US20070123645A1 - Ultraviolet curable silver composition and related method - Google Patents
Ultraviolet curable silver composition and related method Download PDFInfo
- Publication number
- US20070123645A1 US20070123645A1 US11/637,572 US63757206A US2007123645A1 US 20070123645 A1 US20070123645 A1 US 20070123645A1 US 63757206 A US63757206 A US 63757206A US 2007123645 A1 US2007123645 A1 US 2007123645A1
- Authority
- US
- United States
- Prior art keywords
- silver
- composition
- silver composition
- amount
- acrylated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 457
- 239000000203 mixture Substances 0.000 title claims abstract description 369
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 311
- 239000004332 silver Substances 0.000 title claims abstract description 311
- 238000000034 method Methods 0.000 title abstract description 66
- 239000000178 monomer Substances 0.000 claims description 82
- 239000004593 Epoxy Substances 0.000 claims description 54
- 125000004122 cyclic group Chemical group 0.000 claims description 50
- 125000001931 aliphatic group Chemical group 0.000 claims description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 38
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 230000001737 promoting effect Effects 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 17
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000080 wetting agent Substances 0.000 claims description 4
- 239000002318 adhesion promoter Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 37
- 238000000576 coating method Methods 0.000 abstract description 30
- 239000002245 particle Substances 0.000 description 52
- 238000002156 mixing Methods 0.000 description 47
- 239000011248 coating agent Substances 0.000 description 29
- 239000000463 material Substances 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 238000009826 distribution Methods 0.000 description 11
- 238000007747 plating Methods 0.000 description 10
- 238000003847 radiation curing Methods 0.000 description 9
- 230000005855 radiation Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 0 [1*]C(C(=O)O[2*])=C([H])[H] Chemical compound [1*]C(C(=O)O[2*])=C([H])[H] 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical group COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- -1 plating Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- FYYZTOOGFNLGII-UHFFFAOYSA-N (1,6-dihydroxy-1-prop-2-enoyloxyhexyl) prop-2-enoate Chemical compound OCCCCCC(O)(OC(=O)C=C)OC(=O)C=C FYYZTOOGFNLGII-UHFFFAOYSA-N 0.000 description 3
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 3
- 108091092920 SmY RNA Proteins 0.000 description 3
- 241001237710 Smyrna Species 0.000 description 3
- JZMPIUODFXBXSC-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCOC(N)=O JZMPIUODFXBXSC-UHFFFAOYSA-N 0.000 description 3
- WGOQVOGFDLVJAW-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCOC(N)=O WGOQVOGFDLVJAW-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 125000005409 triarylsulfonium group Chemical group 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- 208000032365 Electromagnetic interference Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005112 continuous flow technique Methods 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/064—Polymers containing more than one epoxy group per molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- 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
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- 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
- the present invention relates to silver-containing compositions and more particularly to photocurable silver-containing compositions, to methods for making and applying a photocurable silver-containing compositions as a coating on a substrate.
- a coating, plating or layer of silver or a silver-containing compound there are many instances in which it is necessary or desirable to apply a coating, plating or layer of silver or a silver-containing compound to a substrate.
- Examples of such applications would include electrode plating for switches such as those used on pressure-sensitive switches or control panels, for example, as are used on appliances such as microwave ovens, conventional ovens, and the like.
- Such silver plating also is commonly used in the semiconductor fabrication arts to apply silver metalizations on silicon or germanium semiconductor wafers.
- substrates include, without limitation, such things as polyesters, polycarbonates, vinyls, ceramics, glass, and the like.
- the predominant approach heretofore used in applying silver to substrates has involved using a solvent-based silver solution to the substrate, and chemically or thermally curing the solution to evaporate the solvent. This leaves the solid silver plating on the substrate.
- an object of the present invention is to provide a silver composition and method in which silver can be disposed on a substrate without requiring a toxic solvent.
- Another object of the invention is to provide a silver composition and method in which disposition of the silver layer can be done more quickly and efficiently than prior art solvent-based techniques.
- Another object of the invention is to provide a silver composition and method in which a silver coating may be created which has more predictable and uniform layer thickness relative to prior art solvent-based systems.
- a silver composition is provided for deposition as a coating, plating, film or layer on a substrate.
- the terms coating, plating, film and layer in the context of this document are used to refer generally to a covering on the surface of a substrate, which covering may be of a variety of thicknesses depending on the application and the design goals.
- a photocurable silver composition comprises a photocurable organic mixture, a photoinitiator, a silver powder, and a silver flake composition.
- the silver flake composition is present in an amount of at least 20% of the weight of the silver powder present in the composition. Incorporation of silver flake composition in an amount of at least 20% results in films with superior conductivity. Resistivities as low as 0.03 ohm/sq at 1 mil are achieved.
- the photocurable silver composition preferably comprises an aliphatic acrylated oligomer, wherein the aliphatic acrylated oligomer is present in an amount of about 3% to 8% based on the weight of the silver composition. All percentages of the silver composition as expressed in this document, unless otherwise stated, refer to the mass percentage of the stated component to the total mass of the silver composition in its fluid uncured state at standard temperature and pressure.
- the silver composition also preferably comprises an acrylated epoxy oligomer, wherein the acrylated epoxy oligomer is present in an amount of about 2% to 4% of the silver composition.
- the silver composition also preferably comprises an isoborny 1 acrylate monomer in an amount of about 4% to 8% of the silver composition, a photoinitiator in an amount of about 3% to 6% of the silver composition, a flow promoting agent in an amount of about 0.1% to 2% of the silver composition, a silver powder in an amount of about 50% to 60% of the silver composition, and a silver flake composition in an amount of about 25% to 35% of the silver composition.
- the aliphatic acrylated oligomer preferably comprises a urethane oligomer.
- the aliphatic acrylated oligomer is present in an amount of about 8% of the silver composition.
- the acrylated epoxy oligomer is preferably present in an amount of about 3% of the silver composition.
- the isobornyl acrylate monomer is preferably present in an amount of about 5% of the silver composition.
- the photoinitiator is preferably present in an amount of about 5% of the silver composition.
- the flow promoting agent is preferably present in an amount of about 1% of the silver composition.
- the silver powder preferably but optionally is present in an amount of about 52% of the silver composition.
- the silver powder has a particle size range of about 5 microns to about 15 microns.
- the silver powder has a particle distribution such that about 5% to 20% of the particles have a particle size of less than about 4.7 microns, about 30% to 60% of the particles have a particle size of less than about 7.6 microns, and about 70% to 95% of the particles have a particle size of less than about 14.9 microns.
- the silver powder has a particle distribution such that about 10% of the particles have a particle size of less than about 4.7 microns, about 50% of the particles have a particle size of less than about 7.6 microns, and about 90% of the particles have a particle size of less than about 14.9 microns.
- the silver flake is present in an amount of about 30% of the silver composition.
- the silver flake has a particle size range of about 5 microns to about 32 microns.
- the silver flake preferably has a flake distribution such that about 10% of the particles have a particle size of less than about 5.5 microns, about 50% of the particles have a particle size of less than about 12.5 microns, and about 90% of the particles have a particle size of less than about 32.0 microns.
- an adhesion promoter is present in about 1 to 4% of the silver composition. This further refinement improves adhesion to substrates coated with transparent conductors such as indium tin oxide (ITO).
- ITO indium tin oxide
- a photocurable silver composition suitable for producing a coating that is capable of shielding electromagnetic radiation is provided.
- This embodiment is preferably applied to a substrate by spraying.
- the silver composition comprises an acrylated epoxy oligomer, wherein the acrylated epoxy oligomer is present in an amount of about 2% to 8% of the silver composition.
- the silver composition preferably comprises an isobornyl acrylate monomer in an amount of about 15% to 30% of the silver composition, an photoinitiator in an amount of about 3% to 7% of the silver composition, a flow promoting agent in an amount of about 0.1% to 2% of the silver composition, a silver powder in an amount of about 20% to 40% of the silver composition, and a silver flake composition in an amount of about 20% to 40% of the silver composition.
- a photocurable silver composition suitable for producing a coating that is capable of forming resistive links on circuit boards is provided.
- This embodiment of the invention preferably does not contain any urethane
- the silver composition comprises an acrylated epoxy oligomer having, wherein the acrylated epoxy oligomer is present in an amount of about 16% to 20% of the silver composition.
- the silver composition also comprises an isoborny 1 acrylate monomer in an amount of about 8% to 14% of the silver composition, an photoinitiator in an amount of about 4% to 8% of the silver composition, a flow promoting agent in an amount of about 0.1% to 2% of the silver composition, a silver powder in an amount of about 25% to 38% of the silver composition, and a silver flake composition in an amount of about 20% to 40% of the silver composition.
- a photocurable silver composition suitable for producing a coating that is capable resistive links on circuit boards contains urethane.
- the silver composition comprises an aliphatic acrylated oligomer (a urethane), wherein the aliphatic acrylated oligomer is present in an amount of about 7% to 11% of the silver composition.
- the silver composition further comprises an acrylated epoxy oligomer, wherein the acrylated epoxy oligomer is present in an amount of about 1% to 4% of the silver composition.
- the silver composition also comprises an isobornyl acrylate monomer in an amount of about 12% to 25% of the silver composition, a photoinitiator in an amount of about 2% to 4% of the silver composition, a flow promoting agent in an amount of about 0.0% to 4% of the silver composition, an antimony tin oxide powder in an amount of 7% to 19%, a silver powder in an amount of about 24% to 30% of the silver composition, and a silver flake composition in an amount of about 15% to 30% of the silver composition.
- the silver composition further comprises a polyacrylic oligomer/acrylate monomer blend in an amount of about 5% to 10%.
- a photocurable silver composition suitable for producing a coating that is capable black colored resistive links on circuit boards comprises an aliphatic acrylated oligomer, wherein the aliphatic acrylated oligomer is present in an amount of about 7% to 11% of the silver composition
- the silver composition further comprises an acrylated epoxy oligomer having, wherein the acrylated epoxy oligomer is present in an amount of about 2% to 4% of the silver composition.
- the silver composition also comprises an isobornyl acrylate monomer in an amount of about 10% to 14% of the silver composition, a photoinitiator in an amount of about 13% to 15% of the silver composition, a flow promoting agent in an amount of about 0.1% to 2% of the silver composition, a conductive carbon black powder in an amount of 5% to 12%, a wetting agent in an amount of about 0.5 to 3% of the silver composition, a silver powder in an amount of about 30% to 40% of the silver composition, and a silver flake composition in an amount of about 15% to 25% of the silver composition.
- an isobornyl acrylate monomer in an amount of about 10% to 14% of the silver composition
- a photoinitiator in an amount of about 13% to 15% of the silver composition
- a flow promoting agent in an amount of about 0.1% to 2% of the silver composition
- a conductive carbon black powder in an amount of 5% to 12%
- a wetting agent in an amount of about 0.5 to 3% of the silver
- a method for making a photocurable silver composition.
- the method comprises a first step of combining and mixing an isoborny 1 acrylate monomer and a photoinitiator to create a first mixture.
- the isobornyl acrylate monomer is present in an amount of about 4% to 8% of the silver composition, and the photoinitiator is present in an amount of about 3% to 6% of the silver composition.
- the method includes a second step of combining and mixing an aliphatic acrylated oligomer and an acrylated epoxy oligomer to create a second mixture.
- the aliphatic acrylated oligomer is present in an amount of about 3% to 8% of the silver composition and the acrylated epoxy oligomer is present in an amount of about 2% to 4% of the silver composition.
- the method includes a third step of combining and mixing a silver powder and a silver flake composition to create a third mixture.
- the silver powder is present in an amount of about 50% to 60% of the silver composition and the silver flake composition is present in an amount of about 25% to 35% of the silver composition.
- the method further includes a fourth step of combining and mixing a flow promoting agent in an amount of about 0.1% to 2% of the silver composition, and a fifth step of combining the first, second, third and fourth mixtures to create the silver composition.
- the first, second, third and fourth steps are performed sequentially.
- the method in its various forms may be carried out on a batch basis, for example, in a mixing vessel or similar process equipment suitable for batch processing. It may also be carried out in other forms, for example, such as continuous flow regimes.
- another method for making a photocurable silver composition.
- This method comprises a first step of combining and mixing an isobornyl acrylate monomer and a photoinitiator to create a first composition, wherein the isobornyl acrylate monomer is present in an amount of about 4% to 8% of the silver composition, and the photoinitiator is present in an amount of about 3% to 6% of the silver composition.
- This method also includes a second step of combining with the first composition and mixing an aliphatic acrylated oligomer and an acrylated epoxy oligomer to create a second mixture.
- the aliphatic acrylated oligomer is present in an amount of about 3% to 8% of the silver composition and the acrylated epoxy oligomer is present in an amount of about 2% to 4% of the silver composition.
- the method further includes a third step of combining with the second composition and mixing a silver powder and a silver flake composition to create a third composition.
- the silver powder is present in an amount of about 50% to 60% of the silver composition and the silver flake composition is present in an amount of about 25% to 35% of the silver composition.
