂向ELD溶液扩散使得待沉积的金属与基材结合不牢，从而造成涂层质量不佳，形成金属层剥离或金属凸块，这一问题在金属层变厚的时候尤为突出。因此，改变柔性基材的表面性质使其能更有效地摄取催化剂组分并提高待沉积金属和基材的结合度是很有必要的。
现在主要有两种普遍的方法对塑料进行表面修饰，分别为表面改性和表面添加。表面改性是指改变表面的粗糙度或是在原表面通过原位氧化反应产生活性官能团，例如化学蚀刻、氧等离子体处理。(A.Garcia,T.Berthelot,P.Viel,A.Mesnage,P.Jégou,F.Nekelson,Sébastien  Roussel,S.Palacin,ACS Appl.Mater.Interfaces 2010,2,1177-1183.；J.B.Park,J.S.Oh,E.L.Gil,S.J.Kyoung,J.T.Lim,G.Y.Yeom,J.Electrochem.Soc.,2010,157,D614-D619.)表面添加是指在原有塑料表面添加一层额外的活性层，典型的表面添加包括聚合物接枝(A.Garcia,J.Polesel-Maris,P.Viel,S.Palacin,T.Berthelot,Adv.Funct.Mater.2011,21,2096–2102.；A.Garcia,T.Berthelot,P.Viel,P.Jégou,S.Palacin,ChemPhysChem 2011,12,2973–2978.)，表面硅烷化(S.Sawada,Y.Masuda,P.Zhu,K.Koumoto,Langmuir 2006,22,332-337.；Y.Chang,C.Yang,X.-Y.Zheng,D.-Y.Wang,Z.-G.Yang,ACS Appl.Mater.Interfaces 2014,6,768-772.)和聚电解质逐层沉积(K.Cheng,M.-H.Yang,W.W.W.Chiu,C.-Y.Huang,J.Chang,T.-F.Ying,Y.Yang,Macromol.Rapid Commun.2005,26,247–264.；T.C.Wang,B.Chen,M.F.Rubner,R.E.Cohen Langmuir 2001,17,6610-6615.)等。
如上所述，对柔性基材进行表面修饰主要有两个目的，即实现对催化剂组分有选择且高效的摄取，以及提高基材与金属的结合程度。因此，塑料基材的表面修饰应该至少考虑上述两个方面。一方面，修饰后的表面必须含有能高效抓取催化剂组分的官能团；另一方面，修饰后的表面应对无电镀膜浴液具有化学耐受性并可在原始基材和金属之间充当缓冲层以提高二者的结合度。许多报告已经表明通过不同方法进行表面修饰可以提高金属和有机塑料之间的相容性，但是其中大多数方法要么是工艺流程过于复杂或不够环保，要么是规模化生产有难度，因而距可量产的、低成本的应用还有较大距离。例如，典型的用于印刷电路板表面修饰的含铬蚀刻剂由于对环境有害已被多国禁止使用；含有配体的硅烷基的改性膜不耐酸碱，由于大多数金属镀膜浴液呈碱性，因此硅烷改性膜无法耐受长时间的无电金属沉积过程；刷状聚合物的接枝通常牵涉复杂的步骤及严苛的实验条件要求；聚电解质逐层沉积由于需要进行数十次反复的镀膜操作因而非常耗时且低效。所以，这些方法都不适用于大规模地对大面积柔性塑料进行表面修饰。
尽管P4VP分子也可以被直接涂布到基材表面，但是单纯的物理吸附常常会导致修饰层结合不牢。因此，有必要开发一种更具成本效益的方法提高P4VP分子在基材上的结合度。早在20世纪80年代，人们就已经发现吡啶分子可用于固化环氧树脂(Xue,G.；Ishida,H.；Konig,J.L.Makromol.Chem.,Rapid Commun.7(1986)37；Idem.,Angew.Makromol.Chem.142(1986)17)，随后P4VP又显现出交联环氧树脂的能力(Meng,F.；Zhang,W.；Zheng,S.J.Mater.Sci.40(2005)6367–6373)。基于这个机制，在本发明中我们采用了环氧树脂交联P4VP分子的高分子膜涂覆技术。一方面，环氧树脂具有很强的反应性，可以和聚合物基材形成良好的化学结合和机械结合；另一方面，环氧树脂分子相互之间以及与P4VP分子之间也能发生反应从而在基材上形成牢固的交联的聚合物网络。
