Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
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  • B32B19/00—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica
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  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
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  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/14—Layered products comprising a layer of synthetic resin next to a particulate layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
  • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
  • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
• • 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
  • C08K3/04—Carbon
• • 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
  • H05K1/0275—Security details, e.g. tampering prevention or detection
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/036—Multilayers with layers of different types
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/28—Applying non-metallic protective coatings
  • H05K3/285—Permanent coating compositions
• • 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
• • 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
  • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
  • C08K2003/3045—Sulfates
• • 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
  • C08K3/38—Boron-containing compounds
  • C08K2003/382—Boron-containing compounds and nitrogen
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/28—Applying non-metallic protective coatings
  • H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil

Definitions

• the multilayer film has a first polyimide layer and a second polyimide layer containing a matting agent, submicron carbon black and submicron fumed metal oxide.
• the present disclosure is directed to a multilayer film comprising:
• a first polyimide layer from 8 to 130 microns thick comprising: a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• the multilayer film has an L* color less than 30 and a 60 degree gloss value less than 10.
• FIG. 1 illustrates an adhesive layer in direct contact with the first polyimide layer opposite from the second polyimide layer according to one embodiment of the present disclosure.
• FIG. 2 illustrates a third polyimide layer, an adhesive layer in direct contact with the second polyimide layer on a surface of the second polyimide layer furthest from the first polyimide layer according to one embodiment of the present disclosure.
• the present disclosure is directed to multilayer films that achieve a desired L * color of less than 30 and a 60 degree gloss of less than 10 while maintaining acceptable electrical properties, mechanical properties, and durability to handling and circuit processing.
• the multilayer film comprises a first polyimide layer and a second polyimide layer.
• polyamic acid as used herein is intended to include any polyimide precursor material derived from a combination of dianhydride and diamine and capable of conversion to a polyimide.
• the first polyimide layer is derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide.
• dianhydride as used herein is intended to include precursors, derivatives or analogs thereof, which may not technically be a dianhydride but would
• diamine as used herein is intended to include precursors, derivatives or analogs thereof, which may not technically be a diamine but would nevertheless react with a dianhydride to form a polyamic acid which could in turn be converted into a polyimide.
• the aromatic dianhydride is selected from the group consisting of:
• aromatic dianhydride is selected from the group consisting of:
• examples of suitable aliphatic dianhydrides include but are not limited to: cyclobutane dianhydride; [1 S * ,5R * ,6S * ]-3- oxabicyclo[3.2.1 ]octane-2,4-dione-6-spiro-3-(tetrahydrofuran-2,5-dione); and mixtures thereof.
• the aromatic diamine is selected from the group consisting of: 3,4'-oxydianiline; 1 ,3-bis-(4-aminophenoxy) benzene; 4,4'-oxydianiline; paraphenylenediamine; 1 ,3-diaminobenzene; 2,2'- bis(trifluoromethyl) benzidene; 4,4'-diaminobiphenyl; 4,4'-diaminodiphenyl sulfide; 9,9'-bis(4-amino)fluorine; mixtures and derivatives thereof.
• the aromatic diamine is selected from a group consisting of: 4,4'-diaminodiphenyl propane; 4,4'-diamino diphenyl methane; benzidine; 3,3'-dichlorobenzidine; 3,3'-diamino diphenyl sulfone; 4,4'-diamino diphenyl sulfone; 1 ,5-diamino naphthalene; 4,4'-diamino diphenyl diethylsilane; 4,4'-diamino diphenysilane; 4,4'-diamino diphenyl ethyl phosphine oxide; 4,4'-diamino diphenyl N-methyl amine; 4,4'-diamino diphenyl N-phenyl amine; 1 ,4-diaminobenzene (paraphenylenediamine); 1 ,2-diaminobenzen
• examples of suitable aliphatic diamines include: hexamethylene diamine, dodecane diamine, cyclohexane diamine and mixtures thereof.
• the first polyimide layer comprises a polyimide derived from pyromellitic dianhydride and 4,4'-oxydianiline.
• the first polyimide layer is between and including any two of the following thicknesses: 8, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 1 10, 120 and 130 microns thick. In another embodiment, the first polyimide layer is from 8 to 130 microns thick. In another embodiment, the first polyimide layer is from 10 to 30 microns thick. In another embodiment, the first polyimide layer is from 12 to 25 microns thick.
• the first polyimide layer may optionally contain 1 to 15 wt% low conductivity carbon black. In some embodiments the first polyimide layer contains between and including any two of the following: 1 , 5, 10 and 15 wt% low conductivity carbon black. In yet another embodiment, the first polyimide layer contains 2 to 9 wt% low conductivity carbon black.
• Low conductivity carbon black is intended to mean, channel type black, furnace black or lamp black.
• the low conductivity carbon black is a surface oxidized carbon black.
• One method for assessing the extent of surface oxidation (of the carbon black) is to measure the carbon black's volatile content. The volatile content can be measured by calculating weight loss when calcined at 950°C for 7 minutes.
• a highly surface oxidized carbon black (high volatile content) can be readily dispersed into a polyamic acid solution (polyimide precursor), which in turn can be imidized into a (well dispersed) filled polyimide base polymer of the present disclosure. It is thought that if the carbon black particles (aggregates) are not in contact with each other, then electron tunneling, electron hopping or other electron flow
• the low conductivity carbon black has a volatile content greater than or equal to 1 %. In some embodiments, the low conductivity carbon black has a volatile content greater than or equal to 5, 9, or 13%. In some embodiments, furnace black may be surface treated to increase the volatile content. Typically, a low conductivity carbon black has a pH less than 6.
• a uniform dispersion of isolated, low conductivitycarbon black particles not only decreases the electrical conductivity, but additionally tends to produce uniform color intensity.
• the low conductivity carbon black is milled.
• the mean particle size of the low conductivity carbon black is between (and optionally including) any two of the following sizes: 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and 1 .0 microns.
• the first polyimide layer may optionally contain 1 to 40 wt% pigment or dye. In some embodiments the first polyimide layer contains 1 to 40 wt% of a mixture of pigments and dyes. In some embodiments, the first polyimide layer contains between and including any two of the following: 1 , 5, 10, 15, 20, 25, 30, 35 and 40 wt% pigment, dye or mixtures thereof. In some embodiments, the first polyimide layer contains 1 to 40 wt% of a mixture of at least two of the following: low conductivity carbon black, pigments or dyes.
