WO2020009911A1 - Films composites polymères de couleur foncée - Google Patents

Films composites polymères de couleur foncée Download PDF

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Publication number
WO2020009911A1
WO2020009911A1 PCT/US2019/039699 US2019039699W WO2020009911A1 WO 2020009911 A1 WO2020009911 A1 WO 2020009911A1 US 2019039699 W US2019039699 W US 2019039699W WO 2020009911 A1 WO2020009911 A1 WO 2020009911A1
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Prior art keywords
phthalocyanine
graphene
film
polymer composite
composite film
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English (en)
Inventor
Aruna Zhamu
Bor Z. Jang
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Nanotek Instruments Inc
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Nanotek Instruments Inc
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Priority claimed from US16/025,340 external-priority patent/US11242443B2/en
Priority claimed from US16/025,343 external-priority patent/US11186704B2/en
Application filed by Nanotek Instruments Inc filed Critical Nanotek Instruments Inc
Publication of WO2020009911A1 publication Critical patent/WO2020009911A1/fr
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments

Definitions

  • the present disclosure relates generally to the field of dark-color polymer films that can be used as an optically opaque, non-reflecting substrate layer or coverlay in a micro-electronic device.
  • Carbon black filled polyimide is one example of opaque covering or coverlay films. Toughness, high dielectric strength, opaqueness, and matte surface finish are desirable features of these films. High thermal conductivity (as compared to an unfilled polymer film) is also desirable.
  • the carbon black-filled polymer composite film is an opaque film that can be used as a substrate or a coverlay.
  • the polymer composite film may be a pre-coated on one side with an epoxy adhesive, ready to be
  • the matte black polyimide film may be coated with an acrylic resin.
  • the matte black color of these materials provides an aesthetically pleasing appearance to flexible printed circuit materials while also maintaining dielectric strength, tensile strength and dimensional stability, which are some of the key physical properties.
  • the use of these materials to achieve an opaque coverlay is beneficial in several ways.
  • the black finish of the films may help prevent reverse engineering of the circuits it covers, since the coverlay can make it difficult to identify the exact configuration of the underlying circuit traces. Additionally, the opacity of black polymer films can provide higher yields and cost savings in certain applications. In optical applications, such as headlamps and camera flashes, these matte polymer films can help prevent reflections.
  • the present disclosure provides a black-color polymer composite film comprising a phthalocyanine compound dispersed in a polymer, wherein the phthalocyanine compound occupies a weight fraction of 0.1% to 50% based on the total polymer composite weight.
  • the polymer composite film has a typical thickness from 10 nm to 500 pm, more typically from 100 nm to 200 pm, still more typically from 1 pm to 100 pm.
  • the polymer is selected from the group consisting of polyimide, polyamide, polyoxadiazole, polybenzoxazole, polybenzobisoxazole, polythiazole,
  • polybenzothiazole polybenzobisthiazole, poly(p-phenylene vinylene), polybenzimidazole, polybenzobisimidazole, and combinations thereof.
  • the polymer is not limited to this group of materials.
  • the polymer can be a thermoplastic, thermoset, or rubber matrix material.
  • the phthalocyanine compound is selected from copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochromium phthalocyanine, magnesium phthalocyanine, manganous phthalocyanine, dilithium
  • phthalocyanine aluminum phthalocyanine chloride, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, a metal-free phthalocyanine, or a combination thereof.
  • the black-color polymer composite film further comprises from 0.1% to 30% of a pigment selected from graphene, humic acid, expanded graphite flakes, fine carbon black particles having a medium size from 150 nm to 2 pm, or a combination thereof.
  • the black-color polymer composite film further comprises from 0.1% to 15% by weight of a matting agent dispersed in the polymer based on the total polymer composite weight.
  • the graphene as a pigment material, may contain single-layer or few-layer graphene sheets selected from pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, chemically functionalized graphene, or a combination thereof, wherein the few-layer graphene is defined as a graphene sheet or platelet formed of 2-10 graphene planes.
  • the graphene material used in the composite film contains single-layer or few- layer graphene sheets selected from graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, chemically functionalized graphene, or a combination thereof, wherein the graphene material contains greater than 10% by weight (preferably > 20% by weight) of a non-carbon element (e.g. O, N, H, F, Cl, Br, I, S, B, P, etc.).
  • a non-carbon element e.g. O, N, H, F, Cl, Br, I, S, B, P, etc.
  • the humic acid as a pigment in the black-color polymer composite film, comprises chemically functionalized humic acid molecules (CHA) that contain a chemical functional group selected from a polymer, S0 3 H, COOH, NH 2 , OH, R'CHOH, CHO, CN, COC1, halide, COSH, SH, COOR’, SR', SiR' 3 , Si(-OR'-) y R' 3 -y, Si(-0-SiR' 2 -)OR', R", Li, AIRS.
  • a chemical functionalized humic acid molecules that contain a chemical functional group selected from a polymer, S0 3 H, COOH, NH 2 , OH, R'CHOH, CHO, CN, COC1, halide, COSH, SH, COOR’, SR', SiR' 3 , Si(-OR'-) y R' 3 -y, Si(-0-SiR' 2 -)OR', R", Li, AIR
  • R' is hydrogen, alkyl, aryl, cycloalkyl, or aralkyl, cycloaryl, or poly(alkylether)
  • R" is fluoroalkyl, fluoroaryl, fluorocycloalkyl, fluoroaralkyl or cycloaryl
  • X is halide
  • Z is carboxylate or trifluoroacetate, or a combination thereof.
  • the black-color polymer composite is optically opaque and non-reflecting if containing a matte agent.
