Classifications

• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/24—Electrically-conducting paints
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
• • 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
  • C09D11/00—Inks
  • C09D11/52—Electrically conductive inks
• • 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
  • C09D127/00—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 halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—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 halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/12—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 halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/20—Conductive material dispersed in non-conductive organic material
  • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
• • 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
  • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
  • H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/0806—Silver
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0104—Properties and characteristics in general
  • H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0137—Materials
  • H05K2201/015—Fluoropolymer, e.g. polytetrafluoroethylene [PTFE]
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
  • H05K2201/0203—Fillers and particles
  • H05K2201/0242—Shape of an individual particle
  • H05K2201/0245—Flakes, flat particles or lamellar particles

Definitions

• This invention is directed to a polymer thick film (PTF) conductor composition that performs better when dried at 80oC than when dried at130oC, in contrast to typical PTF conductors. More specifically, the polymer thick film conductor composition may be used in applications 10 where low temperature curing is required.
• PTF polymer thick film
• Conductive PTF circuits have long been used as electrical elements in low voltage circuitry. Although they have been used for years in these types of applications, the use of PTF silver conductors in applications 15 involving curing at temperatures less 90oC is not common. This is
• the typical substrates used are polyester and polycarbonate which can withstand 130oC drying cycles. 20 When a typical PTF conductor is dried at 130oC, it exhibits optimum
• PVDF polyvinylidene difluoride
• PVC polyvinyl chloride
• This invention relates to a polymer thick film conductor composition
• a polymer thick film conductor composition comprising:
• said silver powder is dispersed in said organic medium and wherein the weight percent of the silver powder and the organic medium are based on the total weight of the polymer thick film conductor
• the invention relates to a polymer thick film conductor composition for use in low-temperature substrate electrical circuits.
• a layer of the 20 polymer thick film conductor composition is printed and dried at 80oC on the substrate so as to produce a functioning circuit.
• This polymer thick film conductor composition exhibits inverted cure behavior, i.e., it results in a lower resistivity when dried at 80oC as compared to when dried at 130oC.
• PET polycarbonate
• PC polycarbonate
• PET polyester
• PVDF polyvinylidene difluoride
• the polymer thick film (PTF) conductor composition is comprised of (i) silver powder dispersed in (ii) an organic medium comprising a polymer 2
• powders and printing aids may be added to improve the composition.
• weight percent will be written as wt%.
• the conductive powders in the instant polymer thick film conductor composition are Ag conductor powders and may comprise Ag metal powder, alloys of Ag metal powder, Ag-coated copper powder or mixtures thereof.
• Ag conductor powders may comprise Ag metal powder, alloys of Ag metal powder, Ag-coated copper powder or mixtures thereof.
• silver powder and metal powder include all of the powders enumerated in the previous sentence. 10
• Various particle diameters and shapes of the metal powder are
• the conductive Ag powder may include silver particles of any shape, including particles that are spherical, in the form of flakes (rods, cones, plates), and mixtures thereof.
• the conductive silver powder comprises particles selected 15 from the group consisting of silver flakes, silver-coated copper particles and mixtures thereof.
• the conductive silver powder comprises particles in the form of silver flakes.
• the conductive silver powder comprises a mixture of particles of silver and silver-coated copper. The use of silver-coated copper particles results in 20 increased resistivity but a lower cost than the use of only silver particles and this is useful in certain applications.
• the particle size distribution of the conductive powders may be 1 to 100 microns; in a further embodiment, 2-10 microns.
• the surface area/weight ratio of the silver 25 particles may be in the range of 0.1 -1.0 m 2 /g.
• metals include: gold, nickel, aluminum, platinum, palladium, molybdenum, tungsten, tantalum, tin, 30 indium, lanthanum, gadolinium, boron, ruthenium, cobalt, titanium, yttrium, europium, gallium, sulfur, zinc, silicon, magnesium, barium, cerium, strontium, lead, antimony, conductive carbon, and combinations thereof 3
• metal(s) may comprise up to about 1.0 percent by weight of the total composition.
• silver powder encompasses such additional metals.
• the silver powder is present at 30 to 90 wt%, 40 to 80 wt%, or 58 to 70 wt%, based on the total weight of the composition.
• the organic medium is comprised of a thermoplastic vinylidene 10 difluoride/hexafluoro propylene (VF2/HFP) co-polymer resin dissolved in an organic solvent consisting of triethyl phosphate.