- the method still further includes a fourth step of combining with the third composition and mixing a flow promoting agent in an amount of about 0.1% to 2% of the silver composition.
- This method also may be carried out in a batch format, for example, in a mixing vessel or series of mixing vessels, in a continuous flow regime, or in some combination.
- a method for depositing a silver coating on a substrate.
- the method comprises a first step of applying to the substrate a silver-containing fluid-phase composition (“silver composition”).
- the silver composition comprises an aliphatic acrylated oligomer, wherein the aliphatic acrylated oligomer is present in an amount of about 3% to 8% of the silver composition.
- the silver composition further includes an acrylated epoxy oligomer. The acrylated epoxy oligomer is present in an amount of about 2% to 4% of the silver composition.
- the silver composition also includes an isobornyl acrylate monomer in an amount of about 4% to 8% of the silver composition, a photoinitiator in an amount of about 3% to 6% of the silver composition, and a flow promoting agent in an amount of about 0.1% to 2% of the silver composition.
- the silver composition further includes a silver powder in an amount of about 50% to 60% of the silver composition, and a silver flake composition in an amount of about 25% to 35% of the silver composition.
- the method also includes a second step of illuminating the silver composition on the substrate with light of a wavelength suitable to cause the silver composition to cure into the silver coating.
- light will have a wavelength in the ultraviolet region of the electromagnetic spectrum.
- the silver composition can be selectively deposited on the substrate at specific locations where silver plating is desired. It need not be applied to the entire substrate. It is thus possible, for example, to use the silver coating thus created as metalizations on semiconductor wafers, printed circuit boards, pressure sensitive or pressure activated switches, and the like.
- a method for preparing a liquid-phase silver-containing composition for use in providing a silver-containing coating or plating on a substrate.
- the presently preferred version of the method includes preparing the composition as identified immediately above.
- the method in broad terms includes a first step of combining and mixing the monomer and the photoinitiator in a mixing vessel, a second step of adding to the mixing vessel and blending in the urethane and the epoxy, a third step of adding to the mixing vessel and blending in the silver powder and the silver flake, and a forth step of adding to the mixing vessel and blending in the flow agent.
- a presently preferred photocurable silver composition (“silver composition”) is provided.
- the silver composition includes an aliphatic acrylated oligomer.
- the aliphatic acrylated oligomer is present in an amount of about 3% to 8%, and preferably about 8%, of the silver composition.
- the aliphatic acrylated oligomer preferably comprises a urethane oligomer.
- Suitable aliphatic acrylated oligomers include Radcure Ebecryl 244, Ebecryl 264 and Ebecryl 284 urethanes, commercially available from Radcure UCB Corp.
- the preferred aliphatic acrylated oligomers include Ebecryl 264 and Ebecryl 284.
- Ebecryl 264 is an aliphatic urethane triacrylate supplied as an 85% solution in hexandiol diacrylate.
- Ebecryl 284 is aliphatic urethane diacrylate of 1200 molecular weight diluted with 1,6-hexandiol diacrylate. It is obvious to one skilled in the art that combinations of these materials may also be employed herein.
- This preferred silver composition further includes an acrylated epoxy oligomer.
- the acrylated epoxy oligomer is present in an amount of about 2% to 4%, and preferably about 3%, of the silver composition.
- Suitable acrylated epoxy oligomers include Radcure Ebecryl 3603, commercially available from Radcure UCB Corp.; Sartomer CN120 and CN124, commercially available from Sartomer Corp.; and Echo Resin TME 9310 and 9345, commercially available from Echo Resins.
- the preferred acrylated epoxy oligomer is Ebecryl 3603, which tri-functional acrylated epoxy novolac. Combinations of these materials may also be employed herein.
- the preferred silver composition also includes an isobornyl acrylate monomer preferably present in an amount of about 4% to 8%, and more preferably about 5%, of the silver composition.
- Isobornyl acrylates include the bridge cyclic isobornyl group which is known chemically to be quite bulky.
- Suitable isobornyl acrylate monomers include Sartomer SR423 IBOMA and SR506 IBOA; Radcure IBOA, commercially available from Radcure Corp.; IBOA and IBOMA, commercially available from CPS Chemical; and Genomer 1121, commercially available from Rahn Radiation Curing.
- Preferred isobornyl acrylate monomers include Sartomer SR423 IBOMA and SR506 IBOA; Radcure IBOA, commercially available from Radcure Corp.; IBOA AND IBOMA, commercially available from CPS Chemical; and Genomer 1121, commercially available from Rahn Radiation Curing.
- a non-bridged cyclic acrylate monomer or a non-cylic acrylate monomer may be used in place of the isobornyl acrylate monomer or in combination with the isobornyl acrylate monomer.
- Suitable cyclic acrylate monomers or non-cyclic acrylate monomers are described by the following formula: wherein R 1 is hydrogen or substituted or unsubstituted alkyl; and R 2 is non-cyclic functional group or a non-bridged cyclic group.
- non-cyclic functional groups include substituted or unsubstituted alkyl having more than 4 carbon atoms.
- non-bridged cyclic groups include cycloalkyl, cycloalkenyl, and substituted or unsubstituted aryl.
- R 1 is hydrogen or methyl
- R 2 is phenyl, benzyl, dicylcopentenyl, dicyclopentenyl oxyethyl, cyclohexyl, and naphthyl.
- This preferred silver composition also includes a photoinitiator in an amount of about 3% to 6%, and preferably about 4%, of the silver composition.
- Suitable photoinitiators include Irgacure 184 (1-hydroxycyclohexyl phenyl ketone), 907 (2-methyl-1-[4-(methylthio)phenyl]-2-morpholino propan-1-one), 369 (2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone), 500 (the combination of 1-hydroxy cyclohexyl phenyl ketone and benzophenone), 651 (2,2-dimethoxy-2-phenyl acetophenone), 1700 (the combination of bis(2,6-dimethoxybenzoyl-2,4-,4-trimethyl pentyl phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one), Ciba-Geigy 1700, and
- the preferred photoinitiator is Irgacure 1700 commercially available from Ciba-Geigy of Tarrytown, N.Y.
- the preferred silver composition still further includes a flow promoting agent in an amount of about 0.1% to 2%, and preferably about 1.0%, of the silver composition.
- Suitable flow promoting agents include Genorad 17, commercially available from Rahn Radiation Curing; and Modaflow, commercially available from Monsanto Chemical Co., St. Louis, Mo.
- the preferred flow promoting agent is Modaflow which is an ethyl acrylate and 2-ethylhexyl acrylate copolymer that improves the flow of the composition. Combinations of these materials may also be employed herein.
- the preferred silver composition also includes a silver powder in an amount of about 50% to 60%, and preferably about 52%, of the silver composition.
- the silver powder comprises a plurality of particles.
- the silver powder has a particle size range for these particles of about 5 microns to about 15 microns.
- the silver powder has a particle size range of about 4.7 microns to about 14.9 microns.
- the silver powder particles have a particle size distribution wherein about 10% of the particles have a particle size of less than about 4.7 microns, about 50% of the particles have a particle size of less than about 7.6 microns, and about 90% of the particles have a particle size of less than about 14.9 microns.
- the preferred silver powders are Silver Powder EG-ED and Silver Powder C-ED commercially available from Degussa Corp. of South Plainfield, N.J.
- the preferred silver composition further includes a silver flake composition in an amount of about 25% to 35%, and preferably about 30%, of the silver composition.
- the silver flake composition comprises a plurality of flakes which comprise, and which preferably consist essentially of, silver.
- the silver flake composition according to this embodiment has a particle size range of about 5 microns to about 32 microns. More preferably, the silver flake composition has a particle size range of about 5.5 microns to about 32.0 microns.
- the silver flake particle size distribution preferably is such that about 10% of the particles have a particle size of less than about 5.5 microns, about 50% of the particles have a particle size of less than about 12.5 microns, and about 90% of the particles have a particle size of less than about 32.0 microns.
- the preferred silver flake compositions are Silver Flake #25, Silver Flake #1, and Silver Flake #7A commercially available from Degussa Corp. of South Plainfield, N.J.
- This example provides a preferred silver composition according to the invention that can be used for deposition on the surface of a substrate such as a polymeric membrane, for example, to serve as the electrical contact for a pressure-sensitive switch.
- the silver composition was made from the following components: Component Approximate Mass % Ebecryl 264 7.2 Ebecryl 3603 2.4 IBOA 4.7 Silver Powder EGED 53.4 Silver Flake # 25 27.6 Iragure 1700 3.9 Modaflow 0.8 Total 100.00
- the IBOA and Iragure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm.
- the Ebecryl 264, the Ebecryl 3603, and the Modaflow are introduced into the pan and mixed for 1 to 2 minutes at a speed of 1000 rpm.
- the EGED silver powder, and the Silver Flake #25 are introduced into the pan and are mixed for 1 to 2 minutes at a speed of 1000 rpm.
- the mixing speed is increased to 10,000 rpm and mixed for an additional 5 minutes.
- the washing process includes a first step of loading the powder in a sealable container.
- a mixture consisting of 17% methyl ethyl ketone and 83% silver composition is added to the container and the slurry is mixed with a propeller blade for 5 minutes at 500 rpm.
- the methyl ethyl ketone is poured off and the silver powder is allowed to air dry. During the drying stage the powder is periodically mixed.
- the silver powder according to the presently-preferred composition comprises EGED, commercially available from Degussa Corp. of South Plainfield, N.J. Such silver also may be obtained from other commercial sources, e.g., such as Englehard Chemical Co. of Iselin, N.J.
- the presently preferred silver powder has a grain size distribution ranging from about 5 microns to about 15 microns. This presently preferred silver powder has a particle size distribution as follows: TABLE 1 Silver Powder Particle Size Distribution Size Range (microns) Percentage ⁇ 4.7 10% ⁇ 7.6 50% ⁇ 14.9 90%
- the silver flake according to the presently-preferred composition of Example I comprises SF25, commercially available from Degussa.
- This silver flake composition preferably has a grain size distribution ranging from about 5 microns to about 32 microns. It has a particle size distribution as follows: TABLE 2 Silver Flake Composition Particle Size Distribution Size Range (microns) Percentage ⁇ 5.5 10% ⁇ 12.5 50% ⁇ 32.0 90%
- 10% of the flakes have a size of less than 5.5 microns, 50% of the flakes have a particle size of less than 12.5 microns, and 90% of the flakes have a particle size of less than 32.0 microns.
- This example provides another preferred silver composition according to the invention that can be used for deposition on the surface of a substrate such as those noted above.
- the silver composition was made from the following components: Component Approximate Mass % Ebecryl 264 4.2 Ebecryl 3603 2.7 IBOA 7.7 Silver Powder EGED 53.4 Silver Flake #25 27.6 Iragure 1700 3.8 Modaflow 0.6 Total 100.00
- the IBOA and Iragure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm.
- the Ebecryl 264, the Ebecryl 3603, and the Modaflow are introduced into the pan and mixed for 1 to 2 minutes at a speed of 1000 rpm.
- the EGED silver powder, and the Silver Flake #25 are introduced into the pan and are mixed for 1 to 2 minutes at a speed of 1000 rpm.
- the mixing speed is increased to 10,000 rpm and mixed for an additional 5 minutes.
- This example provides another preferred silver composition according to the invention that can be used for deposition on the surface of a substrate coated with indium tin oxide (ITO).
- the silver composition was made from the following components: Component Approximate Mass % Ebecryl 264 7.0 Ebecryl 3603 2.3 IBOA 4.6 Silver Powder EGED 52.3 Silver Flake # 25 27.0 Iragure 1700 3.8 Modaflow 0.8 Ebecryl 168 2.2 Total 100.00
- the IBOA and Iragure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm.
- the Ebecryl 264, the Ebecryl 3603, and the Modaflow are introduced into the pan and mixed for 1 to 2 minutes at a speed of 1000 rpm.
- the EGED silver powder, and the Silver Flake #25 are introduced into the pan and are mixed for 1 to 2 minutes at a speed of 1000 rpm.
- the Ebecryl 168 is added into the pan and the combination mixed at 1000 rpm for 1 to 2 minutes.
- the mixing speed is increased to 10,000 rpm and mixed for an additional 5 minutes.
- This example contains Ebecryl 168 added as an adhesion promoter.
- This material is a methacrylate ester derivative commercially available from Radcure UCB Corp. of Smyrna, Ga.
- a presently preferred photocurable silver composition (“silver composition”) is provided.
- This composition upon photocuring produces a coating capable of shielding electromagnet interference. Such a coating may be applied to substrates requiring shielding from electromagnetic interferences such as the interior of radio casings.
- the silver composition includes an acrylated epoxy oligomer.
- the acrylated epoxy oligomer is present in an amount of about 2% to 8%, and preferably about 5%, of the silver composition.
- Suitable acrylated epoxy oligomers are the same as listed above.