• useful pigments include but are not limited to the following: Barium Lemon Yellow, Cadmium Yellow Lemon, Cadmium Yellow Lemon, Cadmium Yellow Light, Cadmium Yellow Middle, Cadmium Yellow Orange, Scarlet Lake, Cadmium Red, Cadmium Vermilion, Alizarin Crimson, Permanent Magenta, Van Dyke brown, Raw Umber Greenish, or Burnt Umber.
• useful black pigments include: cobalt oxide, Fe-Mn-Bi black, Fe-Mn oxide spinel black, (Fe,Mn)2O3 black, copper chromite black spinel, lampblack, bone black, bone ash, bone char, hematite, black iron oxide, micaceous iron oxide, black complex inorganic color pigments (CICP), (Ni,Mn,Co)(Cr,Fe)2O4 black, Aniline black, Perylene black, Anthraquinone black, Chromium Green-Black Hematite, Chrome Iron Oxide, Pigment Green 17, Pigment Black 26, Pigment Black 27, Pigment Black 28, Pigment Brown 29, Pigment Brown 35, Pigment Black 30, Pigment Black 32, Pigment Black 33 or mixtures thereof.
• the pigment is lithopone, zinc sulfide, barium sulfate, cobalt oxide, yellow iron oxide, orange iron oxide, red iron oxide, brown iron oxide, hematite, black iron oxide, micaceous iron oxide, chromium (III) green, ultramarine blue, ultramarine violet, ultramarine pink, cyanide iron blue, cadmium pigments or lead chromate pigments.
• the pigment is complex inorganic color pigments (CICP) such as spinel pigments, rutile pigments, zircon pigments or bismuth vanadate yellow.
• useful spinel pigments include but are not limited to: Zn(Fe,Cr)2O4 brown, CoAI2O4 blue, Co(AICr)2O4 blue-green, Co2TiO4 green, CuCr2O4 black or
• useful rutile pigments include but are not limited to: Ti-Ni-Sb yellow, Ti-Mn-Sb brown, Ti-Cr-Sb buff, zircon pigments or bismuth vanadate yellow.
• the pigment is an organic pigment.
• useful organic pigments include but are not limited to: Aniline black (Pigment Black 1 ), Anthraquinone black, Monoazo type, Diazo type, Benzimidazolones, Diarylide yellow, Monoazo yellow salts, Dinitaniline orange, Pyrazolone orange, Azo red, Naphthol red, Azo condensation pigments, Lake pigments, Copper Phthalocyanine blue, Copper Phthalocyanine green, Quinacridones, Diaryl Pyrrolopyrroles, Aminoanthraquinone pigments, Dioxazines, Isoindolinones, Isoindolines, Quinophthalones, phthalocyanine pigments, idanthrone pigments, pigment violet 1 , pigment violet 3, pigment violet 19 or pigment violet 23.
• the organic pigment is a Vat dye pigment, such as but not limited to: perylene, perylene black, perin
• a uniform dispersion of isolated, individual pigment particles (aggregates) tends to produce uniform color intensity.
• the pigment is milled.
• the mean particle size of the pigment is between (and optionally including) any two of the following sizes: 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and 1 .0 microns.
• luminescent (fluorescent or phosphorescent), or pearlescent pigments can be used, alone, or in combination with other pigments or dyes.
• the first polyimide layer further comprises 1 to 20 wt% of a matting agent selected from silica, alumina, zirconia, boron nitride, barium sulfate, polyimide particles, calcium phosphate, talc or mixtures thereof.
• the first polyimide layer further comprises 1 to 20 wt% of a matting agent that is a carbon black having a mean particle size from 2 to 9 micrometers.
• the first polyimide layer further comprises 1 to 20 wt% of a matting agent, the matting agent being a mixture of
• silica alumina, zirconia, boron nitride, barium sulfate, polyimide particles, calcium phosphate, talc or mixtures thereof.
• the first polyimide layer is Kapton® MBC polyimide film manufactured by DuPont.
• the first polyimide layer comprises:
• a chemically converted polyimide in an amount from 71 to 96 wt%, the chemically converted polyimide being derived from: a. at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and b. at least 50 mole percent of an aromatic diamine, based upon a total diamine content of the polyimide;
• a. is present in an amount from 1 .6 to 10 wt%
• b. has a median particle size from 1 .3 to 10 microns
• c. has a density from 2 to 4.5 g/cc.
• the polyamic acid solution is either immersed in or mixed with conversion (imidization) chemicals.
• the conversion chemicals are tertiary amine catalysts (accelerators) and anhydride dehydrating materials.
• the anhydride dehydrating material is acetic anhydride, which is often used in molar excess relative to the amount of amic acid (amide acid) groups in the polyamic acid, typically about 1 .2 to 2.4 moles per equivalent of polyamic acid. In one embodiment, a comparable amount of tertiary amine catalyst is used.
• the tertiary amine catalysts are pyridine and beta-picoline and are typically used in amounts similar to the moles of anhydride dehydrating material. Lower or higher amounts may be used depending on the desired conversion rate and the catalyst used. Tertiary amines having approximately the same activity as the pyridine, and beta- picoline may also be used. These include alpha picoline; 3,4-lutidine; 3,5- lutidine; 4-methyl pyridine; 4-isopropyl pyridine; N,N-dimethylbenzyl amine; isoquinoline; 4-benzyl pyridine, ⁇ , ⁇ -dimethyldodecyl amine, triethyl amine, and the like.
• a variety of other catalysts for imidization are known in the art, such as imidazoles, and may be useful in accordance with the present disclosure.
• the conversion chemicals can generally react at about room temperature or above to convert polyamic acid to polyimide.
• the chemical conversion reaction occurs at temperatures from 15°C to 120°C with the reaction being very rapid at the higher temperatures and relatively slower at the lower temperatures.
• the chemically treated polyamic acid solution can be cast or extruded onto a heated conversion surface or substrate.
• the chemically treated polyamic acid solution can be cast on to a belt or drum.
• the solvent can be evaporated from the solution, and the polyamic acid can be partially chemically converted to polyimide.
• the resulting solution then takes the form of a polyamic acid- polyimide gel.
• the polyamic acid solution can be extruded into a bath of conversion chemicals consisting of an anhydride component (dehydrating agent), a tertiary amine component (catalyst) or both with or without a diluting solvent.