  • a polymer composite film can be used as a substrate layer or covering layer (“coverlay”) in a wide variety of microelectronic devices.
  • coverlay a covering layer
  • a smooth, shiny surface may be more appealing.
  • the polymer composite film if containing substantially oriented phthalocyanine compound molecules, has a surprisingly pleasing appearance.
  • the polymer in the black-color polymer composite film comprises a chemically or thermally converted poiyimide which is derived from at least 50 mole percent of an aromatic dianhydride, based upon a total dianhydride content of the poiyimide, and at least 50 mole percent of an aromatic diamine based upon a total diamine content of the poiyimide.
  • the aromatic dianhydride may be selected from the group consisting of: pyromellitic dianhydride, 3,3 ',4, 4 '-biphenyl tetracarbox lic di anhydride, 3,3 ',4,4'- benzophenone tetracarboxylic dianhydride; 4,4 '-oxydiphthalic anhydride, 3,3 ',4,4 '-diphenyl sulfone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, bisphenol A dianhydride, and mixtures thereof.
  • the aromatic diamine may be selected from the group consisting of: 3 ,4 '-ox dianiline, l,3-bis-(4-aminopbenoxy)benzene, 4,4 '-oxydianiline,
  • the black-color polymer composite film has matte surfaces and a 60-degree gloss value of from 2 to 35.
  • the black-color polymer composite film has a thickness from 1.0 to 40 microns.
  • the film has a thickness from 10 to 40 microns; a 60- degree gloss from 10 to 35; and an optical density greater than or equal to 2.
  • the black-color polymer composite film may be bidirectionally stretched or
  • the polyimide -based black-color polymer composite film has surfaces with a 60- degree gloss from 2 to 35 and uniform color intensity, a thickness from 1.0 to 40 pm, an optical density greater than or equal to 2, and contains an inorganic silica matting agent in an amount of 0.5 to 20% by weight.
  • the disclosure also provides a multilayer film comprising the aforementioned polymer composite film and an adhesive layer.
  • the adhesive layer preferably contains an epoxy resin selected from the group consisting of: bisphenoi A epoxy resin, cresol novolac epoxy resin, phosphorus containing epoxy resin, and mixtures thereof.
  • the multilayer film is a cover!ay film.
  • the disclosure also provides an electronic device containing the polymer composite film or the multilayer film.
  • the disclosure also provides a process for producing the black-color polymer composite film, the process comprising the steps of: (a) mixing a phthalocyanine compound with a polymer or its precursor (monomer, oligomer, intermediate, such as polyamic acid to polyimide) in a liquid to form a slurry or solution and forming the slurry or solution into a wet film under the influence of an orientation-inducing stress field to align molecules of the phthalocyanine compound on a solid substrate, wherein the polymer is selected from the group consisting of polyimide, polyamide, polyoxadiazole, polybenzoxazole, polybenzobisoxazole, polythiazole, polybenzothiazole, polybenzobisthiazole, poly(p-phenylene vinylene), polybenzimidazole, polybenzobisimidazole, and combinations thereof; and (b) removing the liquid from the wet film to form the polymer composite film.
  • step (b) comprises polymerizing or
  • the step of forming a wet film is preferably conducted by spraying, printing, painting, casting or coating.
  • the process preferably contains a roll-to-roll procedure.
  • a process for producing a phthalocyanine compound-filled polymer film comprising the steps of: (a) mixing a phthalocyanine compound with a polymer precursor, a liquid (e.g. water or an organic solvent), and an optional curing agent to obtain a slurry (b) forming the slurry into a phthalocyanine compound-filled precursor polymer composite film and (c) initiating a cure reaction of the a phthalocyanine compound-filled precursor polymer composite film.
  • the curing reaction may be initiated chemically, by heat, by exposure to radiation, or by light.
  • the film- forming process may optionally be carried out under the influence of an orientation-inducing stress field, for example by using a slot-die head, comma coater head, or a pair of reverse-rotating rollers.
  • an orientation-inducing stress field for example by using a slot-die head, comma coater head, or a pair of reverse-rotating rollers.
  • the step of forming the slurry into a wet film may be carried out by a doctor blade-assisted casting, slot die coating, comma coating, reverse-rollers coating, spray coating, spin coating, or screen printing in such a manner that the step is conducted under the influence of an orientation-inducing stress field to align the molecules of the phthalocyanine compound on a solid substrate.
  • the resulting composite film has the
  • phthalocyanine compound molecules being substantially parallel to each other, leading to higher mechanical strength, dielectric strength, and surface smoothness.
  • the step of partially or completely removing the liquid from the wet film may be carried out in vacuum, in an inert atmosphere, in a ventilation environment, or at a temperature from 25°C to 300°C.
  • the converting step (e.g. imidizing step) is preferably carried out by exposure to a temperature from 100°C to 500°C for a period of time sufficient to convert polyamic acid to polyimide and/or to effect crosslinking of the polymer and chemical bonding of the polymer to the phthalocyanine compound, by exposure to light, by exposure to microwave energy, by exposure to radiation, or by combinations thereof.
  • the period of time is preferably from 1 minute to 4 hours.
  • the process may further comprise a step of compressing or stretching the phthalocyanine compound-filled polyimide film during or after said step (d) of imidizing the phthalocyanine compound-filled polyimide film.
  • the process may further comprise a step of adding one or more additional layers of phthalocyanine compound-filled polymer film after completing a first layer of phthalocyanine compound-filled composite film, where the one or more additional layers have the same chemical composition as the first layer or have a different chemical composition.
  • the process may further comprise a step of adding one or more additional layers of precursor composite film after completing a first layer of precursor composite film, where the one or more additional layers have the same chemical composition as said first layer, or have a different chemical composition.