- the preferred acrylated epoxy oligomer is Ebecryl 3603, which tri-functional acrylated epoxy novolac. Combinations of these materials may also be employed herein.
- the preferred silver composition also includes an isobornyl acrylate monomer in an amount of about 15% to 30%, and preferably about 21%, of the silver composition.
- Suitable isobornyl acrylate monomers are the same as listed above.
- Preferred isobornyl acrylate monomers include Sartomer SR423 IBOMA and SR506 IBOA; Radcure IBOA, commercially available from Radcure Corp.; IBOA and IBOMA, commercially available from CPS Chemical; and Genomer 1121, commercially available from Rahn Radiation Curing. Combinations of these materials may also be employed herein.
- a non-bridged cyclic acrylate monomer or a non-cylic acrylate monomer may be used in place of the isobornyl acrylate monomer or in combination with the isobornyl acrylate monomer.
- Suitable cyclic acrylate monomers or non-cyclic acrylate monomers are described by the following formula: wherein R 1 is hydrogen or substituted or unsubstituted alkyl; and R 2 is non-cyclic functional group or a non-bridged cyclic group. Examples of non-cyclic functional groups include substituted or unsubstituted alkyl having more than 4 carbon atoms.
- non-bridged cyclic groups include cycloalkyl, cycloalkenyl, and substituted or unsubstituted aryl.
- R 1 is hydrogen or methyl; and
- R 2 is phenyl, benzyl, dicylcopentenyl, dicyclopentenyl oxyethyl, cyclohexyl, and naphthyl.
- This preferred silver composition also includes a photoinitiator in an amount of about 3% to 7%, and preferably about 5%, of the silver composition.
- Suitable photoinitiators are the same as listed above.
- the preferred photoinitiator is Irgacure 1700 commercially available from Ciba-Geigy of Tarrytown, N.Y. Combinations of these materials may also be employed herein.
- the preferred silver composition still further includes a flow promoting agent in an amount of about 0.1% to 2%, and preferably about 1.0%, of the silver composition.
- a flow promoting agent in an amount of about 0.1% to 2%, and preferably about 1.0%, of the silver composition.
- Suitable flow promoting agents are the same as listed above.
- the preferred flow promoting agent is Modaflow which is an ethyl acrylate and 2-ethylhexyl acrylate copolymer that improves the flow of the composition. Combinations of these materials may also be employed herein.
- the preferred silver composition also includes a silver powder in an amount of about 25% to 40%, and preferably about 36%, of the silver composition.
- the preferred silver powders are Silver Powder EG-ED and Silver Powder C-ED commercially available from Degussa Corp. of South Plainfield, N.J.
- the preferred silver composition further includes a silver flake composition in an amount of about 20% to 40%, and preferably about 30%, of the silver composition.
- the preferred silver flake compositions are Silver Flake #25, Silver Flake #1, and Silver Flake #7A commercially available from Degussa Corp. of South Plainfield, N.J.
- This example provides another preferred silver composition according to the invention that when applied to a surface and subsequently cured by ultraviolet radiation will produce a coating suitable for shielding electromagnetic interference.
- the silver composition was made from the following components: Component Approximate Mass % Ebecryl 3603 5.3 IBOA 21.0 Silver Powder EGED 31.5 Silver Flake # 1 35.7 Iragure 1700 5.3 Modaflow 1.2 Total 100.00
- the IBOA and Iragure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm.
- the Ebecryl 3603, and the Modaflow are introduced into the pan and mixed for 5 minutes at a speed of 5000 rpm.
- the EGED silver powder and the Silver Flake #1 are introduced into the pan and are mixed for 1 to 2 minutes at a speed of 1000 rpm.
- the mixing speed is increased to 10,000 rpm and mixed for an additional 5 to 10 minutes.
- a presently preferred photocurable silver composition (“silver composition”) is provided.
- This composition upon photocuring produces a coating capable of producing resistive links in circuit boards.
- the silver composition includes an acrylated epoxy oligomer.
- the acrylated epoxy oligomer is present in an amount of about 16% to 20%, and preferably about 18%, of the silver composition.
- Suitable acrylated epoxy oligomers are the same as listed above.
- the preferred acrylated epoxy oligomer is Ebecryl 3603, which tri-functional acrylated epoxy novolac. Combinations of these materials may also be employed herein.
- the preferred silver composition also includes an isobornyl acrylate monomer in an amount of about 8% to 14%, and preferably about 11%, of the silver composition.
- Suitable isobornyl acrylate monomers are the same as listed above.
- Preferred isobornyl acrylate monomers include Sartomer SR423 IBOMA and SR506 IBOA; Radcure IBOA, commercially available from Radcure Corp.; IBOA AND IBOMA, commercially available from CPS Chemical; and Genomer 1121, commercially available from Rahn Radiation Curing. Combinations of these materials may also be employed herein.
- a non-bridged cyclic acrylate monomer or a non-cylic acrylate monomer may be used in place of the isobornyl acrylate monomer or in combination with the isobornyl acrylate monomer.
- Suitable cyclic acrylate monomers or non-cyclic acrylate monomers are described by the following formula: wherein R 1 is hydrogen or substituted or unsubstituted alkyl; and R 2 is non-cyclic functional group or a non-bridged cyclic group. Examples of non-cyclic functional groups include substituted or unsubstituted alkyl having more than 4 carbon atoms.
- non-bridged cyclic groups include cycloalkyl, cycloalkenyl, and substituted or unsubstituted aryl.
- R 1 is hydrogen or methyl; and
- R 2 is phenyl, benzyl, dicylcopentenyl, dicyclopentenyl oxyethyl, cyclohexyl, and naphthyl.
- This preferred silver composition also includes a photoinitiator in an amount of about 4% to 8%, and preferably about 6%, of the silver composition.
- Suitable photoinitiators are the same as those listed above.
- the preferred photoinitiator is Irgacure 1700 commercially available from Ciba-Geigy of Tarrytown, N.Y. Combinations of these materials may also be employed herein.
- the preferred silver composition still further includes a flow promoting agent in an amount of about 0.1% to 2%, and preferably about 1.0%, of the silver composition.
- Suitable flow promoting agents are the same as those listed above.
- the preferred flow promoting agent is Modaflow which is an ethyl acrylate and 2-ethylhexyl acrylate copolymer that improves the flow of the composition. Combinations of these materials may also be employed herein.
- the preferred silver composition also includes a silver powder in an amount of about 25% to 35%, and preferably about 30%, of the silver composition.
- the preferred silver powders are Silver Powder EG-ED and Silver Powder C-ED commercially available from Degussa Corp. of South Plainfield, N.J.
- the preferred silver composition further includes a silver flake composition in an amount of about 25% to 38%, and preferably about 34%, of the silver composition.
- the preferred silver flake compositions are Silver Flake #25, Silver Flake #1, and Silver Flake #7A commercially available from Degussa Corp. of South Plainfield, N.J.
- This example provides another preferred silver composition according to the invention that when applied to a surface and subsequently cured by ultraviolet radiation will produce a coating suitable for making resistive links on circuit board.
- the silver composition was made from the following components: Component Approximate Mass % Ebecryl 3603 18.3 IBOA 11.1 Silver Powder EGED 30.0 Silver Flake #1 33.5 Irgacure 1700 6.1 Modaflow 1.0 Total 100.00
- the IBOA and Iragure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm.
- the Ebecryl 3603 and the Modaflow are introduced into the pan and mixed for 5 minutes at a speed of 5000 rpm.
- the EGED silver powder and the Silver Flake #1 are introduced into the pan and are mixed for 1 to 2 minutes at a speed of 1000 rpm.
- the mixing speed is increased to 10,000 rpm and mixed for an additional 5 to 10 minutes.
- a presently preferred photocurable silver composition (“silver composition”) is provided.
- This composition upon photocuring produces a coating capable of producing resistive links in circuit boards.
- the silver composition includes an aliphatic acrylated oligomer.
- the aliphatic acrylated oligomer is present in an amount of about 7% to 11%, and preferably about 9%, of the silver composition.
- the aliphatic acrylated oligomer preferably comprises a urethane oligomer. Suitable aliphatic acrylated oligomers are the same as those listed above.
- the preferred aliphatic acrylated oligomers include Ebecryl 264 and Ebecryl 284.
- Ebecryl 264 is an aliphatic urethane triacrylate supplied as an 85% solution in hexandiol diacrylate.
- Ebecryl 284 is aliphatic urethane diacrylate of 1200 molecular weight diluted with 1,6-hexandiol diacrylate. Combinations of these materials may also be employed herein.
- This preferred silver composition further includes an acrylated epoxy oligomer.
- the acrylated epoxy oligomer is present in an amount of about 1% to 4%, and preferably about 3%, of the silver composition. Suitable acrylated epoxy oligomers are the same as those listed above.
- the preferred acrylated epoxy oligomer is Ebecryl 3603, which tri-functional acrylated epoxy novolac. Combinations of these materials may also be employed herein.
- the preferred silver composition also includes an isobornyl acrylate monomer in an amount of about 12% to 25%, and preferably about 22%, of the silver composition.
- Preferred isobornyl acrylate monomers include Sartomer SR423 IBOMA and SR506 IBOA; Radcure IBOA, commercially available from Radcure Corp.; IBOA and IBOMA, commercially available from CPS Chemical; and Genomer 1121, commercially available from Rahn Radiation Curing. Combinations of these materials may also be employed herein.
- a non-bridged cyclic acrylate monomer or a non-cylic acrylate monomer may be used in place of the isobornyl acrylate monomer or in combination with the isobornyl acrylate monomer.
- Suitable cyclic acrylate monomers or non-cyclic acrylate monomers are described by the following formula: wherein R 1 is hydrogen or substituted or unsubstituted alkyl; and R 2 is non-cyclic functional group or a non-bridged cyclic group. Examples of non-cyclic functional groups include substituted or unsubstituted alkyl having more than 4 carbon atoms.
- non-bridged cyclic groups include cycloalkyl, cycloalkenyl, and substituted or unsubstituted aryl.
- R 1 is hydrogen or methyl; and
- R 2 is phenyl, benzyl, dicylcopentenyl, dicyclopentenyl oxyethyl, cyclohexyl, and naphthyl.
- This preferred silver composition also includes a photoinitiator in an amount of about 2% to 4%, and preferably about 3%, of the silver composition.
- Suitable photoinitiators are the same as those listed above.
- the preferred photoinitiator is Irgacure 1700 commercially available from Ciba-Geigy of Tarrytown, N.Y.
- the preferred silver composition further includes a antimony tin oxide powder in an amount of 7% to 19%, and preferable about 17% of the silver composition.
- the preferred antimony tin oxide powder in Minatec 40 commercially available from EM Industries of Hawthorne, N.Y.
- the preferred silver composition still further includes a flow promoting agent in an amount of about 0.0% to 4%, and preferably about 2.0%, of the silver composition.
- Suitable flow promoting agents are the same as those listed above.
- the preferred flow promoting agent is Modaflow which is an ethyl acrylate and 2-ethylhexyl acrylate copolymer that improves the flow of the composition.
- the preferred silver composition also includes a silver powder in an amount of about 24% to 30%, and preferably about 27%, of the silver composition.
- the preferred silver powders are Silver Powder EG-ED and Silver Powder C-ED commercially available from Degussa Corp. of South Plainfield, N.J.
- the preferred silver composition further includes a silver flake composition in an amount of about 15% to 30%, and preferably about 17%, of the silver composition.
- the preferred silver flake compositions are Silver Flake #25, Silver Flake #1, and Silver Flake #7A commercially available from Degussa Corp. of South Plainfield, N.J.
- This example provides another preferred silver composition according to the invention that when applied to a surface and subsequently cured by ultraviolet radiation will produce a coating suitable for making resistive links on circuit board.
- the silver composition was made from the following components: Component Approximate Mass % Ebecryl 264 8.7 Ebecryl 3603 2.9 IBOA 22.4 Silver Flake # 7A 17.0 Silver powder CED 26.5 Minatec 40 17.2 Iragure 1700 3.3 Modaflow 2.0 Total 100.00
- the IBOA and Iragure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm.
- the Ebecryl 264, the Ebecryl 3603, and the Modaflow are introduced into the pan and mixed for 1 to 2 minutes at a speed of 1000 rpm.
- the CED silver powder, the Minatec 40, and the Silver Flake #7A are introduced into the pan and are mixed for 1 to 2 minutes at a speed of 1000 rpm.
- the mixing speed is increased to 10,000 rpm and mixed for an additional 5 minutes.
- This example provides another preferred silver composition according to the invention that when applied to a surface and subsequently cured by ultraviolet radiation will produce a coating suitable for making resistive links on circuit board.
- the silver composition was made from the following components: Component Approximate Mass % Ebecryl 284 8.4 Ebecryl 3603 1.7 Ebecryl 754 8.4 IBOA 15.7 Silver Powder CED 25.0 Silver Flake # 7A 28.5 Iragure 1700 2.5 Minatec 40 9.8 Total 100.00
- the IBOA and Iragure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm.