发明内容
本发明的目的是提供一种简单的一步完成的基于溶液的涂覆方法，该方法适用于对不同尺寸的薄膜进行大规模表面修饰，在极大地降低薄膜处理成本的同时还能满足高质量金属沉积的要求。
本发明的另一个目的是提供一种有效的涂层以确保在柔性基材表面能便利地制作出厚度超过7微米的沉积铜层而不产生剥落，这一点在其他改性表面难以实现，而本发明通过提高浸涂时的结合程度形成较厚的修饰层从而实现这个目标。
本发明还有一个目的是提供一种与印刷技术相容的薄膜涂层。该涂层允许通过激光印刷、喷墨印刷、丝网印刷、凹版印刷及类似技术制作掩模版或直接将功能性催化剂沉积到薄膜表面，从而促使金属图案样式的形成。
这些目的及通过本发明达成的其它目的将在下文详述。
在本发明中，基于热引发的环氧树脂与吡啶环之间的交联反应，我们使用SU-8分子和聚(4-乙烯基吡啶)(P4VP)作为成膜溶液的主要成分，其中SU-8作为固化剂和粘合剂，P4VP作为金属配体，随后将该溶液浸涂于塑料基材的表面再进行固化。
本发明中，理想的薄膜涂层组合物包括以下一种或多种成分：聚(4-乙烯基吡啶)，SU-8，1，4-二氧六环，2-丙醇及乙醇。
根据本发明，一种对薄膜基材，例如聚酯纤维薄膜、聚酰亚胺薄膜、聚氯乙烯薄膜、半压纹薄膜及聚氯乙烯薄膜类似物，进行涂覆的方法包括以下步骤：将1)聚(4-乙烯基吡啶)、2)SU-8溶于1，4-二氧六环和2-丙醇的混合物形成均匀的涂层溶液；将足量所述涂层溶液通过浸涂、旋涂、刮刀涂布、喷墨印刷、丝网印刷及类似方法涂布于基材表面以在基材上形成均匀薄膜涂层；将基材上的薄膜涂层置于炉中烘烤。针对上述不同的涂膜技术，为了使含有聚(4-乙烯基吡啶)、SU-8、1，4-二氧六环及2-丙醇的涂层溶液达到所需的性能，如表面张力、黏度等，一个可选但更理想的方案是在所述涂层溶液中掺入下述一种或几种成分：甘油、乙醇、聚乙烯吡咯烷酮、聚乙二醇、表面活性剂等。
聚(4-乙烯基吡啶)(P4VP)是一种用于摄取过渡金属离子的优良表面改性剂，由于其具有良好的醇溶性、螯合力以及配位金属加载能力。4-乙烯基吡啶，作为一种有反应活性的单体，可以通过紫外光或等离子体引发原位聚合，因此可用于基材的表面修饰。
SU-8作为桥接剂可将P4VP分子锚定于基材表面。由于存在强力的共价结合，如此形成的涂层可与基材良好黏合。此外，作为环氧基团开环反应的结果，碳氧键将成为主要的键合类型。相较于其他聚合物接枝的硅氧键和酯基团，碳氧醚键更耐碱性。这对于后续的碱性镀 液中化学镀铜沉积是非常有益的。
优选地，将聚(4-乙烯基吡啶)(P4VP)溶解于2-丙醇制成均匀的溶液，理想浓度为1w/v％～8w/v％，最好是3w/v％～6w/v％。优选地，将SU-8溶解于1，4-二氧六环也制成均匀的溶液，理想浓度为0.1w/v％～2w/v％，最好是0.3w/v％～1w/v％。优选地，上述两种溶液混合形成透明的涂层溶液。理想的涂层溶液含有0.5w/v％～4w/v％的P4VP和0.05w/v％～1w/v％的SU-8，最好是1.5w/v％～3w/v％的P4VP和0.15w/v％～0.5w/v％的SU-8。
本发明的涂层组合物中各组分的浓度范围如下，以质量/体积计：
成分 理想范围(w/v％) 优选范围(w/v％)
聚(4-乙烯基吡啶)(P4VP) 0.5‐4 1.5‐3
SU‐8 0.05‐1 0.15‐0.5
1,4‐二氧六环 47‐50 48.25‐49.75
2‐丙醇 47‐50 48.25‐49.75