• a gel film is formed and the percent conversion of amic acid groups to imide groups in the gel film depends on contact time and temperature but is usually about 10 to 75 percent complete.
• the gel film typically must be dried at elevated temperature (from about 200°C, up to about 550°C), which will tend to drive the imidization to completion.
• elevated temperature from about 200°C, up to about 550°C
• the use of both a dehydrating agent and a catalyst is preferred for facilitating the formation of a gel film and achieve desired conversion rates.
• the second polyimide layer comprises 25 to 50 wt% of a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide.
• the second polyimide layer comprises between and including any two of the following: 25, 30, 35, 40, 45 and 50 wt% of a polyimide.
• the second polyimide layer comprises 33 to 39 wt% of a polyimide.
• the aromatic dianhydride is selected from the group consisting of:
• aromatic dianhydride is selected from the group consisting of:
• examples of suitable aliphatic dianhydrides include but are not limited to: cyclobutane dianhydride; [1 S*,5R*,6S*]-3- oxabicyclo[3.2.1 ]octane-2,4-dione-6-spiro-3-(tetrahydrofuran-2,5-dione); and mixtures thereof.
• the aromatic diamine is selected from the group consisting of: 3,4'-oxydianiline; 1 ,3-bis-(4-aminophenoxy) benzene; 4,4'-oxydianiline; paraphenylenediamine; 1 ,3-diaminobenzene; 2,2'- bis(trifluoromethyl) benzidene; 4,4'-diaminobiphenyl; 4,4'-diaminodiphenyl sulfide; 9,9'-bis(4-amino)fluorine; mixtures and derivatives thereof.
• the aromatic diamine is selected from a group consisting of: 4,4'-diaminodiphenyl propane; 4,4'-diamino diphenyl methane; benzidine; 3,3'-dichlorobenzidine; 3,3'-diamino diphenyl sulfone; 4,4'-diamino diphenyl sulfone; 1 ,5-diamino naphthalene; 4,4'-diamino diphenyl diethylsilane; 4,4'-diamino diphenysilane; 4,4'-diamino diphenyl ethyl phosphine oxide; 4,4'-diamino diphenyl N-methyl amine; 4,4'-diamino diphenyl N-phenyl amine; 1 ,4-diaminobenzene (paraphenylene diamine); 1 ,2-diaminobenzene
• examples of suitable aliphatic diamines include: hexamethylene diamine, dodecane diamine, cyclohexane diamine and mixtures thereof.
• the second polyimide layer comprises a polyimide derived from pyromellitic dianhydride and 4,4'-oxydianiline or derived from pyromellitic dianhydride, 4,4'-oxydianiline and
• the second polyimide layer comprises a polyimide derived from 3,3',4,4'-biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-oxydianiline and
• the second polyimide layer comprises a polyimide derived from i) blocks of pyromellitic dianhydride and 4,4'-oxydianiline and ii) blocks of pyromellitic dianhydride and paraphenylenediamine.
• the second polyimide layer comprises a polyimide derived from 3,3',4,4'-biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine.
• the first polyimide layer comprises a polyimide derived from pyromellitic dianhydride and 4,4'-oxydianiline
• the second polyimide layer comprises a polyimide derived from a polyimide derived from
• the second polyimide layer is thinner than the first polyimide layer.
• the second polyimide layer is highly filled, and the first polyimide layer must provide mechanical support. Thus it is desirable to have a thin second polyimide layer.
• the second polyimide layer is from 0.5 to 20 microns thick. In some embodiments, the second polyimide layer is between and including any two of the following thicknesses: 0.5, 1 , 5, 10, 15, and 20 microns thick. In yet another embodiment, the second layer is from 0.7 to 10 microns thick. In some embodiments, the second layer is from 0.7 to 3 microns thick.
• the second layer is in direct contact with the first polyimide layer.
• direct contact is intended to mean two surfaces adjacent to each other without an intervening material or adhesive layer between the two surfaces.
• the second polyimide layer comprises greater than 0 and less than 20 wt% of at least one submicron carbon black.
• the term "submicron" is intended to mean less than one micron in all dimensions.
• the second polyimide layer comprises from 5 to 15wt% of at least one submicron carbon black.
• the second polyimide layer comprises greater than 7 and less than 1 1 wt% of at least one submicron carbon black.
• the second polyimide layer comprises from 8 to 10 wt% of at least one submicron carbon black.
• the submicron carbon black for the purpose of the present disclosure, is intended to be the colorant.
• One of ordinary skill in the art could also envision the use of other colorants (pigments or dyes) to create any desired color.
• the same pigment or dye used in the second polyimide layer may be used in the first polyimide layer.
• the colorant in the second polyimide layer could be different from any colorant that may be used in the first polyimide layer.
• the second polyimide layer comprises15 to 35 wt% of polyimide particle matting agent.
• the second polyimide layer comprises between and including any two of the following: 15, 16, 17, 18, 19, 20, 25, 30, 31 , 32, 33, 34 and 35 wt% of polyimide particle matting agent.
• the second polyimide layer comprises 19 to 31 wt% of polyimide particle matting agent.
• the second polyimide layer comprises a mixture of polyimide particle matting agents or a mixture of polyimide particle matting agent and another matting agent such as, silica, alumina, zirconia, boron nitride, barium sulfate, calcium phosphate and talc.
• the polyimide particle matting agent has a median particle size of 2 to 1 1 microns. In some embodiments, the polyimide particle matting agent has a median particle size between and including any two of the following: 2, 3, 4, 5, 6, 7, 8, 9, 10 and 1 1 microns. In some embodiments the average particle size is 2 to 1 1 microns.
• the particle size of the polyimide particle matting agent can be measured in the slurries by laser diffraction using either a Horiba LA-930 (Horiba, Instruments, Inc., Irvine CA) or a Malvern Mastersizer 3000 (Malvern Instruments, Inc., Westborough, MA).
• the polyimide particle matting agent is derived from at least one aromatic dianhydride and at least one aromatic diamine. In one
• the polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4'-oxydianiline.
• the polyimide particle matting agent is a pigmented polyimide particle matting agent.
• Pigmented polyimide particles are comprised of a polyimide and a colorant. Pigmented polyimide particles have a color different from the polyimide by itself. Virtually any colorant can be used, including but not limited to inorganic pigments, complex inorganic color pigments, organic pigments, and dyes.