- the Ebecryl 754, Ebecryl 284, the Ebecryl 3603, and the Modaflow are introduced into the pan and mixed for 1 to 2 minutes at a speed of 1000 rpm.
- the CED silver powder, and the Silver Flake #7A are introduced into the pan and are mixed for 1 to 2 minutes at a speed of 1000 rpm.
- the mixing speed is increased to 10,000 rpm and mixed for an additional 5 minutes.
- Ebecryl 754 is a polyacrylic oligomer/acrylate monomer blend commercially available from Radcure UCB Corp. of Smyrna, Ga.
- a presently preferred photocurable silver composition (“silver composition”) is provided.
- This composition upon photocuring produces a dark-colored coating capable of producing resistive links in circuit boards.
- the silver composition includes an aliphatic acrylated oligomer.
- the aliphatic acrylated oligomer is present in an amount of about 7% to 11%, and preferably about 9%, of the silver composition.
- the aliphatic acrylated oligomer preferably comprises a urethane oligomer. Suitable aliphatic acrylated oligomers are the same as those listed above.
- the preferred aliphatic acrylated oligomers include Ebecryl 264 and Ebecryl 284.
- Ebecryl 264 is an aliphatic urethane triacrylate supplied as an 85% solution in hexandiol diacrylate.
- Ebecryl 284 is aliphatic urethane diacrylate of 1200 molecular weight diluted with 1,6-hexandiol diacrylate. Combinations of these materials may also be employed herein.
- This preferred silver composition further includes an acrylated epoxy oligomer.
- the acrylated epoxy oligomer is present in an amount of about 2% to 4%, and preferably about 3%, of the silver composition. Suitable acrylated epoxy oligomers are the same as those listed above.
- the preferred acrylated epoxy oligomer is Ebecryl 3603, which tri-functional acrylated epoxy novolac.
- the preferred silver composition also includes an isoborny 1 acrylate monomer in an amount of about 10% to 14%, and preferably about 12%, of the silver composition.
- Preferred isobornyl acrylate monomers include Sartomer SR423 IBOMA and SR506 IBOA; Radcure IBOA, commercially available from Radcure Corp.; IBOA AND IBOMA, commercially available from CPS Chemical; and Genomer 1121, commercially available from Rahn Radiation Curing.
- a non-bridged cyclic acrylate monomer or a non-cylic acrylate monomer may be used in place of the isobornyl acrylate monomer or in combination with the isobornyl acrylate monomer.
- Suitable cyclic acrylate monomers or non-cyclic acrylate monomers are described by the following formula: wherein R 1 is hydrogen or substituted or unsubstituted alkyl; and R 2 is non-cyclic functional group or a non-bridged cyclic group.
- non-cyclic functional groups include substituted or unsubstituted alkyl having more than 4 carbon atoms.
- non-bridged cyclic groups include cycloalkyl, cycloalkenyl, and substituted or unsubstituted aryl.
- R 1 is hydrogen or methyl
- R 2 is phenyl, benzyl, dicylcopentenyl, dicyclopentenyl oxyethyl, cyclohexyl, and naphthyl.
- This preferred silver composition also includes a photoinitiator in an amount of about 13% to 15%, and preferably about 14%, of the silver composition.
- the preferred photoinitiator is Irgacure 1700 commercially available from Ciba-Geigy of Tarrytown, N.Y.
- the preferred silver composition further includes a carbon black powder in an amount of 5% to 12%, and preferable about 7% of the silver composition.
- the preferred carbon black powder is Printex L commercially available from EM Industries of Hawthorne, N.Y.
- the preferred silver composition further includes a wetting agent in an amount of 0.5% to 3%, and preferable about 1.5% of the silver composition.
- the preferred wetting agent is BYK 207 L commercially available from Byk-Chemie of Wallingford, Conn.
- the preferred silver composition still further includes a flow promoting agent in an amount of about 0.1% to 2%, and preferably about 1.0%, of the silver composition.
- the preferred flow promoting agent is Modaflow which is an ethyl acrylate and 2-ethylhexyl acrylate copolymer that improves the flow of the composition. It is obvious to one skilled in the art that combinations of these materials may also be employed herein.
- the preferred silver composition also includes a silver powder in an amount of about 30% to 40%, and preferably about 36%, of the silver composition.
- the preferred silver powders are Silver Powder EG-ED and Silver Powder C-ED commercially available from Degussa Corp. of South Plainfield, N.J.
- the preferred silver composition further includes a silver flake composition in an amount of about 15% to 25%, and preferably about 18%, of the silver composition.
- the preferred silver flake compositions are Silver Flake #25, Silver Flake #1, and Silver Flake #7A commercially available from Degussa Corp. of South Plainfield, N.J.
- This example provides another preferred silver composition according to the invention that when applied to a surface and subsequently cured by ultraviolet radiation will produce a coating suitable for making black colored resistive links on circuit board.
- the silver composition was made from the following components: Component Approximate Mass % Ebecryl 264 8.8 Ebecryl 3603 2.5 Printex L 7.3 Byk 207 1.5 IBOA 11.6 Silver Powder EGED 35.7 Silver Flake # 25 18.4 Iragure 1700 13.5 Modaflow 0.7 Total 100.00
- the IBOA and Iragure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm.
- the Ebecryl 264, the Ebecryl 3603, and the Modaflow are introduced into the pan and mixed for 1 to 2 minutes at a speed of 1000 rpm.
- the EGED silver powder, the Silver Flake #25, and the Printex L are introduced into the pan and are mixed for 1 to 2 minutes at a speed of 1000 rpm.
- the BYK 207 in introduced and mixed for 5 minutes at a speed of 10,000 rpm.
- compositions have been described as “comprising” the stated component.
- each of those components consists essentially of, and more preferably they consist exclusively of, the stated components, and from the stated sources.
- the silver-containing composition as described above is referred to as being a “fluid phase” composition. This is meant to indicate that the composition is flowable as is a liquid, but is not otherwise limiting.
- the silver composition comprises a liquid.
- the composition for example, generally will be a slurry, in which the silver metal grains (powder and flakes) are solid-phase particles suspended in the liquid phase or phases of the urethane, epoxy, and any other liquid or essentially liquid components.
- a method for making a photocurable silver composition.
- the method includes a first step of combining and mixing an isobornyl acrylate monomer and a photoinitiators to create a first mixture.
- the isoborny 1 acrylate monomer is present in an amount of about 4% to 8% of the silver composition, and the photoinitiator is present in an amount of about 4% to 6% of the silver composition.
- This preferred method preferably but optionally is carried out using a mixing vessel of appropriate size, depending upon the desired batch size.
- This first step of the preferred method is carried out by placing the components into the vessel while stirring, e.g., by a suitable impeller.
- the method includes a second step of combining and mixing an aliphatic acrylated oligomer and an acrylated epoxy oligomer to create a second mixture.
- the aliphatic acrylated oligomer is present in an amount of about 3% to 8% of the silver composition and the acrylated epoxy oligomer is present in an amount of about 2% to 4% of the silver composition.
- this second step is carried out sequentially after the first step, and involves blending in these components into the first mixture, i.e., from the first step.
- the method further includes a third step of combining and mixing a silver powder and a silver flake composition to create a third mixture.
- the silver powder is present in an amount of about 50% to 60% of the silver composition and the silver flake composition is present An amount of about 25% to 35% of the silver composition.
- This step also preferably is carried out in the vessel, preferably sequentially after completion of the second step.
- the method further includes a fourth step of combining and mixing a flow promoting agent in an amount of about 0.1% to 2% of the silver composition, and a fifth step of combining the first, second, third and fourth mixtures to create the silver composition.
- steps also preferably would be performed sequentially by adding the cited components into the vessel while mixing with the impeller.
- the first, second, third and fourth steps are performed sequentially. This is not, however, limiting. Different processing orders may be used in accordance with the method.
- the method in its various forms may be carried out on a batch basis, for example, in a mixing vessel or similar process equipment suitable for batch processing. It may also be carried out in other forms, for example, such as continuous flow regimes, e.g., using known continuous flow processing equipment and configurations for mixing these components, preferably but optionally in the sequential order identified above.
- an ultraviolet curable silver composition comprises a first step of combining and mixing an isobornyl acrylate monomer and a photoinitiator to create a first composition, wherein the isobornyl acrylate monomer is present in an amount of about 4% to 8% of the silver composition, and the photoinitiator is present in an amount of about 3% to 6% of the silver composition.
- This method also includes a second step of combining with the first composition and mixing an aliphatic acrylated oligomer and an acrylated epoxy oligomer to create a second mixture.
- the aliphatic acrylated oligomer is present in an amount of about 3% to 8% of the silver composition and the acrylated epoxy oligomer is present in an amount of about 2% to 4% of the silver composition.
- the method further includes a third step of combining with the second composition and mixing a silver powder and a silver flake composition to create a third composition.
- the silver powder is present in an amount of about 50% to 60% of the silver composition and the silver flake composition is present in an amount of about 25% to 35% of the silver composition.
- the method still further includes a fourth step of combining with the third composition and mixing a flow promoting agent in an amount of about 0.1% to 2% of the silver composition.
- a method for preparing a liquid-phase silver-containing composition for use in providing a silver-containing coating, plating, film or layer on a substrate.
- the presently-preferred version of the method includes preparing either of the preferred silver compositions as identified in the examples above.
- the preferred version of this method includes a first step of combining and mixing the monomer and the photoinitiator in a mixing vessel.
- the method includes a second step of adding to the mixing vessel and blending into the previously-added components the urethane and the epoxy.
- the method also includes a third step of adding to the mixing vessel and blending into the components therein the silver powder and the silver flake.
- the preferred method further includes a fourth step of adding to the mixing vessel and blending into its previously-added components the flow agent.
- a method for depositing a silver coating on a substrate.
- the method comprises a first step of applying a silver-containing fluid-phase composition (“silver composition”) to the substrate.
- silver composition a silver-containing fluid-phase composition
- Each of the silver compositions described above are suitable for application to the substrate.
- the silver composition that is applied to the substrate comprises an aliphatic acrylated oligomer, the aliphatic acrylated oligomer being present in an amount of about 3% to 8% of the silver composition; an acrylated epoxy oligomer, the acrylated epoxy oligomer being present in an amount of about 2% to 4% of the silver composition; an isobornyl acrylate monomer in an amount of about 4% to 8% of the silver composition; a photoinitiator in an amount of about 3% to 6% of the silver composition; a flow promoting agent in an amount of about 0.1% to 2% of the silver composition; a silver powder in an amount of about 50% to 60% of the silver composition; and a silver flake composition in an amount of about 25% to 35% of the silver composition.
- the preferred silver compositions according to this method are those described herein, for example, including the compositions described in the examples.
- the silver composition may be applied to the substrate using a number of different techniques.
- the silver composition may be applied, for example, by direct brush application, or it may be sprayed onto the substrate surface. It also may be applied using a screen printing technique.
- screen printing technique a “screen” as the term is used in the screen printing industry is used to regulate the flow of liquid composition onto the substrate surface.
- the silver composition typically would be applied to the screen as the latter contacts the substrate. The silver composition flows through the silk screen to the substrate, whereupon it adheres to the substrate An the desired film thickness.
- Screen printing techniques suitable for this purpose include known techniques, but wherein the process is adjusted in ways known to persons of ordinary skill in the art to accommodate the viscosity, flowability, and other properties of the liquid-phase composition, the substrate and its surface properties, etc.
- Flexographic techniques for example, using pinch rollers to contact the silver composition with a rolling substrate, also may be used.
- the method includes a second step of illuminating the silver-containing fluid-phase composition on the substrate with an ultraviolet light to cause the silver-containing fluid-phase composition to cure into the silver coating.
- This illumination may be carried out in any number of ways, provided the ultraviolet light or radiation impinges upon the silver composition so that the silver composition is caused to polymerize to form the coating, layer, film, etc., and thereby cures.
- Such formed layers have a resistivity from 0.03 to 0.50 ohms/sq at 1 mil.
- Curing preferably takes place by free radical polymerization, which is initiated by an ultraviolet radiation source.
- the photoinitiator preferably comprises a photoinitiator, as described above.
- ultraviolet light sources may be used, depending on the application.
- Preferred ultraviolet radiation sources for a number of applications include known ultraviolet lighting equipment with energy intensity settings of, for example, 125 watts, 200 watts, and 300 watts per square inch.
Abstract
Description
- This application is a continuation of U.S. application Ser. No. 10/721,577, filed Nov. 24, 2003, which is a continuation-in-part of U.S. application Ser. No. 09/904,361 filed Jul. 12, 2001 which is a continuation-in-part of U.S. application Ser. No. 09/413,577 filed on Oct. 6, 1999 which is a continuation-in-part of U.S. application Ser. No. 09/291,774, filed Apr. 14, 1999; the entire disclosures of each of these applications is hereby incorporated by reference.
- The present invention relates to silver-containing compositions and more particularly to photocurable silver-containing compositions, to methods for making and applying a photocurable silver-containing compositions as a coating on a substrate.