  • the process is preferably carried out as a continuous or roll-to-roll process.
  • the polyimide precursor material may be selected from aromatic diamines, aliphatic diamines, and mixtures thereof in combination with aromatic dianhydrides.
  • the process slurry may further comprise a monomer, an oligomer, a polymer, a photosensitizer, or a combination thereof.
  • the slurry or suspension may further comprises a cure agent or anhydride selected from benzenetrtracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, diethylenetriaminepentaacetic dianhydride (DTPA), ethylenediaminetetraacetic dianhydride (EDTA), mellitic acid dianhydride (MADA), naphthalenetetracarboxylic dianhydride, oxydibenzoic dianhydride, oxydiphthalic anhydride (ODPA), phthalic anhydride, pyromellitic dianhydride (PMDA) and combinations thereof.
  • a cure agent or anhydride selected from benzenetrtracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, diethylenetriaminepent
  • the liquid may comprise water, acetone, g-butyrolactone, chlorobenzene, cyclopentyl methyl ether, dihydrolevoglucosenone, dimethylacetamide (DMAc), ethanol, N-methyl-2- pyrrolidone (NMP), hexafluorisopropanol (HFIP), butylated hydroxytoluene (BHT),
  • the slurry or suspension may further comprise a matting agent, a colorant, a reinforcement material or other additive at total non-graphene oxide additive weight of 0.1 weight percent to 15 weight percent of the total weight of the dried film.
  • the disclosure also provides a phthalocyanine compound-polyimide film made by the invented process described in the foregoing, having a thickness preferably from 1 pm to 200 pm (can be as thin as 10 nm or as thick as several mm.
  • the phthalocyanine compound-filled polyimide film may have a modulus from 1000 to 6000 MPa. More typically from 2,000 to 5,000 MPa.
  • the phthalocyanine compound-filled polyimide film may have a dielectric strength greater than 1,500 V/mil, more typically greater than 3,000, and further more typically greater than 5000 V/mil.
  • the phthalocyanine compound- filled polyimide film may have a dielectric strength from 3000 V/mil to 7000 V/mil.
  • the phthalocyanine compound-filled polyimide film may have multiple layers of varying compositions.
  • the disclosure also provides a process for producing a phthalocyanine compound-filled polymer film comprising the steps of: (a) mixing phthalocyanine compound (along with other optional ingredients, such as graphene sheets, expanded graphite platelets, and humic acid molecules) with a polymer precursor material and a liquid to form a slurry or suspension, wherein the graphene sheets are selected from graphene oxide, reduced graphene oxide, chemically reduced graphene oxide, fluorinated graphene, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene, and combinations thereof; (b) forming the slurry or suspension into a wet film; (c) partially or completely removing the liquid from the wet film to form a precursor polymer composite film; and (d) initiating a cure reaction of the film to obtain a phthalocyanine compound-filled composite film.
  • phthalocyanine compound (along with other optional ingredients, such as graphene sheets, expanded graphite plate
  • the polymer is preferably selected from the group consisting of polyimide, polyamide, polyoxadiazole, polybenzoxazole, polybenzobisoxazole, polythiazole, polybenzothiazole, polybenzobisthiazole, poly(p-phenylene vinylene), polybenzimidazole, polybenzobisimidazole, and combinations thereof.
  • the disclosure also provides a phthalocyanine compound-reinforced polymer film. In the composite film, the phthalocyanine compound molecules are substantially parallel to each other and, hence, exhibit a high elastic modulus, high tensile strength, and high dielectric strength.
  • the disclosure also provides an electronic device (e.g. smart phone, smart watch, tablet computer, etc.) containing the black-color polymer composite film.
  • an electronic device e.g. smart phone, smart watch, tablet computer, etc.
  • the inventive process is typically conducted in such a manner that the resulting phthalocyanine compound-filled carbon precursor polymer composite film exhibits an optical birefringence less than 1.4.
  • the optical birefringence is less than 1.2.
  • FIG. 1(A) Chemical formula of H2Pc (as an example of metal-free phthalocyanine compounds);
  • FIG. 1(B) Chemical formula of FePc (as an example of metal phthalocyanine compounds).
  • FIG. 2 Chemical reactions associated with production of PBO.
  • FIG. 3 Chemical reactions associated with production of polyimide (PI).
  • substantially and its variations are defined as being largely, but not necessarily wholly, what is specified as understood by one of ordinary skill in the art, and in one non-limiting embodiment“substantially” refers to ranges within 10%, within 5%, within 1%, or within 0.5% of a referenced range.
  • a* and b* color coordinates are substantially 0.
  • the present disclosure provides a black-color polymer composite film comprising a phthalocyanine compound dispersed in a polymer, wherein the phthalocyanine compound occupies a weight fraction from 1% to 50% based on the total polymer composite weight.
  • the polymer is selected from the group consisting of polyimide, polyamide, polyoxadiazole, polybenzoxazole, polybenzobisoxazole, polythiazole, polybenzothiazole, polybenzobisthiazole, poly(p-phenylene vinylene), polybenzimidazole, polybenzobisimidazole, and combinations thereof.
  • the phthalocyanine compound may be selected from a metal phthalocyanine compound (such as copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochromium phthalocyanine, magnesium phthalocyanine, manganous phthalocyanine, dilithium
  • a metal phthalocyanine compound such as copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochromium phthalocyanine, magnesium phthalocyanine, manganous phthalocyanine, dilithium
  • phthalocyanine aluminum phthalocyanine chloride, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, or silver phthalocyanine), or a metal-free phthalocyanine (e.g. hydrogen phthalocyanine), or a combination thereof.