• Triethyl phosphate is a critical component of the instant polymer thick film conductor composition. Changing the solvent to something other than triethyl phosphate will render the composition ineffective in providing a suitable thick film
• the organic medium is present at 10 to 70 wt%, 20 to 60 wt%, or 30 to 42 wt%, based on the total weight of the composition.
• thermoplastic VF2/HFP resin is 10-60 wt% and the triethyl phosphate is 40-90 wt% of the total weight of the organic medium. In another embodiment the thermoplastic VF2/HFP resin is 20- 45 wt% and the triethyl phosphate is 55-80 wt% of the total weight of the organic medium and in still another embodiment the thermoplastic
• 25 VF2/HFP resin is 25-35 wt% and the triethyl phosphate is 65-75 wt% of the total weight of the organic medium.
• the polymer resin is typically added to the organic solvent by mechanical mixing to form the organic medium.
• Various powders may be added to the PTF conductor composition 5 to improve adhesion, modify the rheology and increase the low shear
• the PTF conductor composition also referred to as a“paste”, is typically deposited on a substrate, such as PVDF or PVC, that is
• the substrate can also be a sheet of a composite material made up of a combination of plastic sheet with optional metallic or dielectric layers deposited thereupon.
• the deposition of the PTF conductor composition is performed typically by screen printing, but other deposition techniques such as stencil 15 printing, syringe dispensing or coating techniques can be utilized. In the case of screen-printing, the screen mesh size controls the thickness of the deposited thick film.
• a thick film composition comprises a functional phase that imparts appropriate electrically functional properties to
• the functional phase comprises electrically
• the composition is fired to burn out both the polymer and the solvent of the organic medium and to impart the electrically functional properties.
• the composition is fired to burn out both the polymer and the solvent of the organic medium and to impart the electrically functional properties.
• the PTF conductor composition is processed for a time and at a temperature necessary to remove all solvent.
• the deposited thick film is dried by exposure to heat at 80 o C for typically 5 min.
• Substrates such as polyvinyl chloride and polyvinylidene difluoride which can only be exposed to approximately 80oC maximum temperature 5
• conductor composition is printed and dried as per the conditions described above. Several layers can be printed and dried.
• the PTF conductor composition was prepared in the following
• 34.31 wt% of the organic medium was used and was prepared by mixing 32.5 wt% vinylidene difluoride/hexafluoro propylene copolymer resin, ADS2 (Arkema, Inc. King of Prussia, PA), with 67.5 wt% triethyl phosphate (Eastman Chemicals, Kingsport, TN.) organic solvent. The 15 wt% of the resin and the triethyl phosphate are based on the total weight of the organic medium. The molecular weight of the resin was
• This composition was mixed for 30 minutes on a planetary mixer, 25 and then subjected to several passes on the three roll-mill to provide the PTF conductor composition.
• a circuit was then fabricated as follows. On a 5 mil thick PET substrate, the PTF conductor composition was used to print a pattern of a series of serpentine silver lines using a 280 mesh stainless steel screen. 30 The patterned lines were dried at 80 o C for 5 min. in a forced air box oven.
• the circuit was inspected and tested for resistivity and adhesion.
• Example 5 A circuit was produced exactly as described in Example 1. The only difference was that the conductive pattern was dried at 130 o C for 10 min. As can be seen in Table 1 , the properties of the PTF silver composition were worse when dried at 130 o C as compared to those when dried at 80 o C. Results are shown in Table I.
• a circuit was produced exactly as described in Example 1. The only difference was that dibasic esters were used as the organic solvent instead of triethyl phosphate. Results of drying at 130 o C vs 80 o C were typical of a PTF conductor (better performance at higher temperatures). 15 The excellent performance at 80 o C was not seen. Results are shown in Table I.
• a circuit was produced exactly as described in Example 1. The only difference was that a commercial silver conductor paste, DuPont 20 5025 (DuPont Co., Wilmington, DE) was used to form the circuit. Results of drying at 130 o C vs 80 o C were typical of a PTF conductor (better performance at higher temperatures). The excellent performance at 80 o C was not seen. Results are shown in Table I.
• Example 25 A circuit was produced exactly as described in Example 1 with the exception that the composition used here had an approximate 50/50 blend of flake silver and silver-coated copper (Ames Corporation; 3 ⁇ m average particle size). As can be seen in Table 1 , the resistivity of the PTF silver composition was higher when dried at 130 o C as compared to that when 30 dried at 80 o C. Excellent adhesion was found. Results are shown in Table I.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Dispersion Chemistry (AREA)
• Medicinal Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Conductive Materials (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Parts Printed On Printed Circuit Boards (AREA)

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• 2015
  • 2015-06-11 US US14/736,791 patent/US9718966B2/en not_active Expired - Fee Related
  • 2015-07-02 EP EP15745018.0A patent/EP3170188B1/en active Active
  • 2015-07-02 WO PCT/US2015/039012 patent/WO2016010744A1/en not_active Ceased
  • 2015-07-02 JP JP2017502579A patent/JP6517915B2/ja not_active Expired - Fee Related
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