- There are many instances in which it is necessary or desirable to apply a coating, plating or layer of silver or a silver-containing compound to a substrate. Examples of such applications would include electrode plating for switches such as those used on pressure-sensitive switches or control panels, for example, as are used on appliances such as microwave ovens, conventional ovens, and the like. Such silver plating also is commonly used in the semiconductor fabrication arts to apply silver metalizations on silicon or germanium semiconductor wafers. Other examples of such substrates include, without limitation, such things as polyesters, polycarbonates, vinyls, ceramics, glass, and the like.
- The predominant approach heretofore used in applying silver to substrates has involved using a solvent-based silver solution to the substrate, and chemically or thermally curing the solution to evaporate the solvent. This leaves the solid silver plating on the substrate.
- This conventional approach is disadvantageous in a number of respects. Of perhaps the greatest concern is the fact that the solvents currently used for this purpose are toxic. They require special handling and disposal facilities and techniques, and correspondingly increase inefficiencies and costs. Even while observing these special handling techniques, they present hazards to workers using these toxic materials. The solvent-based compositions and methods also are disadvantageous in that it can be difficult to predict the uniformity and thickness of the resultant silver plating after the solvent has evaporated. This leads to quality and performance variations.
- Accordingly, an object of the present invention is to provide a silver composition and method in which silver can be disposed on a substrate without requiring a toxic solvent.
- Another object of the invention is to provide a silver composition and method in which disposition of the silver layer can be done more quickly and efficiently than prior art solvent-based techniques.
- Another object of the invention is to provide a silver composition and method in which a silver coating may be created which has more predictable and uniform layer thickness relative to prior art solvent-based systems.
- To achieve the foregoing objects, and in accordance with the purposes of the invention as embodied and broadly described in this document, a silver composition is provided for deposition as a coating, plating, film or layer on a substrate. The terms coating, plating, film and layer in the context of this document are used to refer generally to a covering on the surface of a substrate, which covering may be of a variety of thicknesses depending on the application and the design goals.
- In accordance with one aspect of the invention, a photocurable silver composition is provided. The silver composition comprises a photocurable organic mixture, a photoinitiator, a silver powder, and a silver flake composition. The silver flake composition is present in an amount of at least 20% of the weight of the silver powder present in the composition. Incorporation of silver flake composition in an amount of at least 20% results in films with superior conductivity. Resistivities as low as 0.03 ohm/sq at 1 mil are achieved.
- The photocurable silver composition preferably comprises an aliphatic acrylated oligomer, wherein the aliphatic acrylated oligomer is present in an amount of about 3% to 8% based on the weight of the silver composition. All percentages of the silver composition as expressed in this document, unless otherwise stated, refer to the mass percentage of the stated component to the total mass of the silver composition in its fluid uncured state at standard temperature and pressure.
- The silver composition also preferably comprises an acrylated epoxy oligomer, wherein the acrylated epoxy oligomer is present in an amount of about 2% to 4% of the silver composition.
- The silver composition also preferably comprises an isoborny 1 acrylate monomer in an amount of about 4% to 8% of the silver composition, a photoinitiator in an amount of about 3% to 6% of the silver composition, a flow promoting agent in an amount of about 0.1% to 2% of the silver composition, a silver powder in an amount of about 50% to 60% of the silver composition, and a silver flake composition in an amount of about 25% to 35% of the silver composition.
- In accordance with this aspect of the invention, the aliphatic acrylated oligomer preferably comprises a urethane oligomer. In presently preferred versions of the silver composition, the aliphatic acrylated oligomer is present in an amount of about 8% of the silver composition.
- The acrylated epoxy oligomer is preferably present in an amount of about 3% of the silver composition. The isobornyl acrylate monomer is preferably present in an amount of about 5% of the silver composition. The photoinitiator is preferably present in an amount of about 5% of the silver composition. The flow promoting agent is preferably present in an amount of about 1% of the silver composition.
- In presently preferred embodiments according to this aspect of the invention, the silver powder preferably but optionally is present in an amount of about 52% of the silver composition. In these preferred embodiments, the silver powder has a particle size range of about 5 microns to about 15 microns. In a more preferred embodiment, the silver powder has a particle distribution such that about 5% to 20% of the particles have a particle size of less than about 4.7 microns, about 30% to 60% of the particles have a particle size of less than about 7.6 microns, and about 70% to 95% of the particles have a particle size of less than about 14.9 microns. In the most preferred embodiment, the silver powder has a particle distribution such that about 10% of the particles have a particle size of less than about 4.7 microns, about 50% of the particles have a particle size of less than about 7.6 microns, and about 90% of the particles have a particle size of less than about 14.9 microns.
- According to the presently preferred embodiments, the silver flake is present in an amount of about 30% of the silver composition. Preferably the silver flake has a particle size range of about 5 microns to about 32 microns. The silver flake preferably has a flake distribution such that about 10% of the particles have a particle size of less than about 5.5 microns, about 50% of the particles have a particle size of less than about 12.5 microns, and about 90% of the particles have a particle size of less than about 32.0 microns.
- In a further refinement of the presently preferred embodiment, an adhesion promoter is present in about 1 to 4% of the silver composition. This further refinement improves adhesion to substrates coated with transparent conductors such as indium tin oxide (ITO).
- In accordance with another aspect of the invention, a photocurable silver composition suitable for producing a coating that is capable of shielding electromagnetic radiation is provided. This embodiment is preferably applied to a substrate by spraying. The silver composition comprises an acrylated epoxy oligomer, wherein the acrylated epoxy oligomer is present in an amount of about 2% to 8% of the silver composition. The silver composition preferably comprises an isobornyl acrylate monomer in an amount of about 15% to 30% of the silver composition, an photoinitiator in an amount of about 3% to 7% of the silver composition, a flow promoting agent in an amount of about 0.1% to 2% of the silver composition, a silver powder in an amount of about 20% to 40% of the silver composition, and a silver flake composition in an amount of about 20% to 40% of the silver composition.
- In accordance with another aspect of the invention, a photocurable silver composition suitable for producing a coating that is capable of forming resistive links on circuit boards is provided. This embodiment of the invention preferably does not contain any urethane The silver composition comprises an acrylated epoxy oligomer having, wherein the acrylated epoxy oligomer is present in an amount of about 16% to 20% of the silver composition. The silver composition also comprises an isoborny 1 acrylate monomer in an amount of about 8% to 14% of the silver composition, an photoinitiator in an amount of about 4% to 8% of the silver composition, a flow promoting agent in an amount of about 0.1% to 2% of the silver composition, a silver powder in an amount of about 25% to 38% of the silver composition, and a silver flake composition in an amount of about 20% to 40% of the silver composition.
- In accordance with yet another aspect of the invention, a photocurable silver composition suitable for producing a coating that is capable resistive links on circuit boards is provided. This embodiment contains urethane. The silver composition comprises an aliphatic acrylated oligomer (a urethane), wherein the aliphatic acrylated oligomer is present in an amount of about 7% to 11% of the silver composition. The silver composition further comprises an acrylated epoxy oligomer, wherein the acrylated epoxy oligomer is present in an amount of about 1% to 4% of the silver composition. The silver composition also comprises an isobornyl acrylate monomer in an amount of about 12% to 25% of the silver composition, a photoinitiator in an amount of about 2% to 4% of the silver composition, a flow promoting agent in an amount of about 0.0% to 4% of the silver composition, an antimony tin oxide powder in an amount of 7% to 19%, a silver powder in an amount of about 24% to 30% of the silver composition, and a silver flake composition in an amount of about 15% to 30% of the silver composition. In a further refinement of this embodiment, the silver composition further comprises a polyacrylic oligomer/acrylate monomer blend in an amount of about 5% to 10%.
- In accordance with yet another aspect of the invention, a photocurable silver composition suitable for producing a coating that is capable black colored resistive links on circuit boards is provided. The silver composition comprises an aliphatic acrylated oligomer, wherein the aliphatic acrylated oligomer is present in an amount of about 7% to 11% of the silver composition The silver composition further comprises an acrylated epoxy oligomer having, wherein the acrylated epoxy oligomer is present in an amount of about 2% to 4% of the silver composition. The silver composition also comprises an isobornyl acrylate monomer in an amount of about 10% to 14% of the silver composition, a photoinitiator in an amount of about 13% to 15% of the silver composition, a flow promoting agent in an amount of about 0.1% to 2% of the silver composition, a conductive carbon black powder in an amount of 5% to 12%, a wetting agent in an amount of about 0.5 to 3% of the silver composition, a silver powder in an amount of about 30% to 40% of the silver composition, and a silver flake composition in an amount of about 15% to 25% of the silver composition.
- In accordance with another aspect of the invention, a method is provided for making a photocurable silver composition. The method comprises a first step of combining and mixing an isoborny 1 acrylate monomer and a photoinitiator to create a first mixture. The isobornyl acrylate monomer is present in an amount of about 4% to 8% of the silver composition, and the photoinitiator is present in an amount of about 3% to 6% of the silver composition.
- The method includes a second step of combining and mixing an aliphatic acrylated oligomer and an acrylated epoxy oligomer to create a second mixture. The aliphatic acrylated oligomer is present in an amount of about 3% to 8% of the silver composition and the acrylated epoxy oligomer is present in an amount of about 2% to 4% of the silver composition.
- The method includes a third step of combining and mixing a silver powder and a silver flake composition to create a third mixture. The silver powder is present in an amount of about 50% to 60% of the silver composition and the silver flake composition is present in an amount of about 25% to 35% of the silver composition.
- The method further includes a fourth step of combining and mixing a flow promoting agent in an amount of about 0.1% to 2% of the silver composition, and a fifth step of combining the first, second, third and fourth mixtures to create the silver composition.
- Preferably, but optionally, the first, second, third and fourth steps are performed sequentially. The method in its various forms may be carried out on a batch basis, for example, in a mixing vessel or similar process equipment suitable for batch processing. It may also be carried out in other forms, for example, such as continuous flow regimes.
- In accordance with another aspect of the invention, another method is provided for making a photocurable silver composition. This method comprises a first step of combining and mixing an isobornyl acrylate monomer and a photoinitiator to create a first composition, wherein the isobornyl acrylate monomer is present in an amount of about 4% to 8% of the silver composition, and the photoinitiator is present in an amount of about 3% to 6% of the silver composition. This method also includes a second step of combining with the first composition and mixing an aliphatic acrylated oligomer and an acrylated epoxy oligomer to create a second mixture. The aliphatic acrylated oligomer is present in an amount of about 3% to 8% of the silver composition and the acrylated epoxy oligomer is present in an amount of about 2% to 4% of the silver composition.
- The method further includes a third step of combining with the second composition and mixing a silver powder and a silver flake composition to create a third composition. The silver powder is present in an amount of about 50% to 60% of the silver composition and the silver flake composition is present in an amount of about 25% to 35% of the silver composition.
- The method still further includes a fourth step of combining with the third composition and mixing a flow promoting agent in an amount of about 0.1% to 2% of the silver composition.
- This method also may be carried out in a batch format, for example, in a mixing vessel or series of mixing vessels, in a continuous flow regime, or in some combination.
- In accordance with yet another aspect of the invention, a method is provided for depositing a silver coating on a substrate. The method comprises a first step of applying to the substrate a silver-containing fluid-phase composition (“silver composition”). The silver composition comprises an aliphatic acrylated oligomer, wherein the aliphatic acrylated oligomer is present in an amount of about 3% to 8% of the silver composition. The silver composition further includes an acrylated epoxy oligomer. The acrylated epoxy oligomer is present in an amount of about 2% to 4% of the silver composition. The silver composition also includes an isobornyl acrylate monomer in an amount of about 4% to 8% of the silver composition, a photoinitiator in an amount of about 3% to 6% of the silver composition, and a flow promoting agent in an amount of about 0.1% to 2% of the silver composition. The silver composition further includes a silver powder in an amount of about 50% to 60% of the silver composition, and a silver flake composition in an amount of about 25% to 35% of the silver composition.
- The method also includes a second step of illuminating the silver composition on the substrate with light of a wavelength suitable to cause the silver composition to cure into the silver coating. Preferably light will have a wavelength in the ultraviolet region of the electromagnetic spectrum.
- In accordance with this method, the silver composition can be selectively deposited on the substrate at specific locations where silver plating is desired. It need not be applied to the entire substrate. It is thus possible, for example, to use the silver coating thus created as metalizations on semiconductor wafers, printed circuit boards, pressure sensitive or pressure activated switches, and the like.
- According to another aspect of the invention, a method is provided for preparing a liquid-phase silver-containing composition for use in providing a silver-containing coating or plating on a substrate. The presently preferred version of the method includes preparing the composition as identified immediately above. The method in broad terms includes a first step of combining and mixing the monomer and the photoinitiator in a mixing vessel, a second step of adding to the mixing vessel and blending in the urethane and the epoxy, a third step of adding to the mixing vessel and blending in the silver powder and the silver flake, and a forth step of adding to the mixing vessel and blending in the flow agent.