  • metal-free phthalocyanine e.g. hydrogen phthalocyanine
  • FIG. 1(A) Illustrated in FIG. 1(A) is the chemical formula of H2Pc (as an example of metal-free phthalocyanine compounds).
  • FIG. 1(B) shows the chemical formula of FePc (as an example of metal phthalocyanine compounds).
  • This group of material has a distinct characteristic that it is a planar, aromatic molecule that has low electrical and thermal conductivities. The thinness of these molecules (typically from 0.4 nm to 1.5 nm) makes it possible to produce polymer composite films as thin as 10 nm. We have routinely produced polymer composite films from 10 nm to 500 pm, more typically from 100 nm to 200 pm, and still more typically from 1 pm to 100 pm (desirably from 1 to 8 pm for certain applications).
  • transition metal for use in the presently invented polymer composite film, transition metal
  • phthalocyanine compounds such as iron phthalocyanine (FePc), nickel phthalocyanine (NiPc), manganous phthalocyanine (MnPc), and cobalt phthalocyanine, are particularly desirable due to their ability to impart high dielectric constants or high dielectric strength to polymers. They are also found to be chemically compatible with the graphene materials.
  • Phthalocyanine compounds may be dissolved or dispersed in a wide variety of solvents, including water, polar organic solvents (DMF, DMSO, DMAc, THF, acetone, acetonitrile, chloroform, etc.), and some acids (e.g. acetic acid, formic acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, etc.) that are commonly used to dissolve or disperse the precursor (e.g. monomer) to a polymer or the polymer itself.
  • solvents including water, polar organic solvents (DMF, DMSO, DMAc, THF, acetone, acetonitrile, chloroform, etc.
  • acids e.g. acetic acid, formic acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, etc.
  • the phthalocyanine compound can be readily dispersed in a polymer matrix by dissolving the phthalocyanine compound and the polymer (or its precursor) in a solvent to form a solution, forming the solution into a film shape, removing the solvent to form a polymer composite film or a precursor composite film, and, if necessary or appropriate, converting the precursor into the polymer (e.g. converting polyamic acid to polyimide) to obtain the final polymer composite film.
  • converting the precursor into the polymer e.g. converting polyamic acid to polyimide
  • the black-color polymer composite film further comprises from 0.5% to 30% of a pigment selected from graphene, humic acid, expanded graphite flakes, fine carbon black particles having a medium size from 150 nm to 2 pm, or a combination thereof. Expanded graphite flakes and carbon black are more well-known in the art.
  • the graphene materials may be selected from a single-layer sheet or multi-layer platelet of graphene, graphene oxide, graphene fluoride, hydrogenated graphene, nitrogenated graphene, pristine graphene, doped graphene, boron doped graphene, nitrogen doped graphene, chemically treated graphene, reduced graphene oxide, functionalized graphene or graphene oxide, or a combination thereof.
  • nanographene platelets (NGPs) or“graphene materials” collectively refer to single-layer and multi-layer versions of graphene, graphene oxide, graphene fluoride, hydrogenated graphene, nitrogenated graphene, doped graphene, etc.
  • the thickness of an NGP is no greater than 100 nm and, in the present application, no greater than 10 nm (preferably no greater than 5 nm).
  • the NGP may be single-layer graphene. In the presently defined NGPs, there is no limitation on the length and width, but they are preferably smaller than 10 pm and more preferably smaller than lpm. We have been able to produce NGPs with length smaller than 100 nm or larger than 10 pm.
  • the NGP can be pristine graphene (with essentially 0% oxygen content) or graphene oxide (typically from 10 up to approximately 53% by weight oxygen). Graphene oxide can be thermally or chemically reduced to become reduced graphene oxide (typically with an oxygen content of 1-10%, mostly below 5% by weight).
  • the oxygen content or non-carbon content is preferably in the range from 5% to 45% by weight, and more preferably in the range from 10% to 35% by weight.
  • Graphene materials may be produced by using the following recommended procedures: (a) dispersing or immersing a laminar graphite material (e.g., natural graphite powder) in a mixture of an intercalant and an oxidant (e.g., concentrated sulfuric acid and nitric acid, respectively) to obtain a graphite intercalation compound (GIC) or graphite oxide (GO);
  • a laminar graphite material e.g., natural graphite powder
  • an oxidant e.g., concentrated sulfuric acid and nitric acid, respectively
  • steps (a) to (b) are the most commonly used steps to obtain exfoliated graphite and graphene oxide platelets in the field.
  • Step (d) is essential to the production of curved graphene sheets. Oxidized NGPs or GO platelets may be chemically reduced to recover conductivity properties using hydrazine as a reducing agent, before, during, or after chemical functionalization.
  • Nitrogenated graphene, nitrogen-doped graphene, or boron-doped graphene can be produced from chemical synthesis, chemical vapor deposition (CVD), or ion implantation.
  • nitrogen-doped graphene can be produced from CVD using CH 4 as a carbon source, NH 3 as a nitrogen source, nano-scaled Cu/Ni particles (or Cu, Ni, or Cu/Ni, foil) as a catalyst.
  • Boron-doped graphene can be produced by boron ion implantation.
  • graphene means a material comprising one or more planar sheets of bonded carbon atoms that are densely packed in a hexagonal crystal lattice in which carbon atoms are bonded together through strong in-plane covalent bonds, and further containing an intact ring structure throughout a majority of the interior. Preferably at least 80% of the interior aromatic bonds are intact. In the c-axis (thickness) direction, these graphene planes may be weakly bonded together through van der Waals forces. Graphene may contain non-carbon atoms at their edges or surface, for example OH and COOH functionalities.