附图说明
图1a为使用P4VP和SU-8混合物涂覆PET薄膜的流程示意图；
图1b为纯净的透明PET膜薄；
图1c为使用P4VP和SU-8改性的PET薄膜；
图1d为经1h化学镀铜的覆有铜层的PET薄膜。
图2a分别为P4VP、P4VP和SU-8复合涂层、未经NaOH处理的P4VP和SU-8复合涂层、经1M NaOH处理1小时固化后的P4VP和SU-8复合涂层的FT-IR光谱图；
图2b为水与纯净PET薄膜的接触角示图；
图2c为水与改性PET薄膜的接触角示意图；
图2d为水与氢氧化钠固化处理后改性PET薄膜的接触角示意图；
图3a为采用激光打印机在改性基材表面印刷墨粉掩模版以生产柔性电路的示意图；
图3b、图3c分别为同一片PET薄膜的两个不同侧面上的两个电路样式。
图4a、图4b为经10min镀铜的铜层表面SEM图像；
图4c、图4d分别为经30min、1h镀铜后的铜层表面SEM图像；
图4e、图4f分别为经1h、12h铜沉积的铜层横截面SEM图像。
图5为铜层表面电阻率及铜层厚度随电镀时间的变化曲线图。
图6为随电镀时间变化的不同厚度铜层横截面SEM图像。
下面的实施例说明了本发明及其在印刷电子产品制造中的应用。
具体实施方式
实施例1：
将聚(4-乙烯基吡啶)(P4VP)溶解于2-丙醇制成4w/v％的溶液，将SU-8溶解于1，4-二氧六环制成0.4w/v％的溶液。然后将上述两种溶液按1:1比例混合得到透明溶液。最终溶液含有2w/v％P4VP和0.2w/v％SU-8。
透明PET薄膜经乙醇和丙酮1:1混合溶液清洗，随后，使用氧等离子体处理后浸涂，或者不使用氧等离子体处理直接将其浸入成膜溶液进行浸涂。30秒后，将薄膜从溶液中缓缓抽出并在空气中干燥。接下来，将浸涂后的薄膜置于120℃炉中20分钟以便P4VP和SU－8发生原位交联反应。涂层的厚度可通过调节P4VP和SU-8在2-丙醇及1，4-二氧六环混合溶剂中的浓度来控制。
涂覆过程结束后，PET薄膜展示出具有良好的表面均匀性的光滑的表面。PET基材上的薄膜涂层具有良好的持久均匀性、很小的粘性以及出色的附着力。
成分 百分比 用量
聚(4-乙烯基吡啶)(P4VP) 2w/v％ 2g
SU-8 0.2w/v％ 0.2g
1,4-二氧六环 50v/v％ 50mL
2-丙醇 50v/v％ 50mL
为了展示本发明涂层的功能，将AgNO3溶解于去离子水中配制成1w/v％的AgNO3溶液，涂覆有涂层的PET薄膜浸入上述AgNO3溶液10秒钟以摄取银离子。随后用水清洗薄膜数次以除去未与吡啶配体结合的游离银离子。薄膜经干燥后放入化学镀铜镀液中保持不同的时间。化学镀铜镀液含有CuSO4·5H2O(14g/L)、NaOH(12g/L)、酒石酸钾钠(16g/L)、EDTA·2Na(20g/L)、HCHO(16.5mL/L)、2,2’-联吡啶(20mg/L)以及亚铁氰化钾(10mg/L)。
图1a显示了使用P4VP和SU-8混合物涂覆PET薄膜的流程示意图。氧等离子体用于在表面引入含氧基团和自由基从而活化表面。理论上，这些被氧等离子体激发的活性基团可以和SU-8的环氧基团反应形成共价键。图1b和1c分别显示了纯净的透明PET膜薄和使用P4VP及SU-8改性的PET薄膜的数码相片。从中可见，即使被涂上一层P4VP和SU-8复合材料，薄膜依然柔韧且高度透明。P4VP和SU-8薄层复合材料的加入并没有显著影响PET薄膜的外观和机械性能。
为了进一步展示本发明涂层组分的内在原理，使用FT-IR光谱仪6700(Thermo Scientific Co.)进行了傅立叶变换红外光谱(FT-IR)分析。水与不同基材的接触角通过 Ramé-Hart测角仪测量。