• Useful black colorants include carbon black, graphite, aniline black, and perylene black.
• Useful white colorants include titanium dioxide.
• the colorant may be incorporated into the polyimide particles, such as by absorption, or dispersed as a separate phase within the polyimide particles. Some or all of the colorant may be on the surface of the polyimide particles.
• Pigmented polyimide particles may be produced by a variety of methods, including but not limited to the following: incorporation of the colorant into the polyimide particles during the process of particle formation by precipitation from solution; absorption, imbibition, or diffusion of the colorant into the polyimide particles; coating of the colorant onto the polyimide particles.
• the pigmented polyimide particles may contain from 1 wt% to 70 wt% colorant. In some embodiments, the pigmented polyimide particles may contain from 1 wt% to 50 wt% colorant.
• Pigmented polyimide particle matting agents useful in the present disclosure include those disclosed in U.S. Pat. application 2014/0220335, the disclosure of which are hereby incorporated by reference.
• the second polyimide layer comprises 15 to 35 wt% of pigmented polyimide particle matting agent. In some
• the second polyimide layer comprises between and including any two of the following: 15, 16, 17, 18, 19, 20, 25, 30, 31 , 32, 33, 34 and 35 wt% of pigmented polyimide particle matting agent. In another embodiment, comprises 19 to 31 wt% of pigmented polyimide particle matting agent.
• the pigmented polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4'-oxydianiline. In some embodiments, the pigmented polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4'-oxydianiline and graphite as the colorant (pigment).
• the polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4'-oxydianiline and the polyimide of the second polyimide layer is derived from pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine.
• the pigmented polyimide particle matting agent is derived from pyromellitic dianhydride, 4,4'-oxydianiline and colorant and the polyimide of the second polyimide layer is derived from pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine.
• the pigmented polyimide particle matting agent is derived from pyromellitic dianhydride, 4,4'-oxydianiline and graphite and the polyimide of the second polyimide layer is derived from pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine.
• the multilayer film in accordance with the present disclosure has a first polyimide layer and a second polyimide layer as described above.
• the multilayer film has an L* color less than 30 and a 60 degree gloss value less than 10 as well as durability to handling and circuit processing.
• the L* color is measured using a HunterLab ColorQuest® XE color meter (Hunter Associates Laboratory, Inc.) in the reflectance, specular included mode and reported in the CIELAB 10 D65 system, as L*, a*, b*.
• a L* value of 0 is pure black, while a L* value of 100 is pure white.
• the 60 degree gloss was measured using a Micro-TRI-gloss glossmeter (from BYK- Gardner).
• Figure 1 illustrates one embodiment of the present disclosure, a multilayer film comprising an adhesive layer 60 in direct contact with the first polyimide layer 10 opposite the second polyimide layer 20, wherein the second polyimide layer comprises a polyimide particle matting agent 30, a submicron carbon black 40 and a submicron fumed metal oxide 50.
• the adhesive layer is an epoxy adhesive selected from the group consisting of: Bisphenol A type epoxy resin, cresol novolac type epoxy resin, phosphorus containing epoxy resin, and mixtures thereof.
• an adhesive layer is as thick as or thicker than the first polyimide layer or the second polyimide layer. In some embodiments the adhesive layer is from 8 to 300 microns thick.
• the adhesive is a mixture of two or more epoxy resins. In some embodiments, the adhesive is a mixture of the same epoxy resin having different molecular weights.
• the epoxy adhesive contains a hardener. In some embodiments, the epoxy adhesive contains a catalyst. In some embodiments, the epoxy adhesive contains an elastomer toughening agent. In some embodiments, the epoxy adhesive contains a flame retardant.
• the multilayer film further comprises a third polyimide layer.
• the third polyimide layer is from 0.5 to 20 microns thick. In another embodiment, the third polyimide layer is between and including any two of the following thicknesses: 0.5, 1 , 5, 10, 15 and 20 micron thick. In some embodiments, the third polyimide layer is from 0.7 to 10 microns thick. In some embodiments, the third polyimide layer is from 0.7 to 3 microns thick. In some embodiments, the multilayer film further comprises a third polyimide layer from 0.5 to 20 microns thick in direct contact with the first polyimide layer opposite the second polyimide layer.
• a third polyimide layer is particularly desired when the multilayer film is coextruded.
• the third polyimide layer when similar to or the same as the second polyimide layer helps prevent curl.
• the third polyimide layer may be the same as, or different from, the second polyimide layer.
• the multilayer film further comprises a third polyimide layer from 0.5 to 20 microns thick in direct contact with the first polyimide layer opposite the second polyimide layer, the third polyimide layer comprising:
• a matting agent or mixture thereof ii) a matting agent or mixture thereof.
• the matting agent in the third polyimide layer is selected from silica, alumina, zirconia, boron nitride, barium sulfate, polyimide particles, calcium phosphate, talc or mixtures thereof.
• the matting agent in the third polyimide layer is a carbon black having a mean particle size from 2 to 9 microns.
• the matting agent in the third polyimide layer is a mixture of i) carbon black having a mean particle size from 2 to 9 microns; and
• the matting agent in the third polyimide layer is polyimide particle matting agent.
• the matting agent in the third polyimide layer is pigmented polyimide particle matting agent.
• the third polyimide layer comprises 15 to 35 wt% of polyimide particle matting agent. In some embodiments, the third polyimide layer comprises between and including any two of the following: 15, 16, 17, 18, 19, 20, 25, 30, 31 , 32, 33, 34 and 35 wt% of polyimide particle matting agent. In another embodiment, the third polyimide layer comprises 19 to 31 wt% of polyimide particle matting agent. In some embodiments, the third polyimide layer comprises a mixture of polyimide particle matting agents or a mixture of polyimide particle matting agent and another matting agent such as, silica, alumina, zirconia, boron nitride, barium sulfate, calcium phosphate and talc.
• the polyimide particle matting agent has a median particle size of 2 to 1 1 microns. In some embodiments, the polyimide particle matting agent has a median particle size between and including any two of the following: 2, 3, 4, 5, 6, 7, 8, 9, 10 and 1 1 microns. In some embodiments the average particle size is 2 to 1 1 microns.
• the particle size of the polyimide particle matting agent can be measured in the slurries by laser diffraction using either a Horiba LA-930 (Horiba, Instruments, Inc., Irvine CA) or a Malvern Mastersizer 3000 (Malvern Instruments, Inc., Westborough, MA).