  • graphene includes pristine graphene, graphene oxide, reduced graphene oxide, halogenated graphene including graphene fluoride and graphene chloride, nitrogenated graphene, hydrogenated graphene, doped graphene, functionalized graphene, and combinations thereof.
  • non-carbon elements comprise 0 to 25 weight % of graphene sheets.
  • doped graphene encompasses graphene having less than 10% of a non-carbon element. This non-carbon element can include hydrogen, oxygen, nitrogen, magnesium, iron, sulfur, fluorine, bromine, iodine, boron, phosphorus, sodium, and combinations thereof.
  • Graphene may comprise single-layer graphene or few-layer graphene, wherein the few-layer graphene is defined as a graphene platelet formed of less than 10 graphene planes. Graphene may also comprise graphene nanoribbons.“Pristine graphene” encompasses graphene sheets having essentially zero % of non-carbon elements. “Nanographene platelet” (NGP) refers to a graphene having a thickness from less than 0.34 nm (single layer) to 100 nm (multi-layer).
  • Graphene oxide refers to a graphene material comprising up to 53% oxygen by weight. Functional groups may be found primarily at the edges of graphene oxide platelets. Graphene oxide may comprise single-layer graphene oxide or few-layer graphene oxide, wherein the few- layer graphene is defined as a graphene platelet formed of less than 10 graphene planes.
  • Graphene oxide platelets may have a lateral dimension of lOOnm, 500nm, lpm, 2pm or may be larger or smaller.
  • Graphene oxide may be chemically reduced, for example by addition of ascorbic acid and exposure to a temperature of about 80°C, or may by thermally reduced by exposure to light, radiation, or a heat energy at a temperature from about 80°C to 3300°C.
  • substantially and its variations are defined as being largely but not necessarily wholly what is specified as understood by one of ordinary skill in the art, and in one non-limiting embodiment substantially refers to ranges within 10%, within 5%, within 1%, or within 0.5% of a referenced range.
  • HA is an organic matter commonly found in soil and can be extracted from the soil using a base (e.g. KOH). HA can also be extracted from a type of coal called leonardite, which is a highly oxidized version of lignite coal. HA extracted from leonardite contains a number of oxygenated groups (e.g. carboxyl groups) located around the edges of the graphene- like molecular center (SP core of hexagonal carbon structure). This material is slightly similar to graphene oxide (GO) which is produced by strong acid oxidation of natural graphite. HA has a typical oxygen content of 5% to 42% by weight (other major elements being carbon, hydrogen, and nitrogen).
  • GO graphene oxide
  • Non-aqueous solvents for humic acid include polyethylene glycol, ethylene glycol, propylene glycol, an alcohol, a sugar alcohol, a polyglycerol, a glycol ether, an amine-based solvent, an amide-based solvent, an alkylene carbonate, an organic acid, or an inorganic acid.
  • pigments include the following: barium lemon yellow, cadmium yellow lemon, 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) 2 0 3 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), CuCr 2 0 4 black, (Ni,Mn,Co)(Cr,Fe) 2 0 4 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 black 30, pigment black 32, pigment black 33 or mixtures thereof. These are but some of the many useful pigments.
  • the black-color polymer composite film further comprises from 0.5% to 15% by weight of a matting agent dispersed in the polymer based on the total polymer composite weight.
  • Silica is an inorganic material available as solid particles that can be ground and filtered to desired particle size ranges. The irregular shape and porosity of silica particles and low cost make this material a good choice as a matting agent.
  • Other potential matting agents can include: (a) other ceramics, such as, borides, nitrides, carbides and other oxides (e.g., alumina, titania, silicon nitride, etc.); and (b) organic particles, provided the organic particle can withstand the processing temperature of a chemically converted polyimide (processing temperatures of from about 250°C. to about 550°C, depending upon the particular polyimide process chosen) or synthesis temperatures of other polymers.
  • a chemically converted polyimide processing temperatures of from about 250°C. to about 550°C, depending upon the particular polyimide process chosen
  • synthesis temperatures of other polymers is polyimide particles.
  • the amount of matting agent, median particle size and density must be sufficient to produce the desired 60-degree gloss value.
  • the base film 60-degree gloss value is between and optionally including any two of the following: 2, 5, 10, 15, 20, 25, 30 and 35. In some embodiments, the base film 60-degree gloss value is from 10 to 35.
  • the disclosure also provides a process for producing an opaque phthalocyanine compound-filled polymer film having a high dielectric constant and/or a high dielectric strength.
  • the polymer film may contain polyimide.
  • the process for producing a phthalocyanine compound-filled polymer film comprises the steps of:
  • a phthalocyanine compound (optionally along with graphene sheets, humic acid molecules, expanded graphite platelets, and/or fine carbon black particles) with a polymer precursor, a liquid (e.g. water or other solvent), and an optional curing agent to obtain a slurry;
  • the mixing step (step (a)) can be accomplished by dissolving a polymer, monomer, oligomer, polymer precursor material (e.g. polyimide precursor material) in a solvent to form a solution and then dispersing or dissolving the phthalocyanine compound in the solution to form a suspension, slurry, or solution.
  • the polymer is in the amount of 0.1%-l0% by weight in the polymer- solvent solution prior to mixing with the phthalocyanine compound.
  • the phthalocyanine compound may occupy 1% to 30% (more typically 3% to 20% and most desirably 5%-l0%) by weight of the slurry.
  • a high shear mixer may be used for this process.
  • Heat may be applied to the slurry during this process. Cooling may be applied.
  • phthalocyanine compound may be added to the slurry prior to adding the polymer, after adding the polymer, or simultaneously.