图2a显示了基材上涂布的P4VP及其复合材料的FT-IR光谱，不同的光谱在峰的位置和强度上有些差异。通过参照不同官能团的标准红外吸收图谱，我们从上述光谱图中可以得到许多信息。位于871cm-1处的峰与苯环的吸收峰良好对应，表明SU-8被成功地引入了复合涂层。我们还可以看到，经过固化后，915cm-1处的环氧基团几乎完全消失，表明强反应活性的环氧基团在相对较高的固化温度下几乎耗尽。再者，1664cm-1处属于酰胺基团的振动吸收增强，进一步表明吡啶基团与环氧基团之间发生了交联反应并生成了新的含有酰胺基团的产物，这与其他研究报告一致。此外，对所有涂层来说，在1500cm-1和1600cm-1之间，均存在两个属于P4VP分子吡啶环的强吸收峰。固化前后，这两个峰的位置和强度均无明显变化，说明在固化过程中仅有少量吡啶配体被环氧基团消耗，这是由于P4VP在复合材料中含量相对高出许多的缘故，因此还有大量剩余的吡啶配体可以在接下来的步骤中用于摄取催化剂组分。图2a还显示了经1M NaOH处理1小时固化后的P4VP和SU-8复合涂层的FT-IR光谱。该光谱与未经NaOH处理的样品光谱几乎一致，说明最初的涂层依然很好地留存在基材的表面，并且在一定程度上可以抵御碱性溶液的腐蚀。图2b显示了水与纯净PET薄膜的接触角大约为46度。表面改性后接触角增加到77度左右，这大概是由于引入了疏水性的SU-8的缘故。经NaOH处理后，接触角略微减小但依然明显大于纯净PET薄膜的接触角。
显然，本发明的涂层改变了PET的表面能并且使得PET更加疏水。也许增强的疏水性不利于薄膜的润湿性，但可以防止水性油墨的过度扩散，当改性薄膜被用作喷墨印刷的基材时，这也将有助于提高印刷油墨在基材上的分辨率。
在接下来的实施例2中，会制作出一个基于本发明涂层组分的功能电路。所进行的扫描电子显微镜(SEM)研究可进一步展示本发明的功能。
实施例2：
涂层组分和涂覆方法与实施例1完全一致。
涂有涂层的PET薄膜通过浸入1w/v％AgNO3溶液10秒被激活，随后干燥以备印刷。商用惠普激光打印机HP6700被用于印刷墨粉掩模版。印刷后，薄膜被置于90℃炉中1min以稳定墨粉掩模版，随后被浸入化学镀铜镀液不同的时间。暴露区域将被镀上铜层，同时，由于掩模版覆盖区域催化剂失活，铜层不会形成。在获得一定厚度的铜质样式后，掩模版层可在丙酮中超声洗脱或是用二氯甲烷或四氢呋喃直接洗脱。
图3为通过使用激光打印机在改性基材表面印刷墨粉掩模版以生产柔性电路的详细示意图。图3b和图3c显示了同一片PET薄膜的两个不同侧面上的两个电路样式。绿色区域 为印刷的墨粉。
扫描电镜SEM图像与能量色散X射线光谱(EDX)使用日立S-4500场发射扫描电子显微镜(FE-SEM)在5kV加速电压下获得。图4显示了按所述方法沉积的铜层的SEM图像。经10min镀铜的铜层表面形态如图4a和图4b所示。铜层表面可见许多小坑，这可能是由于化学镀铜过程中产生的氢气泡的软模板效应引起的。
此外，还研究了铜层厚度随电镀时间的变化，相应的图像和曲线如图5和图6所示。同时也显示了不同厚度对应的电导率。从中可见，在2小时内铜层持续生长，并且在第一个小时内具有更快的生长率，这是由于此时镀铜液中铜离子初始浓度及pH值较高。随着化学镀铜过程的进行，铜离子和氢氧根离子持续被消耗，铜层的生长逐步减慢直至所有铜离子消耗殆尽。
我们发现在12小时化学镀铜之后，铜层的厚度可达到7微米，随后我们研究了铜层的表面电阻。
我们发现相应的表面电阻随着铜层厚度的增加极速减小。经1h镀铜后，铜层的表面电阻可达0.021Ω/平方米。根据方程式ρ＝Rs·t,其中ρ为体积电阻率，Rs为表面电阻率，t为金属层厚度，我们可以计算出沉积铜的体积电阻率ρ。根据厚度和相应的表面电阻率数据，可计算出经10min沉积的铜层的体积电阻率约为4.8×10-8Ω·m，这是普通铜体积电阻率的2.7倍。随着铜层厚度的增加，体积电阻率显著下降并逐步接近普通铜的体积电阻率。当镀铜时间增至1h时，铜层的体积电阻率变为约2.8×10-8Ω·m，是普通铜体积电阻率的1.6倍。