- Silver Compositions
- Reference will now be made in detail to presently preferred compositions or embodiments and methods of the invention, which constitute the best modes of practicing the invention presently known to the inventor.
- In accordance with one aspect of the invention, a presently preferred photocurable silver composition (“silver composition”) is provided. In this preferred embodiment, the silver composition includes an aliphatic acrylated oligomer. The aliphatic acrylated oligomer is present in an amount of about 3% to 8%, and preferably about 8%, of the silver composition. The aliphatic acrylated oligomer preferably comprises a urethane oligomer. Suitable aliphatic acrylated oligomers include Radcure Ebecryl 244, Ebecryl 264 and Ebecryl 284 urethanes, commercially available from Radcure UCB Corp. of Smyrna, Ga.; Sartomer CN961, CN963, CN964, CN 966, CN982 and CN 983, commercially available from Sartomer Corp. of Exton, Pa.; TAB FAIRAD 8010, 8179, 8205, 8210, 8216, 8264, M-E-15, UVU-316, commercially available from TAB Chemicals of Chicago, Ill.; and Echo Resin ALU-303, commercially available from Echo Resins of Versaille, Mo.; and Genomer 4652, commercially available from Rahn Radiation Curing of Aurora, Ill. The preferred aliphatic acrylated oligomers include Ebecryl 264 and Ebecryl 284. Ebecryl 264 is an aliphatic urethane triacrylate supplied as an 85% solution in hexandiol diacrylate. Ebecryl 284 is aliphatic urethane diacrylate of 1200 molecular weight diluted with 1,6-hexandiol diacrylate. It is obvious to one skilled in the art that combinations of these materials may also be employed herein.
- This preferred silver composition further includes an acrylated epoxy oligomer. The acrylated epoxy oligomer is present in an amount of about 2% to 4%, and preferably about 3%, of the silver composition. Suitable acrylated epoxy oligomers include Radcure Ebecryl 3603, commercially available from Radcure UCB Corp.; Sartomer CN120 and CN124, commercially available from Sartomer Corp.; and Echo Resin TME 9310 and 9345, commercially available from Echo Resins. The preferred acrylated epoxy oligomer is Ebecryl 3603, which tri-functional acrylated epoxy novolac. Combinations of these materials may also be employed herein.
- The preferred silver composition also includes an isobornyl acrylate monomer preferably present in an amount of about 4% to 8%, and more preferably about 5%, of the silver composition. Isobornyl acrylates include the bridge cyclic isobornyl group which is known chemically to be quite bulky. Suitable isobornyl acrylate monomers include Sartomer SR423 IBOMA and SR506 IBOA; Radcure IBOA, commercially available from Radcure Corp.; IBOA and IBOMA, commercially available from CPS Chemical; and Genomer 1121, commercially available from Rahn Radiation Curing. Preferred isobornyl acrylate monomers include Sartomer SR423 IBOMA and SR506 IBOA; Radcure IBOA, commercially available from Radcure Corp.; IBOA AND IBOMA, commercially available from CPS Chemical; and Genomer 1121, commercially available from Rahn Radiation Curing. Alternatively, a non-bridged cyclic acrylate monomer or a non-cylic acrylate monomer may be used in place of the isobornyl acrylate monomer or in combination with the isobornyl acrylate monomer. Suitable cyclic acrylate monomers or non-cyclic acrylate monomers are described by the following formula:
wherein R1 is hydrogen or substituted or unsubstituted alkyl; and R2 is non-cyclic functional group or a non-bridged cyclic group. Examples of non-cyclic functional groups include substituted or unsubstituted alkyl having more than 4 carbon atoms. Examples of non-bridged cyclic groups include cycloalkyl, cycloalkenyl, and substituted or unsubstituted aryl. Preferably R1 is hydrogen or methyl; and R2 is phenyl, benzyl, dicylcopentenyl, dicyclopentenyl oxyethyl, cyclohexyl, and naphthyl. - This preferred silver composition also includes a photoinitiator in an amount of about 3% to 6%, and preferably about 4%, of the silver composition. Suitable photoinitiators include Irgacure 184 (1-hydroxycyclohexyl phenyl ketone), 907 (2-methyl-1-[4-(methylthio)phenyl]-2-morpholino propan-1-one), 369 (2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone), 500 (the combination of 1-hydroxy cyclohexyl phenyl ketone and benzophenone), 651 (2,2-dimethoxy-2-phenyl acetophenone), 1700 (the combination of bis(2,6-dimethoxybenzoyl-2,4-,4-trimethyl pentyl phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one), Ciba-Geigy 1700, and DAROCUR 1173 (2-hydroxy-2-methyl-1phenyl-1-propane) and 4265 (the combination of 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one), available commercially from Ciba-Geigy Corp., Tarrytown, N.Y.; CYRACURE UVI-6974 (mixed triaryl sulfonium hexafluoroantimonate salts) and UVI-6990 (mixed triaryl sulfonium hexafluorophosphate salts) available commercially from Union Carbide Chemicals and Plastics Co. Inc., Danbury, Conn.; and Genocure CQ, Genocure BOK, and GenocureMBF, commercially available from Rahn Radiation Curing. The preferred photoinitiator is Irgacure 1700 commercially available from Ciba-Geigy of Tarrytown, N.Y.
- The preferred silver composition still further includes a flow promoting agent in an amount of about 0.1% to 2%, and preferably about 1.0%, of the silver composition. Suitable flow promoting agents include Genorad 17, commercially available from Rahn Radiation Curing; and Modaflow, commercially available from Monsanto Chemical Co., St. Louis, Mo. The preferred flow promoting agent is Modaflow which is an ethyl acrylate and 2-ethylhexyl acrylate copolymer that improves the flow of the composition. Combinations of these materials may also be employed herein.
- The preferred silver composition also includes a silver powder in an amount of about 50% to 60%, and preferably about 52%, of the silver composition. The silver powder comprises a plurality of particles. In this preferred silver composition, the silver powder has a particle size range for these particles of about 5 microns to about 15 microns. In some embodiments, the silver powder has a particle size range of about 4.7 microns to about 14.9 microns. Preferably, the silver powder particles have a particle size distribution wherein about 10% of the particles have a particle size of less than about 4.7 microns, about 50% of the particles have a particle size of less than about 7.6 microns, and about 90% of the particles have a particle size of less than about 14.9 microns. The preferred silver powders are Silver Powder EG-ED and Silver Powder C-ED commercially available from Degussa Corp. of South Plainfield, N.J.
- The preferred silver composition further includes a silver flake composition in an amount of about 25% to 35%, and preferably about 30%, of the silver composition. The silver flake composition comprises a plurality of flakes which comprise, and which preferably consist essentially of, silver. The silver flake composition according to this embodiment has a particle size range of about 5 microns to about 32 microns. More preferably, the silver flake composition has a particle size range of about 5.5 microns to about 32.0 microns. The silver flake particle size distribution preferably is such that about 10% of the particles have a particle size of less than about 5.5 microns, about 50% of the particles have a particle size of less than about 12.5 microns, and about 90% of the particles have a particle size of less than about 32.0 microns. The preferred silver flake compositions are Silver Flake #25, Silver Flake #1, and Silver Flake #7A commercially available from Degussa Corp. of South Plainfield, N.J.
- This example provides a preferred silver composition according to the invention that can be used for deposition on the surface of a substrate such as a polymeric membrane, for example, to serve as the electrical contact for a pressure-sensitive switch. The silver composition was made from the following components:
Component Approximate Mass % Ebecryl 264 7.2 Ebecryl 3603 2.4 IBOA 4.7 Silver Powder EGED 53.4 Silver Flake # 25 27.6 Iragure 1700 3.9 Modaflow 0.8 Total 100.00 - In this example the IBOA and Iragure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm. Next, the Ebecryl 264, the Ebecryl 3603, and the Modaflow are introduced into the pan and mixed for 1 to 2 minutes at a speed of 1000 rpm. In the next step, the EGED silver powder, and the Silver Flake #25 are introduced into the pan and are mixed for 1 to 2 minutes at a speed of 1000 rpm. Finally, the mixing speed is increased to 10,000 rpm and mixed for an additional 5 minutes.
- For best results, the silver powder is washed prior to addition to the mixture. The washing process includes a first step of loading the powder in a sealable container. A mixture consisting of 17% methyl ethyl ketone and 83% silver composition is added to the container and the slurry is mixed with a propeller blade for 5 minutes at 500 rpm. The methyl ethyl ketone is poured off and the silver powder is allowed to air dry. During the drying stage the powder is periodically mixed.
- The silver powder according to the presently-preferred composition comprises EGED, commercially available from Degussa Corp. of South Plainfield, N.J. Such silver also may be obtained from other commercial sources, e.g., such as Englehard Chemical Co. of Iselin, N.J. The presently preferred silver powder has a grain size distribution ranging from about 5 microns to about 15 microns. This presently preferred silver powder has a particle size distribution as follows:
TABLE 1 Silver Powder Particle Size Distribution Size Range (microns) Percentage <4.7 10% <7.6 50% <14.9 90% - As this table indicates, within a sample of the silver powder, 10% of the grains have a size of less than 4.7 microns, 50% of the grains have a particle size of less than 7.6 microns, and 90% of the grains have a particle size of less than 14.9 microns.
- The silver flake according to the presently-preferred composition of Example I comprises SF25, commercially available from Degussa. This silver flake composition preferably has a grain size distribution ranging from about 5 microns to about 32 microns. It has a particle size distribution as follows:
TABLE 2 Silver Flake Composition Particle Size Distribution Size Range (microns) Percentage <5.5 10% <12.5 50% <32.0 90% - As indicated in Table 2, within a sample of the silver flake, 10% of the flakes have a size of less than 5.5 microns, 50% of the flakes have a particle size of less than 12.5 microns, and 90% of the flakes have a particle size of less than 32.0 microns.
- This example provides another preferred silver composition according to the invention that can be used for deposition on the surface of a substrate such as those noted above. The silver composition was made from the following components:
Component Approximate Mass % Ebecryl 264 4.2 Ebecryl 3603 2.7 IBOA 7.7 Silver Powder EGED 53.4 Silver Flake #25 27.6 Iragure 1700 3.8 Modaflow 0.6 Total 100.00 - In this example the IBOA and Iragure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm. Next, the Ebecryl 264, the Ebecryl 3603, and the Modaflow are introduced into the pan and mixed for 1 to 2 minutes at a speed of 1000 rpm. In the next step, the EGED silver powder, and the Silver Flake #25 are introduced into the pan and are mixed for 1 to 2 minutes at a speed of 1000 rpm. Finally, the mixing speed is increased to 10,000 rpm and mixed for an additional 5 minutes.
- This example provides another preferred silver composition according to the invention that can be used for deposition on the surface of a substrate coated with indium tin oxide (ITO). The silver composition was made from the following components:
Component Approximate Mass % Ebecryl 264 7.0 Ebecryl 3603 2.3 IBOA 4.6 Silver Powder EGED 52.3 Silver Flake # 25 27.0 Iragure 1700 3.8 Modaflow 0.8 Ebecryl 168 2.2 Total 100.00 - In this example the IBOA and Iragure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm. Next, the Ebecryl 264, the Ebecryl 3603, and the Modaflow are introduced into the pan and mixed for 1 to 2 minutes at a speed of 1000 rpm. In the next step, the EGED silver powder, and the Silver Flake #25 are introduced into the pan and are mixed for 1 to 2 minutes at a speed of 1000 rpm. In the next step, the Ebecryl 168 is added into the pan and the combination mixed at 1000 rpm for 1 to 2 minutes. Finally, the mixing speed is increased to 10,000 rpm and mixed for an additional 5 minutes.
- This example contains Ebecryl 168 added as an adhesion promoter. This material is a methacrylate ester derivative commercially available from Radcure UCB Corp. of Smyrna, Ga.
- Silver Composition for Producing a Coating Capable Of Shielding Electromagnetic Interference
- In accordance with another aspect of the invention, a presently preferred photocurable silver composition (“silver composition”) is provided. This composition upon photocuring produces a coating capable of shielding electromagnet interference. Such a coating may be applied to substrates requiring shielding from electromagnetic interferences such as the interior of radio casings. In this preferred embodiment, the silver composition includes an acrylated epoxy oligomer. The acrylated epoxy oligomer is present in an amount of about 2% to 8%, and preferably about 5%, of the silver composition. Suitable acrylated epoxy oligomers are the same as listed above. The preferred acrylated epoxy oligomer is Ebecryl 3603, which tri-functional acrylated epoxy novolac. Combinations of these materials may also be employed herein.