  • the slurry may also be created by dissolving a phthalocyanine compound-polymer composite, or by dissolving a phthalocyanine compound-polymer precursor composite.
  • the polymer precursor material may be selected from the group consisting of a precursor (e.g. monomer or oligomer) to polyimide, polyamide, polyoxadiazole, polybenzoxazole, polybenzobisoxazole, polythiazole, polybenzothiazole, polybenzobisthiazole, poly(p-phenylene vinylene), polybenzimidazole, polybenzobisimidazole, precursors thereof, derivatives thereof, and combinations thereof.
  • the polymer film precursor material may be 3, 4 '-oxy dianiline.
  • the polymer precursor material may be an aromatic diamines, aliphatic diamines, or mixture thereof in combination with an aromatic dianhydrides.
  • the polymer film precursor material may be a polyimide precursor material.
  • Polyimide precursor materials may include aromatic diamines, aliphatic diamines, and mixtures thereof in combination with aromatic dianhydrides.
  • Polyimide precursor materials may include a catalyst or a dehydrating agent.
  • Polyimide precursor materials may include 3,4'-oxydianiline (ODA) combined with pyromellitic dianhydride (PMDA) in about a 1 : 1 molar ratio to create polyamic acid.
  • ODA 3,4'-oxydianiline
  • PMDA pyromellitic dianhydride
  • Polyimide precursor materials may include l,2,3,4-cyclopentanetetracarboxylic acid dianhydride (CPDA), 5-diaminobenzoic acid, 2,4-diaminobenzenesulfonic acid, 1, 10- diaminodecane, 1, 12-diaminododecane, 1, 13-diaminotridecane, 1, 14- diaminotetradecane, 1, 2,5,6-naphthalenetetracarboxylic, 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5- diaminopentane, 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 9- diaminonane, l,l-bis(2,3- dicarboxyphenyl)ethane dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,
  • HFDA bis(aminophenyl)hexafluoropropane
  • 2,5-diaminobenzenesulfonic acid 2,5-dimethyl- hexamethylenediamine, 2-methyl-l, 5-diaminopentane
  • 3,3 4,4'-benzophenonetetracarboxylic acid 3,3 ', 4,4'-biphenyltetracarboxylic acid, 3,3 ',4, 4 '-biphenyl tetracarboxylic dianhydride
  • benzenetrtracarboxylic dianhydride benzidine, bicyclooct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride (BODA), biphenyltetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl) methane dianhydride, bis(3,4-dicarboxyphenyl) sulfone dianhydride, bis(aminopropyl) tetramethyl- disiloxane, bisphenol A dianhydride, cyclobutane dianhydride, cyclobutanetetra-carboxylic acid dianhydride (CBDA), cyclohexane diamine, diethylenetriaminepentaacetic dianhydride (DTPA), dodecane diamine, hexamethylene diamine, mellitic acid dianhydride (MADA), meta- bis(aminophenoxydiphenyl)sulfone (m-BAPS), meta-
  • naphthalenetetracarboxylic dianhydride oxydibenzoic dianhydride, oxydiphthalic anhydride (ODPA), oxydiphthalic dianhydride, para-bis(aminophenoxydiphenyl)sulfone (p-BAPS), phthalic anhydride, pyridine, pyromellitic acid, pyromellitic dianhydride (PMDA), derivatives thereof, and combinations thereof.
  • the slurry of step (a) may further comprise a polymer matting agent or a coloring agent.
  • Polymer matting agents may include nanoscaled inorganic particles, carbon black, finely ground polymer particles, and combinations thereof.
  • Silica and surface-treated silica may be used as matting agents, optionally in combination with other matting agents.
  • U.S. Patent No. 8,574,720 issued 11/5/2013 for complete description of matting agents for polymer films, and methods of using said matting agents, applicable in the instant disclosure.
  • the slurry of step (a) may further comprise an additive selected from graphene, expanded graphite flakes, carbon nanotube, humic acid, carbon black, acetylene black, etc.
  • the solvent of mixing step (a) may comprise water, acetone, g-butyrolactone, chlorobenzene, cyclopentyl methyl ether, dihydrolevoglucosenone (Cyrene) dimethylacetamide (DMAc), ethanol, N-methyl-2-pyrrolidone (NMP), hexafluorisopropanol (HFIP), butylated hydroxytoluene (BHT), dimethylformamide (DMF), dimethylsulfoxide (DMSO), methanol, methyl acetate, methyl ethyl ketone, methylene chloride, piperazine, sodium trifluoroacetate (NaTFA), tert-butanol, tetrahydrofuran (THF), 1,2, 4 -trichlorobenzene (TCB), triethylamine (TEA), triethyl phosphate, toluene, derivatives thereof, and mixtures thereof.
  • DMAc
  • the solvent of mixing step (a) may comprise a solvent pair, including cyclohexanone- methanol, cyclohexanone-ethanol, cyclopentanone-methanol, cyclopentanone-ethanol, g- butyrolactone-methanol, g-butyrolactone-ethanol, g-butyrolactone-water, g-valerolactone- methanol, g-valerolactone-ethanol, and g-valerolactone-water, as taught in Duereh, Alif, et al. "Replacement of hazardous chemicals used in engineering plastics with safe and renewable hydrogen-bond donor and acceptor solvent-pair mixtures.” ACS Sustainable Chemistry & Engineering 3.8 (2015): 1881-1889.
  • Film-forming can be conducted by casting or coating the slurry into a thin film on a solid substrate such as PET film.
  • the film-forming process may optionally be carried out under the influence of an orientation-inducing stress field, for example by slot-die coating, reverse-roll coating, comma coating, or casting the slurry with a doctor blade to form a thin film of desired thickness.