此外，当铜层厚度达到7微米时，铜层的电导率可达到接近普通铜电导率的70％。因此，增厚的铜层不仅增强了铜层的传导，也改善了传导率。高传导将会明显地减少电能损耗并大大有利于在柔性电子器件中装载高功率的电子元器件。
在下述的实施例3-13中，每个配方中的组分都被均匀混合制成涂层溶液，并如实施例1和实施例2所述涂覆于PET薄膜，形成表面光滑的、可持久耐碱性溶液的、黏性极小的并能与金属强力结合的薄膜涂层。
实施例3：
成分 百分比 用量
聚(4-乙烯基吡啶)(P4VP) 3w/v％ 3g
SU‐8 0.2w/v％ 0.2g
1,4‐二氧六环 50v/v％ 50mL
2‐丙醇 50v/v％ 50mL
实施例4：
成分 百分比 用量
聚(4-乙烯基吡啶)(P4VP) 4w/v％ 4g
SU‐8 0.2w/v％ 0.2g
1,4‐二氧六环 50v/v％ 50mL
2‐丙醇 50v/v％ 50mL
实施例5：
成分 百分比 用量
聚(4-乙烯基吡啶)(P4VP) 2w/v％ 2g
SU‐8 0.1w/v％ 0.1g
1,4‐二氧六环 50v/v％ 50mL
2‐丙醇 50v/v％ 50mL
实施例6：
成分 百分比 用量
聚(4-乙烯基吡啶)(P4VP) 2w/v％ 2g
SU‐8 0.15w/v％ 0.15g
1,4‐二氧六环 50v/v％ 50mL
2‐丙醇 50v/v％ 50mL
实施例7：
成分 百分比 用量
聚(4-乙烯基吡啶)(P4VP) 2.5w/v％ 2.5g
SU‐8 0.2w/v％ 0.2g
1,4‐二氧六环 50v/v％ 50mL
2‐丙醇 50v/v％ 50mL
实施例8：
成分 百分比 用量
聚(4-乙烯基吡啶)(P4VP) 1w/v％ 1g
SU‐8 0.2w/v％ 0.2g
1,4‐二氧六环 50v/v％ 50mL
2‐丙醇 50v/v％ 50mL
实施例9：
成分 百分比 用量
聚(4-乙烯基吡啶)(P4VP) 2w/v％ 2g
SU‐8 0.05w/v％ 0.05g
1,4‐二氧六环 50v/v％ 50mL
2‐丙醇 50v/v％ 50mL
实施例10：
成分 百分比 用量
聚(4-乙烯基吡啶)(P4VP) 3w/v％ 3g
SU‐8 0.3w/v％ 0.3g
1,4‐二氧六环 50v/v％ 50mL
2‐丙醇 50v/v％ 50mL
实施例11：
成分 百分比 用量
聚(4-乙烯基吡啶)(P4VP) 3.5w/v％ 3.5g
SU‐8 0.3w/v％ 0.3g
1,4‐二氧六环 50v/v％ 50mL
2‐丙醇 50v/v％ 50mL
实施例12：
成分 百分比 用量
聚(4-乙烯基吡啶)(P4VP) 3w/v％ 3g
SU‐8 0.4w/v％ 0.4g
1,4‐二氧六环 50v/v％ 50mL
2‐丙醇 50v/v％ 50mL
实施例13：
成分 百分比 用量
聚(4-乙烯基吡啶)(P4VP) 3w/v％ 3g
SU‐8 0.6w/v％ 0.6g
1,4‐二氧六环 50v/v％ 50mL
2‐丙醇 50v/v％ 50mL
对于本发明涂层溶液的制备,亦可将本发明涂层组合物的各个组分直接加入溶剂然后混匀形成涂层溶液。
理想情况下，分别制备的溶液应以1:1的比例混合。
我们发现改性PET薄膜表面由于结合了大量P4VP分子，故而携有大量吡啶配体，这些吡啶配体可以有效地从溶液中捕获各种过渡金属离子。我们知道，Pd2+和Ag+离子是化学镀铜的两种典型催化剂。它们可以被吡啶配体中氮原子的孤对电子进攻并形成强力的配位键。例如，一旦改性PET薄膜被浸入AgNO3溶液，银离子将被化学吸附至PET表面。不同于单纯的物理吸附，化学键要强大得多且被吸附的银离子几乎无法脱离表面。图1d显示了经1h化学镀铜的覆有铜层的PET薄膜。如图所示，铜层可被很好地镀在整个PET基材上并具有良好的柔韧性。