• the polyimide particle matting agent is derived from at least one aromatic dianhydride and at least one aromatic diamine. In one
• the polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4'-oxydianiline.
• the polyimide particle matting agent is a pigmented polyimide particle matting agent.
• Pigmented polyimide particles are comprised of a polyimide and a colorant. Pigmented polyimide particles have a color different from the polyimide by itself. Virtually any colorant can be used, including but not limited to inorganic pigments, complex inorganic color pigments, organic pigments, and dyes.
• Useful black colorants include carbon black, graphite, aniline black, and perylene black.
• Useful white colorants include titanium dioxide.
• the colorant may be incorporated into the polyimide particles, such as by absorption, or dispersed as a separate phase within the polyimide particles. Some or all of the colorant may be on the surface of the polyimide particles.
• Pigmented polyimide particles may be produced by a variety of methods, including but not limited to the following: incorporation of the colorant into the polyimide particles during the process of particle formation by precipitation from solution; absorption, imbibition, or diffusion of the colorant into the polyimide particles; coating of the colorant onto the polyimide particles.
• the pigmented polyimide particles may contain from 1 to 70 wt% colorant. In some embodiments, the pigmented polyimide particles may contain from 1 to 50 wt% colorant.
• Pigmented polyimide particle matting agents useful in the present disclosure include those disclosed in U.S. Pat. application 2014/0220335, the disclosure of which are hereby incorporated by reference.
• the third polyimide layer comprises 15 to 35 wt% of pigmented polyimide particle matting agent. In some embodiments, the third polyimide layer comprises between and including any two of the following: 15, 16, 17, 18, 19, 20, 25, 30, 31 , 32, 33, 34 and 35 wt% of pigmented polyimide particle matting agent. In another embodiment, comprises 19 to 31 wt% of pigmented polyimide particle matting agent.
• the pigmented polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4'-oxydianiline. In some embodiments, the pigmented polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4'-oxydianiline and graphite as the colorant (pigment).
• the polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4'-oxydianiline and the polyimide of the third polyimide layer is derived from pyromellitic
• the pigmented polyimide particle matting agent is derived from pyromellitic dianhydride, 4,4'-oxydianiline and colorant and the polyimide of the third polyimide layer is derived from pyromellitic
• the pigmented polyimide particle matting agent is derived from pyromellitic dianhydride, 4,4'-oxydianiline and graphite and the polyimide of the third polyimide layer is derived from pyromellitic
• the third polyimide layer comprises a polyimide derived from pyromellitic dianhydride and 4,4'-oxydianiline. In another embodiment, the third polyimide layer comprises a polyimide derived from pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine. In another embodiment, the second polyimide layer comprises a polyimide derived from 3,3',4,4'-biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine.
• the third polyimide layer comprises a polyimide derived from i) blocks of pyromellitic dianhydride and 4,4'-oxydianiline and ii) blocks of pyromellitic dianhydride and paraphenylenediamine.
• the multilayer film further comprises a third polyimide layer from 0.5 to 20 microns thick in direct contact with the first polyimide layer opposite the second polyimide layer; the third polyimide layer comprises:
• a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• Figure 2 illustrates another embodiment of the present disclosure, a multilayer film comprising a third polyimide layer 70 in direct contact with the first polyimide layer 10, an adhesive layer 60 in direct contact with the second polyimide layer 20 on a surface of the second polyimide layer furthest from the first polyimide layer 10, wherein the second polyimide layer and the third polyimide layer comprises a polyimide particle matting agent 30, a submicron carbon black 40 and a submicron fumed metal oxide 50.
• an adhesive layer 60 may be in direct contact with the third polyimide layer 70 on a surface of the third polyimide furthest from the first polyimide layer 10.
• the multilayer film comprises:
• a first polyimide layer from 8 to 130 microns thick comprising: a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide; b. a second polyimide layer from 0.5 to 20 microns thick in direct contact with the first polyimide layer, the second polyimide layer comprising:
• a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• the multilayer film has an L * color less than 30 and a 60 degree gloss value less than 10.
• the multilayer film comprises:
• a first polyimide layer from 8 to 130 microns thick comprising: a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide; b. a second polyimide layer from 0.5 to 20 microns thick in direct contact with the first polyimide layer, the second polyimide layer comprising:
• a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• an adhesive layer in direct contact with the first polyimide layer opposite the second polyimide layer; wherein the adhesive layer is an epoxy resin selected from the group consisting of: Bisphenol A type epoxy resin, cresol novolac type epoxy resin, phosphorus containing epoxy resin, and mixtures thereof;and wherein the multilayer film has an L * color less than 30 and a 60 degree gloss value less than 10.
• the multilayer film comprises: a. a first polyimide layer from 8 to 130 microns thick comprising: a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide; b. a second polyimide layer from 0.5 to 20 microns thick in direct contact with the first polyimide layer, the second polyimide layer comprising:
• a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• a third polyimide layer from 0.5 to 20 microns thick in direct contact with the first polyimide layer opposite the second polyimide layer, the third polyimide layer comprising: i) 25 to 50 wt% of a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• the multilayer film comprises:
• a first polyimide layer from 8 to 130 microns thick comprising: a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• a third polyimide layer from 0.5 to 20 microns thick in direct contact with the first polyimide layer opposite the second polyimide layer, the third polyimide layer comprising: i) 25 to 50 wt% of a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• an adhesive layer in direct contact an adhesive layer in direct contact with the second polyimide layer on a surface of the second polyimide layer opposite from the first polyimide layer; wherein the adhesive layer is an epoxy resin selected from the group consisting of: Bisphenol A type epoxy resin, cresol novolac type epoxy resin, phosphorus containing epoxy resin, and mixtures thereof; and
• the multilayer film has an L * color less than 30 and a 60 degree gloss value less than 10.
• the multilayer film comprises: a. a first polyimide layer from 8 to 130 microns thick comprising: a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide; b. a second polyimide layer from 0.5 to 20 microns thick in direct contact with the first polyimide layer, the second polyimide layer comprising:
• a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• an adhesive layer in direct contact an adhesive layer in direct contact with the third polyimide layer on a surface of the third polyimide layer opposite from the first polyimide layer; wherein the adhesive layer is an epoxy resin selected from the group consisting of: Bisphenol A type epoxy resin, cresol novolac type epoxy resin, phosphorus containing epoxy resin, and mixtures thereof; and
• the multilayer film has an L * color less than 30 and a 60 degree gloss value less than 10.