- The preferred silver composition also includes an isobornyl acrylate monomer in an amount of about 15% to 30%, and preferably about 21%, of the silver composition. Suitable isobornyl acrylate monomers are the same as listed above. Preferred isobornyl acrylate monomers include Sartomer SR423 IBOMA and SR506 IBOA; Radcure IBOA, commercially available from Radcure Corp.; IBOA and IBOMA, commercially available from CPS Chemical; and Genomer 1121, commercially available from Rahn Radiation Curing. Combinations of these materials may also be employed herein. Alternatively, a non-bridged cyclic acrylate monomer or a non-cylic acrylate monomer may be used in place of the isobornyl acrylate monomer or in combination with the isobornyl acrylate monomer. Suitable cyclic acrylate monomers or non-cyclic acrylate monomers are described by the following formula:
wherein R1 is hydrogen or substituted or unsubstituted alkyl; and R2 is non-cyclic functional group or a non-bridged cyclic group. Examples of non-cyclic functional groups include substituted or unsubstituted alkyl having more than 4 carbon atoms. Examples of non-bridged cyclic groups include cycloalkyl, cycloalkenyl, and substituted or unsubstituted aryl. Preferably R1 is hydrogen or methyl; and R2 is phenyl, benzyl, dicylcopentenyl, dicyclopentenyl oxyethyl, cyclohexyl, and naphthyl. - This preferred silver composition also includes a photoinitiator in an amount of about 3% to 7%, and preferably about 5%, of the silver composition. Suitable photoinitiators are the same as listed above. The preferred photoinitiator is Irgacure 1700 commercially available from Ciba-Geigy of Tarrytown, N.Y. Combinations of these materials may also be employed herein.
- The preferred silver composition still further includes a flow promoting agent in an amount of about 0.1% to 2%, and preferably about 1.0%, of the silver composition. Suitable flow promoting agents are the same as listed above. The preferred flow promoting agent is Modaflow which is an ethyl acrylate and 2-ethylhexyl acrylate copolymer that improves the flow of the composition. Combinations of these materials may also be employed herein.
- The preferred silver composition also includes a silver powder in an amount of about 25% to 40%, and preferably about 36%, of the silver composition. The preferred silver powders are Silver Powder EG-ED and Silver Powder C-ED commercially available from Degussa Corp. of South Plainfield, N.J.
- The preferred silver composition further includes a silver flake composition in an amount of about 20% to 40%, and preferably about 30%, of the silver composition. The preferred silver flake compositions are Silver Flake #25, Silver Flake #1, and Silver Flake #7A commercially available from Degussa Corp. of South Plainfield, N.J.
- This example provides another preferred silver composition according to the invention that when applied to a surface and subsequently cured by ultraviolet radiation will produce a coating suitable for shielding electromagnetic interference. The silver composition was made from the following components:
Component Approximate Mass % Ebecryl 3603 5.3 IBOA 21.0 Silver Powder EGED 31.5 Silver Flake # 1 35.7 Iragure 1700 5.3 Modaflow 1.2 Total 100.00 - In this example the IBOA and Iragure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm. Next, the Ebecryl 3603, and the Modaflow are introduced into the pan and mixed for 5 minutes at a speed of 5000 rpm. In the next step, the EGED silver powder and the Silver Flake #1 are introduced into the pan and are mixed for 1 to 2 minutes at a speed of 1000 rpm. Finally, the mixing speed is increased to 10,000 rpm and mixed for an additional 5 to 10 minutes.
- Non-Urethane Containing Silver Composition for Producing Resistive Links
- In accordance with another aspect of the invention, a presently preferred photocurable silver composition (“silver composition”) is provided. This composition upon photocuring produces a coating capable of producing resistive links in circuit boards. In this preferred embodiment, the silver composition includes an acrylated epoxy oligomer. The acrylated epoxy oligomer is present in an amount of about 16% to 20%, and preferably about 18%, of the silver composition. Suitable acrylated epoxy oligomers are the same as listed above. The preferred acrylated epoxy oligomer is Ebecryl 3603, which tri-functional acrylated epoxy novolac. Combinations of these materials may also be employed herein.
- The preferred silver composition also includes an isobornyl acrylate monomer in an amount of about 8% to 14%, and preferably about 11%, of the silver composition. Suitable isobornyl acrylate monomers are the same as listed above. Preferred isobornyl acrylate monomers include Sartomer SR423 IBOMA and SR506 IBOA; Radcure IBOA, commercially available from Radcure Corp.; IBOA AND IBOMA, commercially available from CPS Chemical; and Genomer 1121, commercially available from Rahn Radiation Curing. Combinations of these materials may also be employed herein. Alternatively, a non-bridged cyclic acrylate monomer or a non-cylic acrylate monomer may be used in place of the isobornyl acrylate monomer or in combination with the isobornyl acrylate monomer. Suitable cyclic acrylate monomers or non-cyclic acrylate monomers are described by the following formula:
wherein R1 is hydrogen or substituted or unsubstituted alkyl; and R2 is non-cyclic functional group or a non-bridged cyclic group. Examples of non-cyclic functional groups include substituted or unsubstituted alkyl having more than 4 carbon atoms. Examples of non-bridged cyclic groups include cycloalkyl, cycloalkenyl, and substituted or unsubstituted aryl. Preferably R1 is hydrogen or methyl; and R2 is phenyl, benzyl, dicylcopentenyl, dicyclopentenyl oxyethyl, cyclohexyl, and naphthyl. - This preferred silver composition also includes a photoinitiator in an amount of about 4% to 8%, and preferably about 6%, of the silver composition. Suitable photoinitiators are the same as those listed above. The preferred photoinitiator is Irgacure 1700 commercially available from Ciba-Geigy of Tarrytown, N.Y. Combinations of these materials may also be employed herein.
- The preferred silver composition still further includes a flow promoting agent in an amount of about 0.1% to 2%, and preferably about 1.0%, of the silver composition. Suitable flow promoting agents are the same as those listed above. The preferred flow promoting agent is Modaflow which is an ethyl acrylate and 2-ethylhexyl acrylate copolymer that improves the flow of the composition. Combinations of these materials may also be employed herein.
- The preferred silver composition also includes a silver powder in an amount of about 25% to 35%, and preferably about 30%, of the silver composition. The preferred silver powders are Silver Powder EG-ED and Silver Powder C-ED commercially available from Degussa Corp. of South Plainfield, N.J.
- The preferred silver composition further includes a silver flake composition in an amount of about 25% to 38%, and preferably about 34%, of the silver composition. The preferred silver flake compositions are Silver Flake #25, Silver Flake #1, and Silver Flake #7A commercially available from Degussa Corp. of South Plainfield, N.J.
- To illustrate, the following example sets forth a presently preferred silver composition according to this aspect of the invention.
- This example provides another preferred silver composition according to the invention that when applied to a surface and subsequently cured by ultraviolet radiation will produce a coating suitable for making resistive links on circuit board. The silver composition was made from the following components:
Component Approximate Mass % Ebecryl 3603 18.3 IBOA 11.1 Silver Powder EGED 30.0 Silver Flake #1 33.5 Irgacure 1700 6.1 Modaflow 1.0 Total 100.00 - In this example the IBOA and Iragure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm. Next, the Ebecryl 3603 and the Modaflow are introduced into the pan and mixed for 5 minutes at a speed of 5000 rpm. In the next step, the EGED silver powder and the Silver Flake #1 are introduced into the pan and are mixed for 1 to 2 minutes at a speed of 1000 rpm. Finally, the mixing speed is increased to 10,000 rpm and mixed for an additional 5 to 10 minutes.
- Urethane Containing Silver Composition for Producing Resistive Links
- In accordance with one aspect of the invention, a presently preferred photocurable silver composition (“silver composition”) is provided. This composition upon photocuring produces a coating capable of producing resistive links in circuit boards. In this preferred embodiment, the silver composition includes an aliphatic acrylated oligomer. The aliphatic acrylated oligomer is present in an amount of about 7% to 11%, and preferably about 9%, of the silver composition. The aliphatic acrylated oligomer preferably comprises a urethane oligomer. Suitable aliphatic acrylated oligomers are the same as those listed above. The preferred aliphatic acrylated oligomers include Ebecryl 264 and Ebecryl 284. Ebecryl 264 is an aliphatic urethane triacrylate supplied as an 85% solution in hexandiol diacrylate. Ebecryl 284 is aliphatic urethane diacrylate of 1200 molecular weight diluted with 1,6-hexandiol diacrylate. Combinations of these materials may also be employed herein.
- This preferred silver composition further includes an acrylated epoxy oligomer. The acrylated epoxy oligomer is present in an amount of about 1% to 4%, and preferably about 3%, of the silver composition. Suitable acrylated epoxy oligomers are the same as those listed above. The preferred acrylated epoxy oligomer is Ebecryl 3603, which tri-functional acrylated epoxy novolac. Combinations of these materials may also be employed herein.
- The preferred silver composition also includes an isobornyl acrylate monomer in an amount of about 12% to 25%, and preferably about 22%, of the silver composition. Preferred isobornyl acrylate monomers include Sartomer SR423 IBOMA and SR506 IBOA; Radcure IBOA, commercially available from Radcure Corp.; IBOA and IBOMA, commercially available from CPS Chemical; and Genomer 1121, commercially available from Rahn Radiation Curing. Combinations of these materials may also be employed herein. Alternatively, a non-bridged cyclic acrylate monomer or a non-cylic acrylate monomer may be used in place of the isobornyl acrylate monomer or in combination with the isobornyl acrylate monomer. Suitable cyclic acrylate monomers or non-cyclic acrylate monomers are described by the following formula:
wherein R1 is hydrogen or substituted or unsubstituted alkyl; and R2 is non-cyclic functional group or a non-bridged cyclic group. Examples of non-cyclic functional groups include substituted or unsubstituted alkyl having more than 4 carbon atoms. Examples of non-bridged cyclic groups include cycloalkyl, cycloalkenyl, and substituted or unsubstituted aryl. Preferably R1 is hydrogen or methyl; and R2 is phenyl, benzyl, dicylcopentenyl, dicyclopentenyl oxyethyl, cyclohexyl, and naphthyl. - This preferred silver composition also includes a photoinitiator in an amount of about 2% to 4%, and preferably about 3%, of the silver composition. Suitable photoinitiators are the same as those listed above. The preferred photoinitiator is Irgacure 1700 commercially available from Ciba-Geigy of Tarrytown, N.Y.
- The preferred silver composition further includes a antimony tin oxide powder in an amount of 7% to 19%, and preferable about 17% of the silver composition. The preferred antimony tin oxide powder in Minatec 40 commercially available from EM Industries of Hawthorne, N.Y.
- The preferred silver composition still further includes a flow promoting agent in an amount of about 0.0% to 4%, and preferably about 2.0%, of the silver composition. Suitable flow promoting agents are the same as those listed above. The preferred flow promoting agent is Modaflow which is an ethyl acrylate and 2-ethylhexyl acrylate copolymer that improves the flow of the composition.
- The preferred silver composition also includes a silver powder in an amount of about 24% to 30%, and preferably about 27%, of the silver composition. The preferred silver powders are Silver Powder EG-ED and Silver Powder C-ED commercially available from Degussa Corp. of South Plainfield, N.J.
- The preferred silver composition further includes a silver flake composition in an amount of about 15% to 30%, and preferably about 17%, of the silver composition. The preferred silver flake compositions are Silver Flake #25, Silver Flake #1, and Silver Flake #7A commercially available from Degussa Corp. of South Plainfield, N.J.
- This example provides another preferred silver composition according to the invention that when applied to a surface and subsequently cured by ultraviolet radiation will produce a coating suitable for making resistive links on circuit board. The silver composition was made from the following components:
Component Approximate Mass % Ebecryl 264 8.7 Ebecryl 3603 2.9 IBOA 22.4 Silver Flake # 7A 17.0 Silver powder CED 26.5 Minatec 40 17.2 Iragure 1700 3.3 Modaflow 2.0 Total 100.00 - In this example the IBOA and Iragure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm. Next, the Ebecryl 264, the Ebecryl 3603, and the Modaflow are introduced into the pan and mixed for 1 to 2 minutes at a speed of 1000 rpm. In the next step, the CED silver powder, the Minatec 40, and the Silver Flake #7A are introduced into the pan and are mixed for 1 to 2 minutes at a speed of 1000 rpm. Finally, the mixing speed is increased to 10,000 rpm and mixed for an additional 5 minutes.
- This example provides another preferred silver composition according to the invention that when applied to a surface and subsequently cured by ultraviolet radiation will produce a coating suitable for making resistive links on circuit board. The silver composition was made from the following components:
Component Approximate Mass % Ebecryl 284 8.4 Ebecryl 3603 1.7 Ebecryl 754 8.4 IBOA 15.7 Silver Powder CED 25.0 Silver Flake # 7A 28.5 Iragure 1700 2.5 Minatec 40 9.8 Total 100.00 - In this example the IBOA and Iragure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm. Next, the Ebecryl 754, Ebecryl 284, the Ebecryl 3603, and the Modaflow are introduced into the pan and mixed for 1 to 2 minutes at a speed of 1000 rpm. In the next step, the CED silver powder, and the Silver Flake #7A are introduced into the pan and are mixed for 1 to 2 minutes at a speed of 1000 rpm. Finally, the mixing speed is increased to 10,000 rpm and mixed for an additional 5 minutes.