  • the shear stress may be created by extruding the dispensed slurry through a coating die over a supporting flexible PET substrate.
  • the film may also be formed by spray coating, spin coating, or screen printing.
  • the film may be formed by extruding the slurry into a bath of cure agents or conversion chemicals.
  • the wet film may be from 1 pm to 200 pm in thickness prior to drying, or it may be thicker or thinner.
  • the wet film may preferably be 10 pm, 20 pm, 50 pm or 70pm in thickness.
  • the coating process can be a continuous, roll-to-roll process that is fully automated.
  • the cast or coated film is initially in a wet state and the liquid component is substantially removed after coating or casting.
  • Step (b) of partially or completely removing the solvent liquid may be carried out by heat, ventilation, or by vacuum. This step may be carried out at a temperature from 25°C to 300°C.
  • Step (c) of initiating a cure or conversion reaction may be carried out by exposure to chemicals, by exposure to heat, by exposure to radiation, by exposure to microwaves, by exposure to light, or by combinations thereof.
  • Heat treatment to initiate a cure reaction may involve heating the film to a temperature from 100° to 500°C for a period of time sufficient to effect crosslinking of the polymer precursor to the phthalocyanine compound (and graphene oxide, humic acid, etc. if present) to obtain a phthalocyanine compound- filled polymer film.
  • the heat treatment time may be from 1 minute to 24 hours.
  • the heat treatment time may be 5 minutes, 10 minutes, 1 hour, or may be longer or shorter. Higher heat treatment temperatures require shorter heat treatment times.
  • the heat treatment may be selected from 150°C to 400°C. Preferably, the heat treatment may be carried out at 350°C for 3 to 10 minutes. Heat treatment may be carried out in vacuum, in an inert gas atmosphere, or in standard atmospheric conditions.
  • the finished film may be from 1 pm to 200 pm in thickness prior to drying, or it may be thicker or thinner. The finished film may preferably be 5 pm, 10 pm, 15 pm, 40 pm, 60 pm, 80 pm, or 100 pm in thickness.
  • the step of initiating a cure reaction may cause imidization of the slurry.
  • the reaction may be allowed to progress to from 60% completion of imidization to 100% completion of imidization.
  • the reaction may be allowed to progress to about 80% completion, about 90% completion, or to about 95% completion.
  • the steps of coating and initiating a cure reaction may be repeated one or more times to create a thicker film.
  • the composition of the slurry may be varied between coating steps to create a film having layers with varying properties.
  • the phthalocyanine compound-filled polymer film may be stretched before, during or after initiation of the cure reaction.
  • the phthalocyanine compound-filled polymer film may be compressed before, during or after the initiation of the cure reaction.
  • the phthalocyanine compound-filled polymer film may be peeled from the substrate or may remain with the substrate.
  • the phthalocyanine compound-filled polymer films made from this process may have a tensile modulus from 3000 to 6000 MPa.
  • the phthalocyanine compound-filled polymer film may have a dielectric strength from about 1,500 to about 7,000 V/mil. Preferably, the dielectric strength may be greater than 5000 V/mil.
  • the phthalocyanine compound-filled polymer film has a matte surface finish.
  • phthalocyanine compound-filled films prepared by the disclosed process may be heat treated (carbonized) to increase the thermal or electrical conductivity.
  • heat treated carbonized
  • a process for producing a phthalocyanine compound-filled polymer film may comprise the steps of: (a) mixing a phthalocyanine compound with a polymer precursor material and a liquid to form a slurry or suspension; (b) forming the slurry or suspension into a wet film; (c) partially or completely removing the liquid from the wet film to form a precursor polymer composite film; and (d) initiating a cure reaction of the film to obtain a phthalocyanine compound-filled composite film.
  • the polymer is preferably selected from the group consisting of polyimide, polyamide, polyoxadiazole, polybenzoxazole, polybenzobisoxazole, polythiazole,
  • polybenzothiazole polybenzobisthiazole, poly(p-phenylene vinylene), polybenzimidazole, polybenzobisimidazole, and combinations thereof.
  • Polybenzoxazole (PBO) films were prepared via casting and thermal conversion from its precursor, methoxy-containing polyaramide (MeO-PA). Specifically, monomers of 4, 4’- diamino-3,3’-dimethoxydiphenyl (DMOBPA), and isophthaloyl dichloride (IPC) were selected to synthesize PBO precursors, methoxy-containing polyaramide (MeO-PA) solution.
  • DMOBPA 4, 4’- diamino-3,3’-dimethoxydiphenyl
  • IPC isophthaloyl dichloride
  • This MeO- PA solution for casting was prepared by polycondensation of DMOBPA and IPC in DMAc solution in the presence of pyridine and LiCl at -5°C for 2hr, yielding a 20wt% pale yellow transparent MeO-PA solution.
  • the inherent viscosity of the resultant MeO-PA solution was 1.20 dL/g measured at a concentration of 0.50 g/dl at 25°C. This MeO-PA solution was diluted to a concentration of 15wt by DMAc for casting.
  • the as- synthesized MeO-PA was cast onto a glass surface to form thin films (35-120 pm) under a shearing condition.
  • the cast film was dried in a vacuum oven at 100°C for 4 hr to remove the residual solvent.
  • the resulting film with a thickness of approximately 28-100 mhi was treated at 200°C-350°C under N 2 atmosphere in three steps and annealed for about 2 hr at each step. This heat treatment serves to thermally convert MeO-PA into PBO films.
  • the chemical reactions involved may be illustrated in FIG. 2.