• the multilayer film comprises:
• a first polyimide layer from 8 to 130 microns thick comprising: i) a polyimide derived from at least 50 mole percent of an
• aromatic dianhydride based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• the multilayer film has an L* color less than 30 and a 60 degree gloss value less than 10.
• the multilayer film comprises:
• a first polyimide layer from 8 to 130 microns thick comprising: i) a polyimide derived from at least 50 mole percent of an
• aromatic dianhydride based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• a matting agent selected from silica, alumina, zirconia, boron nitride, barium sulfate, polyimide particles, calcium phosphate, talc or mixtures thereof;
• a second polyimide layer from 0.5 to 20 microns thick in direct contact with the first polyimide layer, the second polyimide layer comprising:
• the multilayer film has an L * color less than 30 and a 60 degree gloss value less than 10.
• the multilayer film comprises:
• a. a first polyimide layer comprising:
• a chemically converted polyimide in an amount from 71 to 96 weight percent, the chemically converted polyimide being derived from: at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• a. is present in an amount from 1 .6 to 10 wt%
• b. has a median particle size from 1 .3 to 10 microns
• c. has a density from 2 to 4.5 g/cc
• b. a second polyimide layer from 0.5 to 20 microns thick in direct contact with the first polyimide layer, the second polyimide layer comprising:
• a polyimide derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• the multilayer film has an L * color less than 30 and a 60 degree gloss value less than 10.
• the multilayer film comprises:
• a. a first polyimide layer comprising:
• a chemically converted polyimide in an amount from 71 to 96 weight percent, the chemically converted polyimide being derived from: at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide;
• a. is present in an amount from 1 .6 to 10 wt%, b. has a median particle size from 1 .3 to 10 microns, and c. has a density from 2 to 4.5 g/cc; b. a second polyimide layer from 0.5 to 20 microns thick in direct contact with the first polyimide layer, the second polyimide layer comprising:
• the multilayer film has an L * color less than 30 and a 60 degree gloss value less than 10.
• the multilayer film comprises:
• a. a first polyimide layer comprising:
• a chemically converted polyimide in an amount from 71 to 96 weight percent, the chemically converted polyimide being derived from: at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the polyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the polyimide; ii) a low conductivity carbon black present in an amount from 2 to 9 wt%; and
• a. is present in an amount from 1 .6 to 10 wt%, b. has a median particle size from 1 .3 to 10 microns, and c. has a density from 2 to 4.5 g/cc;
• a third polyimide layer from 0.5 to 20 microns thick in direct contact with the first polyimide layer opposite the second polyimide layer, the third polyimide layer comprising:
• the multilayer film has an L * color less than 30 and a 60 degree gloss value less than 10.
• the multilayer film comprises:
• a first polyimide layer from 8 to 130 microns thick comprising: a polyimide derived from pyromellitic dianhydride and 4,4'- oxydianiline;
• the multilayer film has an L * color less than 30 and a 60 degree gloss value less than 10.
• the multilayer film comprises:
• a. a first polyimide layer comprising:
• a chemically converted polyimide in an amount from 71 to 96 weight percent, the chemically converted polyimide being derived from pyromellitic dianhydride and 4,4'-oxydianiline; ii) a low conductivity carbon black present in an amount from 2 to 9 wt%; and
• a. is present in an amount from 1 .6 to 10 wt%, b. has a median particle size from 1 .3 to 10 microns, and c. has a density from 2 to 4.5 g/cc;
• the multilayer film has an L * color less than 30 and a 60 degree gloss value less than 10.
• the multilayer film comprises:
• a. a first polyimide layer comprising:
• a chemically converted polyimide in an amount from 71 to 96 weight percent, the chemically converted polyimide being derived from pyromellitic dianhydride and 4,4'-oxydianiline; ii) a low conductivity carbon black present in an amount from 2 to 9 wt%; and
• a. is present in an amount from 1 .6 to 10 wt%, b. has a median particle size from 1 .3 to 10 microns, and c. has a density from 2 to 4.5 g/cc;
• the multilayer film has an L* color less than 30 and a 60 degree gloss value less than 10.
• the multilayer film has an L* color less than 30 and a 60 degree gloss value less than 10.
• the multilayer film comprises:
• a first polyimide layer from 20 to 30 microns thick comprising: a polyimide derived pyromellitic dianhydride and 4,4'-oxydianiline; b. a second polyimide layer from 0.7 to 3 microns thick in direct contact with the first polyimide layer, the second polyimide layer comprising:
• the multilayer film has an L* color less than 30 and a 60 degree gloss value less than 10.
• the multilayer film comprises:
• a first polyimide layer from 20 to 30 microns thick comprising: a polyimide derived pyromellitic dianhydride and 4,4'-oxydianiline; d. a second polyimide layer from 0.7 to 3 microns thick in direct contact with the first polyimide layer, the second polyimide layer comprising:
• the multilayer film has an L * color less than 30 and a 60 degree gloss value less than 10.
• Another embodiment of the present disclosure is a method of producing a multilayer film having an L * color less than 30 and a 60 degree gloss value less than 10; the method comprising:
• the first polyimide layer and the second polyimide layer of the present disclosure can be made by any well-known method in the art for making filled polyimide films.
• the first polyimide layer and the second polyimide layer are made by a thermal conversion process (thermally imidized) in which the polyamic acid solution is heated to temperatures typically greater than 250°C to convert the polyamic acid to a polyimide.
• the first polyimide layer and the second polyimide layer are made by a chemical conversion process (chemically imidized).
• one such method includes preparing a pigment slurry. The slurry may or may not be milled using a ball mill or continuous media mill to reach the desired particle size.
• the slurry may or may not be filtered to remove any residual large particles.
• a polyamic acid prepolymer solution is prepared by reacting dianhydride with a slight excess of diamine.
• the polyamic acid solution is mixed in a high shear mixer with the pigment slurry.
• the amount of the polyamic acid solution, pigment slurry, and finishing solution can be adjusted to achieve the desired loading levels of pigment and the desired viscosity for film formation.
• "Finishing solution” herein denotes a dianyhdride in a polar aprotic solvent which is added to a prepolymer solution to increase the molecular weight and viscosity.