我们发现小凹坑的分布是均匀的但排列是不规则的。随着连续的镀铜，铜层变得越来越厚，小凹坑也会逐渐被填充。图4c和图4d分别展示了30min和1h镀铜后的铜层表面形态。明显随着镀铜时间的增加，铜晶粒长大且铜层变得致密。图4e和图4f分别展示了经1h和12h铜沉积的铜层的横截面。
我们还发现经过1h镀铜之后铜层的厚度约为1.3～1.4μm。同时，在使用了所发明的涂层后，铜层紧密地与基材相贴合且没有发现剥离现象。透明胶带试验被用于检查铜层结合的牢固度，研究发现铜层可以从PET表面被撕下。即使有7微米的厚度，铜层与基材依然具有牢固的结合(图4f)。然而，在其他一些情况下，如对于用氧等离子体或浓NaOH/H2SO4处理过的表面，或者接枝了硅烷/其他小分子的表面，一旦铜层变厚，铜层即容易剥离或在基材上形成鼓包，这将严重影响铜沉积的质量和印刷电路的可靠性。此外，可以看出，随着电镀时间的延长，下层的铜开始转变为连续相，粒状结构逐渐消失，这将有利于电导率的提高。
此外，基于本发明，我们可以在PET基材上获得超厚铜层。不仅如此，如上所述，表面改性完全不影响PET薄膜的透明度和柔韧性。因此，改性薄膜非常适合作为柔性电路印刷用柔性基材。

Claims (10)

  1. 一种用于涂覆聚酯纤维薄膜、聚酰亚胺薄膜、聚氯乙烯薄膜、半压纹薄膜及聚氯乙烯薄膜类似物的涂层组合物，其特征在于：所述涂层组合物包括聚(4-乙烯基吡啶)、SU-8、1，4-二氧六环、2-丙醇；所述聚(4-乙烯基吡啶)在组合物中的重量/体积分数范围约为0.5％-4％，SU-8在组合物中的重量/体积分数范围约为0.05％-1％，1，4-二氧六环在组合物中的体积分数范围约为45％－50％；2-丙醇在组合物中的体积分数范围约为45％－50％。
  2. 根据权利要求1所述的涂层组合物，其特征在于：所述的聚(4-乙烯基吡啶)在组合物中的重量/体积浓度为1.5％-3％。
  3. 根据权利要求1所述的涂层组合物，其特征在于：所述的SU-8在组合物中的重量/体积浓度为0.15％-0.5％。
  4. 根据权利要求1所述的涂层组合物，其特征在于：所述的聚(4-乙烯基吡啶)分子量为60,000至160,000。
  5. 根据权利要求1所述的涂层组合物，其特征在于：所述的1，4-二氧六环在组合物中的体积浓度为48.25％－49.75％。
  6. 根据权利要求1所述的涂层组合物，其特征在于：所述的2-丙醇在组合物中的体积浓度为48.25％－49.75％。
  7. 一种对薄膜基材，例如聚酯纤维薄膜、聚酰亚胺薄膜、聚氯乙烯薄膜、半压纹薄膜及聚氯乙烯薄膜类似物进行涂覆的方法，其特征在于：包括以下步骤：将聚(4-乙烯基吡啶)溶解于2-丙醇，将SU-8溶解于1，4-二氧六环，将上述两溶液混合制成均匀的涂层溶液；所述聚(4-乙烯基吡啶)在组合物中的重量/体积分数范围约为0.5％-4％，SU-8在组合物中的重量/体积分数范围约为0.05％-1％，1，4-二氧六环在组合物中的体积分数范围约为45％－50％；2-丙醇在组合物中的体积分数范围约为45％－50％；
    使用碱性溶液、紫外—臭氧、等离子体及其他诸如打磨、抛光、加热等物理手段对待涂覆的基材进行预处理；
    将足量的所述涂层溶液涂布于所述基材从而在所述基材上形成薄膜涂层，
    干燥所述基材上的薄膜涂层，
    将所述覆有涂层的薄膜在80℃-180℃的温度下烘烤15-40分钟。
  8. 根据权利要求7所述的方法，其特征在于：所述的聚(4-乙烯基吡啶)分子量为60,000至160,000。
  9. 根据权利要求7所述的方法，其特征在于：所述的将涂层溶液涂布于基材上的方法包括旋涂、浸涂、喷涂、空气刮刀涂布、喷墨印刷、凹版印刷及丝网印刷。
  10. 根据权利要求7所述的方法，其特征在于：所述涂布可在基材上进行多次。
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