  • PI poly(amic acid)
  • PAA poly(amic acid)
  • PMDA pyromellitic dianhydride
  • ODA oxydianiline
  • both chemicals were dried in a vacuum oven at room temperature.
  • 4 g of the monomer ODA was dissolved into 21 g of DMF solution (99.8 wt %). This solution was stored at 5°C before use.
  • PBI is prepared by step-growth polymerization from 3,3',4,4'-tetraaminobiphenyl and diphenyl isophthalate (an ester of isophthalic acid and phenol).
  • the PBI used in the present study was in a PBI solution form, which contains 0.7 dl/g PBI polymer dissolved in dimethylacetamide (DMAc).
  • DMAc dimethylacetamide
  • the PBI and phthalocyanine compound-PBI films were cast onto the surface of a glass substrate.
  • the iron phthalocyanine was used in this study.
  • SEM Scanning electron microscopy
  • TEM transmission electron microscopy
  • SAD selected-area electron diffraction
  • BF bright field
  • DF dark-field
  • Emulsion polymerization was found to provide simple and direct route for the preparation phthalocyanine compound-polymer films.
  • a phthalocyanine compound was first dispersed in an aqueous solution containing a statistical oligomer constituted of five butyl acrylate and ten acrylic acid units prepared by reversible addition fragmentation chain transfer (RAFT) polymerization using a trithiocarbonate as RAFT agent. Then, emulsion polymerization was initiated and cast into films, leading to the formation of thin polymer composite films.
  • RAFT reversible addition fragmentation chain transfer
  • Example 5 Polymer composite films containing a phthalocyanine compound and some humic acid or reduced humic acid from leonardite
  • Humic acid can be extracted from leonardite by dispersing leonardite in a basic aqueous solution (pH of 10) with a high yield (in the range from 75%). Subsequent acidification of the solution leads to precipitation of humic acid powder.
  • a basic aqueous solution pH of 10
  • 3 g of leonardite was dissolved by 300 ml of double deionized water containing 1M KOH (or NH4OH) solution under magnetic stirring. The pH value was adjusted to 10. The solution was then filtered to remove any big particles or any residual impurities.
  • a humic acid dispersion containing a FePc compound (15% by wt.), HA (10% by wt.) and a polymer precursor material (e.g. uncured polyamic acid and monomers for phenolic resin, respectively), was dissolved in a common solvent and was cast onto a glass substrate to form a series of precursor composite films. The films were then thermally converted or cured into PI composite and phenolic resin composite films, respectively.
  • a polymer precursor material e.g. uncured polyamic acid and monomers for phenolic resin, respectively
  • Example 6 Measurements of the tensile strength, dielectric strength, and gloss of various polymer composite films A universal testing machine was used to determine the tensile strength and modulus of these materials (ASTM D-882). The dielectric strength of the polymer films was measured according to ASTM D-149. The 60-degree gloss value was measured using Micro -TRI-Gloss meter. These procedures are well-known in the art. The tensile strength of the polymer composite films is found to be from 210 MPa to 330 MPa. The dielectric strength is from 1500 to 7800 V/mil. The 60-degree gloss value is from 2 to 35 for samples containing a matting agent.

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Abstract

L'invention porte sur un film composite polymère de couleur noire comprenant un composé phtalocyanine dispersé dans un polymère choisi dans le groupe constitué par le polyimide, le polyamide, le polyoxadiazole, le polybenzoxazole, le polybenzobisoxazole, le polythiazole, le polybenzothiazole, le polybenzobisthiazole, le poly(p-phénylène vinylène), le polybenzimidazole, le polybenzobisimidazole et des combinaisons de ceux-ci. Le composé phtalocyanine occupe une fraction de 0,1 % à 50 % en poids par rapport au poids total de polymère composite. De préférence, le composé phtalocyanine est choisi parmi la phtalocyanine de cuivre, la phtalocyanine de zinc, la phtalocyanine d'étain, la phtalocyanine de fer, la phtalocyanine de plomb, la phtalocyanine de nickel, la phtalocyanine de vanadyle, la phtalocyanine de fluorochrome, la phtalocyanine de magnésium, la phtalocyanine manganeuse, la phtalocyanine de dilithium, le chlorure de phtalocyanine d'aluminium, la phtalocyanine de cadmium, la phtalocyanine de chlorogallium, la phtalocyanine de cobalt, la phtalocyanine d'argent, une phtalocyanine exempte de métal ou une combinaison de ceux-ci. L'invention concerne également un procédé de production d'un film composite polymère.
PCT/US2019/039699 2018-07-02 2019-06-28 Films composites polymères de couleur foncée Ceased WO2020009911A1 (fr)

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WO2025047132A1 (fr) * 2023-08-29 2025-03-06 東レ株式会社 Composition de résine, film durci, composant électronique et dispositif d'affichage électroluminescent organique

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US20100308284A1 (en) * 2008-03-28 2010-12-09 Dic Corporation Pigment dispersing composition color filter
WO2012042264A2 (fr) * 2010-09-29 2012-04-05 Dzp Technologies Ltd Composition imprimable, procédé et utilisations
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CN113444366A (zh) * 2020-03-27 2021-09-28 杜邦电子公司 单层聚合物膜和电子装置
TWI879920B (zh) * 2020-03-27 2025-04-11 美商杜邦電子股份有限公司 單層聚合物膜及電子裝置
CN113444366B (zh) * 2020-03-27 2025-05-27 杜邦电子公司 单层聚合物膜和电子装置
WO2025047132A1 (fr) * 2023-08-29 2025-03-06 東レ株式会社 Composition de résine, film durci, composant électronique et dispositif d'affichage électroluminescent organique

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