• the dianhydride used is typically the same dianhydride used (or one of the same dianhydrides when more than one is used) to make the prepolymer.
• the mixture can be metered through a slot die and cast or manually cast onto a smooth stainless steel belt or substrate to produce a gel film. Conversion chemicals can be metered in before casting using a slot die. For conversion to greater than 98 percent solids level, the gel film typically must be dried at elevated temperature (convective heating from 200-300°C and radiant heating from 400-800°C), which will tend to drive the imidization to completion.
• the first polyimide layer and the second polyimide layer are independently made by either a thermal conversion process or a chemical conversion process.
• the multilayer film of the present disclosure can be prepared by any well-known method such as but not limited to coextrusion, lamination (laminating single layers together), coating and combinations thereof.
• a description of a coextrusion process for preparing multilayer polyimide films is provided in EP 0659553 A1 to Sutton et al.
• Coating methods include, but are not limited to, spray coating, curtain coating, knife over roll, air knife, extrusion/slot die, gravure, reverse gravure, offset gravure, roll coating, and dip/immersion.
• the multilayer film is prepared by
• the multilayer film is prepared by simultaneously extruding (coextruding) the first polyimide layer and the second polyimide layer.
• the multilayer film is prepared by simultaneously extruding (coextruding) the first polyimide layer, the second polyimide layer and the third polyimide layer.
• the layers are extruded through a single or multi-cavity extrusion die.
• the multilayer film is produced using a single-cavity die. If a single-cavity die is used, the laminar flow of the streams should be of high enough viscosity to prevent comingling of the streams and to provide even layering.
• the multilayer film is prepared by casting from the slot die onto a moving stainless steel belt.
• the belt is then passed through a convective oven, to evaporate solvent and partially imidize the polymer, to produce a "green" film.
• the green film can be stripped off the casting belt and wound up.
• the green film can then be passed through a tenter oven to produce a fully cured polyimide film.
• shrinkage can be minimized by constraining the film along the edges (i.e. using clips or pins).
• the multilayer film is made by coating a solution of silica matting agent, submicron carbon black and submicron fumed metal oxide slurries and polyamic acid on the first polyimide layer.
• the coating is heated to dry.
• the resulting multilayer film is placed on a pin frame to hold it flat.
• the coating can be cured in a batch or continuous oven capable of heating to at least 250°C.
• the oven temperature is ramped to 320°C over a period of 45 to 60 minutes, then transferred to a 400°C oven and held for 5 minutes.
• chemical imidization catalysts and/or dehydrating agents can be added to the coating solution.
• Another embodiment of the present disclosure is, a method of reducing the amount of colorant in a multilayer film and achieving an L * color less than 30 and a 60 degree gloss value less than 10, the method comprising;
• step d imidizing the coating formed in step d to form a second polyimide layer on the first polyimide layer, or imidizing the coating formed in step d and the first polyamic acid green film to form a first polyimide layer and a second polyimide layer, or imidizing the coextruded layers formed in step d to form a first polyimide layer and a second polyimide layer.
• a method of reducing the amount of colorant in a multilayer film and achieving an L * color less than 30 and a 60 degree gloss value less than 10 comprising;
• polyamic acid is derived from pyromellitic dianhydride and 4,4'-oxydianiline, or derived from pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine, or derived from 3,3',4,4'-biphenyl
• step d imidizing the coating formed in step d to form a second polyimide layer on the first polyimide layer, or imidizing the coating formed in step d and the first polyamic acid green film to form a first polyimide layer and a second polyimide layer, or imidizing the coextruded layers formed in step d to form a first polyimide layer and a second polyimide layer; and wherein the second polyimide layer is in direct contact with the first polyimide layer.
• Another embodiment of the present disclosure is a method of reducing the amount of colorant in a multilayer film and achieving an L * color less than 30 and a 60 degree gloss value less than 10, the method comprising:
• step d) forming a multilayer composite by coating the polyamic acid solution formed in step c on to the first polyimide layer, or coating the polyamic acid solution formed in step c on to the first polyamic acid green film, or coextruding the polyamic acid solution formed in step c and the first polyamic acid solution; and f) imidizing the composite formed in step d to produce a first polyimide layer and a second polyimide layer.
• the submicron fumed metal oxide or mixtures thereof can be added directly to the second polyamic acid solution or by preparing a submicron fumed metal oxide slurry which is then added to the second polyamic acid solution.
• the second polyamic acid solution is added to the submicron fumed metal oxide slurry.
• the polyimide particle matting agent, the submicron carbon black and the submicron fumed metal oxide (and slurries thereof) may be combined in any order before coating the polyamic acid solution formed in step c on to the first polyimide layer; or coextruding the polyamic acid solution formed in step c and the first polyamic acid solution.
• the polyamic acid formed in step c can be coated by methods well known in the art such as, but not limited to, spray coating, curtain coating, knife over roll, air knife, extrusion/slot die, gravure, reverse gravure, offset gravure, roll coating, and dip/immersion.
• the coating or coextruded layers can be imidized by thermal conversion or chemical conversion as previously described.
• the first polyamic acid solution is partially dried and partly imidized to form a first polyamic acid green film. Then the polyamic acid solution formed in step c is coated on the first polyamic acid green film and both layers are imidized.
• Another embodiment of the present disclosure is a method of reducing the amount of colorant in a multilayer film and achieving an L * color less than 30 and a 60 degree gloss value less than 10, the method comprising:
• step d) forming a multilayer composite by coating the polyamic acid solution formed in step c on to the first polyimide layer, or coating the polyamic acid solution formed in step c on to the first polyamic acid green film, or coextruding the polyamic acid solution formed in step c and the first polyamic acid solution;
• step d imidizing the composite formed in step d to produce a first polyimide layer and a second polyimide layer;
• Another embodiment of the present disclosure is a method of reducing the amount of colorant in a multilayer film and achieving an L * color less than 30 and a 60 degree gloss value less than 10, the method comprising:
• step d) forming a multilayer composite by coating the polyamic acid solution formed in step c on to the first polyimide layer, or coating the polyamic acid solution formed in step c on to the first polyamic acid green film, or coextruding the polyamic acid solution formed in step c and the first polyamic acid solution;
• step d imidizing the composite formed in step d to produce a first polyimide layer and a second polyimide layer.