- This example contains Ebecryl 754 as an additive. Ebecryl 754 is a polyacrylic oligomer/acrylate monomer blend commercially available from Radcure UCB Corp. of Smyrna, Ga.
- Black Colored Silver Composition for Producing Resistive Links
- In accordance with one aspect of the invention, a presently preferred photocurable silver composition (“silver composition”) is provided. This composition upon photocuring produces a dark-colored coating capable of producing resistive links in circuit boards. In this preferred embodiment, the silver composition includes an aliphatic acrylated oligomer. The aliphatic acrylated oligomer is present in an amount of about 7% to 11%, and preferably about 9%, of the silver composition. The aliphatic acrylated oligomer preferably comprises a urethane oligomer. Suitable aliphatic acrylated oligomers are the same as those listed above. The preferred aliphatic acrylated oligomers include Ebecryl 264 and Ebecryl 284. Ebecryl 264 is an aliphatic urethane triacrylate supplied as an 85% solution in hexandiol diacrylate. Ebecryl 284 is aliphatic urethane diacrylate of 1200 molecular weight diluted with 1,6-hexandiol diacrylate. Combinations of these materials may also be employed herein.
- This preferred silver composition further includes an acrylated epoxy oligomer. The acrylated epoxy oligomer is present in an amount of about 2% to 4%, and preferably about 3%, of the silver composition. Suitable acrylated epoxy oligomers are the same as those listed above. The preferred acrylated epoxy oligomer is Ebecryl 3603, which tri-functional acrylated epoxy novolac.
- The preferred silver composition also includes an isoborny 1 acrylate monomer in an amount of about 10% to 14%, and preferably about 12%, of the silver composition. Preferred isobornyl acrylate monomers include Sartomer SR423 IBOMA and SR506 IBOA; Radcure IBOA, commercially available from Radcure Corp.; IBOA AND IBOMA, commercially available from CPS Chemical; and Genomer 1121, commercially available from Rahn Radiation Curing. Alternatively, a non-bridged cyclic acrylate monomer or a non-cylic acrylate monomer may be used in place of the isobornyl acrylate monomer or in combination with the isobornyl acrylate monomer. Suitable cyclic acrylate monomers or non-cyclic acrylate monomers are described by the following formula:
wherein R1 is hydrogen or substituted or unsubstituted alkyl; and R2 is non-cyclic functional group or a non-bridged cyclic group. Examples of non-cyclic functional groups include substituted or unsubstituted alkyl having more than 4 carbon atoms. Examples of non-bridged cyclic groups include cycloalkyl, cycloalkenyl, and substituted or unsubstituted aryl. Preferably R1 is hydrogen or methyl; and R2 is phenyl, benzyl, dicylcopentenyl, dicyclopentenyl oxyethyl, cyclohexyl, and naphthyl. - This preferred silver composition also includes a photoinitiator in an amount of about 13% to 15%, and preferably about 14%, of the silver composition. The preferred photoinitiator is Irgacure 1700 commercially available from Ciba-Geigy of Tarrytown, N.Y.
- The preferred silver composition further includes a carbon black powder in an amount of 5% to 12%, and preferable about 7% of the silver composition. The preferred carbon black powder is Printex L commercially available from EM Industries of Hawthorne, N.Y.
- The preferred silver composition further includes a wetting agent in an amount of 0.5% to 3%, and preferable about 1.5% of the silver composition. The preferred wetting agent is BYK 207 L commercially available from Byk-Chemie of Wallingford, Conn.
- The preferred silver composition still further includes a flow promoting agent in an amount of about 0.1% to 2%, and preferably about 1.0%, of the silver composition. The preferred flow promoting agent is Modaflow which is an ethyl acrylate and 2-ethylhexyl acrylate copolymer that improves the flow of the composition. It is obvious to one skilled in the art that combinations of these materials may also be employed herein.
- The preferred silver composition also includes a silver powder in an amount of about 30% to 40%, and preferably about 36%, of the silver composition. The preferred silver powders are Silver Powder EG-ED and Silver Powder C-ED commercially available from Degussa Corp. of South Plainfield, N.J.
- The preferred silver composition further includes a silver flake composition in an amount of about 15% to 25%, and preferably about 18%, of the silver composition. The preferred silver flake compositions are Silver Flake #25, Silver Flake #1, and Silver Flake #7A commercially available from Degussa Corp. of South Plainfield, N.J.
- This example provides another preferred silver composition according to the invention that when applied to a surface and subsequently cured by ultraviolet radiation will produce a coating suitable for making black colored resistive links on circuit board. The silver composition was made from the following components:
Component Approximate Mass % Ebecryl 264 8.8 Ebecryl 3603 2.5 Printex L 7.3 Byk 207 1.5 IBOA 11.6 Silver Powder EGED 35.7 Silver Flake # 25 18.4 Iragure 1700 13.5 Modaflow 0.7 Total 100.00 - In this example the IBOA and Iragure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm. Next, the Ebecryl 264, the Ebecryl 3603, and the Modaflow are introduced into the pan and mixed for 1 to 2 minutes at a speed of 1000 rpm. In the next step, the EGED silver powder, the Silver Flake #25, and the Printex L are introduced into the pan and are mixed for 1 to 2 minutes at a speed of 1000 rpm. Finally, the BYK 207 in introduced and mixed for 5 minutes at a speed of 10,000 rpm.
- In describing each of the components in these examples and in this description, the compositions have been described as “comprising” the stated component. Preferably each of those components consists essentially of, and more preferably they consist exclusively of, the stated components, and from the stated sources.
- The silver-containing composition as described above is referred to as being a “fluid phase” composition. This is meant to indicate that the composition is flowable as is a liquid, but is not otherwise limiting. Preferably, the silver composition comprises a liquid. The composition, for example, generally will be a slurry, in which the silver metal grains (powder and flakes) are solid-phase particles suspended in the liquid phase or phases of the urethane, epoxy, and any other liquid or essentially liquid components.
- Method for Preparing Silver Composition
- In accordance with another aspect of the invention, a method is provided for making a photocurable silver composition. In accordance with a preferred version, the method includes a first step of combining and mixing an isobornyl acrylate monomer and a photoinitiators to create a first mixture. The isoborny 1 acrylate monomer is present in an amount of about 4% to 8% of the silver composition, and the photoinitiator is present in an amount of about 4% to 6% of the silver composition.
- This preferred method preferably but optionally is carried out using a mixing vessel of appropriate size, depending upon the desired batch size. A glass or steel lined batch processing vessel of known design and commercial availability typically will suffice.
- This first step of the preferred method is carried out by placing the components into the vessel while stirring, e.g., by a suitable impeller.
- The method includes a second step of combining and mixing an aliphatic acrylated oligomer and an acrylated epoxy oligomer to create a second mixture. The aliphatic acrylated oligomer is present in an amount of about 3% to 8% of the silver composition and the acrylated epoxy oligomer is present in an amount of about 2% to 4% of the silver composition. In accordance with this preferred method, this second step is carried out sequentially after the first step, and involves blending in these components into the first mixture, i.e., from the first step.
- The method further includes a third step of combining and mixing a silver powder and a silver flake composition to create a third mixture. The silver powder is present in an amount of about 50% to 60% of the silver composition and the silver flake composition is present An amount of about 25% to 35% of the silver composition. This step also preferably is carried out in the vessel, preferably sequentially after completion of the second step.
- The method further includes a fourth step of combining and mixing a flow promoting agent in an amount of about 0.1% to 2% of the silver composition, and a fifth step of combining the first, second, third and fourth mixtures to create the silver composition.
- These steps also preferably would be performed sequentially by adding the cited components into the vessel while mixing with the impeller.
- As noted, preferably but optionally, the first, second, third and fourth steps are performed sequentially. This is not, however, limiting. Different processing orders may be used in accordance with the method.
- Also as noted, the method in its various forms may be carried out on a batch basis, for example, in a mixing vessel or similar process equipment suitable for batch processing. It may also be carried out in other forms, for example, such as continuous flow regimes, e.g., using known continuous flow processing equipment and configurations for mixing these components, preferably but optionally in the sequential order identified above.
- In accordance with another aspect of the invention, another method is provided for making an ultraviolet curable silver composition. This method comprises a first step of combining and mixing an isobornyl acrylate monomer and a photoinitiator to create a first composition, wherein the isobornyl acrylate monomer is present in an amount of about 4% to 8% of the silver composition, and the photoinitiator is present in an amount of about 3% to 6% of the silver composition. This method also includes a second step of combining with the first composition and mixing an aliphatic acrylated oligomer and an acrylated epoxy oligomer to create a second mixture. The aliphatic acrylated oligomer is present in an amount of about 3% to 8% of the silver composition and the acrylated epoxy oligomer is present in an amount of about 2% to 4% of the silver composition.
- The method further includes a third step of combining with the second composition and mixing a silver powder and a silver flake composition to create a third composition. The silver powder is present in an amount of about 50% to 60% of the silver composition and the silver flake composition is present in an amount of about 25% to 35% of the silver composition.
- The method still further includes a fourth step of combining with the third composition and mixing a flow promoting agent in an amount of about 0.1% to 2% of the silver composition.
- According to another aspect of the invention, a method is provided for preparing a liquid-phase silver-containing composition for use in providing a silver-containing coating, plating, film or layer on a substrate. The presently-preferred version of the method includes preparing either of the preferred silver compositions as identified in the examples above. The preferred version of this method includes a first step of combining and mixing the monomer and the photoinitiator in a mixing vessel. The method includes a second step of adding to the mixing vessel and blending into the previously-added components the urethane and the epoxy. The method also includes a third step of adding to the mixing vessel and blending into the components therein the silver powder and the silver flake. The preferred method further includes a fourth step of adding to the mixing vessel and blending into its previously-added components the flow agent.
- Method for Depositing a Silver Coating on a Substrate
- In accordance with still another aspect of the invention, a method is provided for depositing a silver coating on a substrate. The method comprises a first step of applying a silver-containing fluid-phase composition (“silver composition”) to the substrate. Each of the silver compositions described above are suitable for application to the substrate.
- In a preferred embodiment, the silver composition that is applied to the substrate comprises an aliphatic acrylated oligomer, the aliphatic acrylated oligomer being present in an amount of about 3% to 8% of the silver composition; an acrylated epoxy oligomer, the acrylated epoxy oligomer being present in an amount of about 2% to 4% of the silver composition; an isobornyl acrylate monomer in an amount of about 4% to 8% of the silver composition; a photoinitiator in an amount of about 3% to 6% of the silver composition; a flow promoting agent in an amount of about 0.1% to 2% of the silver composition; a silver powder in an amount of about 50% to 60% of the silver composition; and a silver flake composition in an amount of about 25% to 35% of the silver composition. The preferred silver compositions according to this method are those described herein, for example, including the compositions described in the examples.
- The silver composition may be applied to the substrate using a number of different techniques. The silver composition may be applied, for example, by direct brush application, or it may be sprayed onto the substrate surface. It also may be applied using a screen printing technique. In such screen printing technique, a “screen” as the term is used in the screen printing industry is used to regulate the flow of liquid composition onto the substrate surface. The silver composition typically would be applied to the screen as the latter contacts the substrate. The silver composition flows through the silk screen to the substrate, whereupon it adheres to the substrate An the desired film thickness. Screen printing techniques suitable for this purpose include known techniques, but wherein the process is adjusted in ways known to persons of ordinary skill in the art to accommodate the viscosity, flowability, and other properties of the liquid-phase composition, the substrate and its surface properties, etc. Flexographic techniques, for example, using pinch rollers to contact the silver composition with a rolling substrate, also may be used.
- The method includes a second step of illuminating the silver-containing fluid-phase composition on the substrate with an ultraviolet light to cause the silver-containing fluid-phase composition to cure into the silver coating. This illumination may be carried out in any number of ways, provided the ultraviolet light or radiation impinges upon the silver composition so that the silver composition is caused to polymerize to form the coating, layer, film, etc., and thereby cures. Such formed layers have a resistivity from 0.03 to 0.50 ohms/sq at 1 mil.
- Curing preferably takes place by free radical polymerization, which is initiated by an ultraviolet radiation source. The photoinitiator preferably comprises a photoinitiator, as described above.
- Various ultraviolet light sources may be used, depending on the application. Preferred ultraviolet radiation sources for a number of applications include known ultraviolet lighting equipment with energy intensity settings of, for example, 125 watts, 200 watts, and 300 watts per square inch.
- Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details, representative devices, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the spirit or scope of the general inventive concept.
Claims (17)
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US11/637,572 US20070123645A1 (en) | 1999-04-14 | 2006-12-12 | Ultraviolet curable silver composition and related method |
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Also Published As
Publication number | Publication date |
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WO2005052692A1 (en) | 2005-06-09 |
US7157507B2 (en) | 2007-01-02 |
US20040106718A1 (en) | 2004-06-03 |
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