• the method of reducing amount of colorant in a multilayer film wherein the second polyimide layer comprises a polyimide derived from pyromellitic dianhydride and 4,4'-oxydianiline or derived from pyromellitic dianhydride, 4,4'-oxydianiline and
• paraphenylenediamine or derived from 3,3',4,4'-biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-oxydianiline and
• paraphenylenediamine or derived from i) blocks of pyromellitic dianhydride and 4,4'-oxydianiline and ii) blocks of pyromellitic dianhydride and paraphenylenediamine.
• Another embodiment of the present disclosure is a method of reducing the amount of colorant in a multilayer film and achieving an L * color less than 30 and a 60 degree gloss value less than 10, the method comprising:
• polyamic acid is derived from pyromellitic dianhydride and 4,4'-oxydianiline, or derived from pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine, or derived from 3,3',4,4'-biphenyl
• step d) forming a multilayer composite by coating the polyamic acid solution formed in step c on to the first polyimide layer, or coating the polyamic acid solution formed in step c on to the first polyamic acid green film, or coextruding the polyamic acid solution formed in step c and the first polyamic acid solution;
• Another embodiment of the present disclosure is a method of reducing the amount of colorant in a multilayer film and achieving an L * color less than 30 and a 60 degree gloss value less than 10, the method comprising:
• step d) forming a multilayer composite by coating the polyamic acid solution formed in step c on to the first polyimide layer, or coating the polyamic acid solution formed in step c on to the first polyamic acid green film, or coextruding the polyamic acid solution formed in step c and the first polyamic acid solution;
• step d imidizing the composite formed in step d to produce a first polyimide layer and a second polyimide layer.
• Another embodiment of the present disclosure is a method of reducing the amount of colorant in a multilayer film and achieving an L * color less than 30 and a 60 degree gloss value less than 10, the method comprising:
• polyamic acid is derived from pyromellitic dianhydride and 4,4'-oxydianiline, or derived from pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine, or derived from 3,3',4,4'-biphenyl
• tetracarboxylic dianhydride pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine, or derived from i) blocks of pyromellitic dianhydride and 4,4'-oxydianiline and ii) blocks of pyromellitic dianhydride and paraphenylenediamine;
• step d) forming a multilayer composite by coating the polyamic acid solution formed in step c on to the first polyimide layer, or coating the polyamic acid solution formed in step c on to the first polyamic acid green film, or coextruding the polyamic acid solution formed in step c and the first polyamic acid solution;
• step d imidizing the composite formed in step d to produce a first polyimide layer and a second polyimide layer.
• the number 1 shall be understood to encompass a range from 0.5 to 1 .4, whereas the number 1 .0 shall be understood to encompass a range from 0.95 to 1 .04, including the end points of the stated ranges. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.
• a carbon black slurry was prepared, consisting of 82 wt. % DMAC, 12 wt. % carbon black powder (Special Black 6, from Orion Engineered Carbons LLC), and 6 wt. % dispersing agent (Byk 9077, from Byk Chemie). The ingredients were thoroughly mixed in a high speed disc-type disperser. The slurry was then processed in a bead mill to disperse any
• Median particle size was 0.14 microns.
• a fumed alumina slurry was prepared, consisting of 76.3 wt. % DMAC, 19.8 wt. % fumed alumina powder (Alu C805, from Evonik), and 3.9 wt. % dispersing agent (Disperbyk 180, from Byk Chemie). The ingredients were thoroughly mixed in a high speed disc-type disperser. The slurry was then processed in a bead mill to disperse any agglomerates and to achieve the desired particle size. Median particle size was 0.3 microns.
• a polyimide particle slurry was prepared from a solution of PMDA 4,4'ODA polyamic acid in pyridine and heating the solution to precipitate the polymer.
• the pyridine solvent was displaced with deionized water and then comminuted in a high shear environment.
• the deionized water was displaced with DMAc to a 3.6 wt. % solids concentration.
• Median particle size was 4.0 microns.
• a pigmented polyimide particle slurry was prepared.
• Graphite powder was dispersed in a solution of PMDA 4,4'ODA polyamic acid in pyridine. The mixture was heated to form a precipitate of polyimide particles containing 40 weight % graphite.
• the pyridine solvent was displaced with deionized water, comminuted in a high shear environment, and then dried. The resulting powder was passed through a 325 mesh screen. The median particle size of the powder passing through the screen was 9.9 microns.
• the powder was dispersed in DMAC to form a 10 wt % dispersion of pigmented polyimide particles.
• Kapton® MBC is an opaque matte black polyimide film manufactured by DuPont. It is based on PMDA 4,4'ODA polyimide, and contains approximately 5 wt. % carbon black and approximately 2 wt. % of a silica matting agent. It is available in various thicknesses.
• the First polyimide layer comprised Kapton® MBC film, as indicated in Table 1 .
• the Second polyimide layer was prepared using the filler slurries as described above and indicated in Table 1 .
• the slurries were thoroughly mixed with polyamic acid solution, described above and indicated in Table 1 , in the appropriate ratio to produce the desired composition after curing.
• the resulting mixture was coated onto the First polyimide layer using a stainless steel casting rod.
• the coating was dried on a hot plate at 100 °C until dry by visual inspection.
• the resulting multilayer film was then placed on a pin frame to hold it flat, and placed in a 120 C oven.
• the oven temperature was ramped to 320 C over a period of 45 to 60 minutes, then transferred to a 400 C oven and held for 5 minutes, then removed from the oven and allowed to cool .
• compositions of the cured films were calculated from the composition of the components in the mixtures, excluding DMAC solvent (which is removed during curing) and accounting for removal of water during conversion of polyamic acid to polyimide.
• the 60 degree gloss was measured using a Micro-TRI-gloss glossmeter (from BYK- Gardner).
• the L * color was measured using a HunterLab ColorQuest® XE color meter (Hunter Associates Laboratory, Inc.) in the reflectance, specular included mode.
• the instrument was standardized prior to each use. Color data from the instrument were reported in the CIELAB 10 D65 system, as L * , a * , b * .
• a L * value of 0 is pure black, while a L * value of 100 is pure white.
• a L * value difference of 1 unit is discernible to the eye.
• Particle size of filler particles in the slurries was measured by laser diffraction using either a Horiba LA-930 (Horiba, Instruments, Inc., Irvine CA) or a Malvern Mastersizer 3000 (Malvern Instruments, Inc.,
• Results are shown in Table 1 .

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