Classifications

• • 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
• • 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
  • C08K5/49—Phosphorus-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/20—Conductive material dispersed in non-conductive organic material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables

Definitions

• the present disclosure relates to a composition for improving the conductivity of a conductive polymer. More specifically, the present invention relates to a conductivity improver containing an organic phosphorus compound.
• the present disclosure provides a conductive material containing a desired combination of conductive components and a base material.
• the disclosure provides, for example:
• (Item 1) A composition for improving the conductivity of a conductive polymer containing a metallic component, which contains an organic phosphorus compound.
• (Item 2) The composition according to the above item, wherein the organic phosphorus compound contains trivalent phosphorus.
• (Item 3) The composition according to any one of the above items, wherein the organic phosphorus compound is phosphine substituted with alkyl, cycloalkyl or aryl.
• the organophosphorus compound is derived from tributylphosphine, trioctylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, cyclohexyldiphenylphosphine, 1,2-bis (diphenylphosphine) ethane, and tricyclohexylphosphine.
• the composition according to any one of the above items, which is one kind or a combination of two or more kinds of phosphine selected from the above group. (Item 4a) The composition according to any one of the above items, wherein the organic phosphorus compound is triphenylphosphine.
• the metal contains silver, copper, gold, aluminum, zinc, nickel, tin, and / or iron.
• the metal is silver.
• the metal oxide is one or more of oxides selected from the group consisting of alumina, tin oxide, indium oxide, zinc oxide, indium-tin oxide, and antimony-tin oxide.
• the metal carbide is one or a combination of two or more carbides selected from the group consisting of tungsten carbide, titanium carbide, molybdenum carbide, tantalum carbide, niobium carbide, vanadium carbide, and zirconium carbide.
• the composition according to any one of the above items. (Item 9) The composition according to any one of the above items, wherein the metallic component is particles having a particle size of 1 ⁇ m to 100 ⁇ m. (Item 10) The composition according to any one of the above items, wherein the polymer matrix in the conductive polymer is a (meth) acrylic polymer, a urethane polymer, an olefin polymer, or an epoxy polymer.
• R 1 is a hydrogen atom or a methyl group and R 2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted non-aryl heterocycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.
• the composition according to any one of the above items. (Item 12a) The composition according to any one of the above items, wherein R 1 is a hydrogen atom.
• (Item 12b) The composition according to any one of the above items, wherein R 2 is a hydrogen atom or a substituted or unsubstituted alkyl group.
• (Item 12c) The composition according to any one of the above items, wherein R 2 is a hydrogen atom or a substituted or unsubstituted C 1 to 6 alkyl group.
• (Section 12d) R 2 is ethyl, A composition according to any one of the above items.
• (Item 13) A sintering accelerator for metallic components containing an organic phosphorus compound.
• (Item 14) The sintering accelerator according to any one of the above items, which comprises one or more of the characteristics described in the above item.
• a conductive material containing a polymer matrix, a metal, and an organic phosphorus compound (Item 16) The conductive material according to any one of the above items, wherein the organic phosphorus compound contains trivalent phosphorus. (Item 17) The conductive material according to any one of the above items, wherein the organic phosphorus compound is phosphine substituted with alkyl, cycloalkyl or aryl.
• the organophosphorus compound is derived from tributylphosphine, trioctylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, cyclohexyldiphenylphosphine, 1,2-bis (diphenylphosphine) ethane, and tricyclohexylphosphine.
• the conductive material according to any one of the above items which is one kind of phosphine or a combination of two or more kinds selected from the above group.
• the conductive material according to any one of the above items, wherein the organic phosphorus compound is triphenylphosphine.
• (Item 18) The conductive material according to any one of the above items, wherein the metal contains silver, copper, gold, aluminum, zinc, nickel, tin, and / or iron.
• (Item 18a) The conductive material according to any one of the above items, wherein the metal is silver.
• Item 19 The conductive material according to any one of the above items, wherein the metal is particles having a particle size of 1 ⁇ m to 100 ⁇ m.
• the polymer matrix is an acrylic polymer, a urethane polymer, an olefin polymer, or an epoxy polymer.
• (Item 20a) The conductive material according to any one of the above items, wherein the polymer matrix is a (meth) acrylic polymer.
• (Item 21) The conductive material according to any one of the above items, wherein the polymer matrix is a homopolymer containing one kind of monomer component or a copolymer containing two or three kinds of monomer components.
• (Item 21a) The conductive material according to any one of the above items, wherein the polymer matrix is a homopolymer.
• the monomer component of the polymer matrix is the formula (1).
• R 1 is a hydrogen atom or a methyl group and R 2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted non-aryl heterocycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.
• the conductive material according to any one of the above items. (Item 22a) The conductive material according to any one of the above items, wherein R 1 is a hydrogen atom.
• the disclosure also provides, for example:
• (Item A1) A composition for improving the conductivity of a conductive polymer containing a metallic component, which contains an organic phosphorus compound.
• (Item A2) The composition according to the preceding item, wherein the organic phosphorus compound contains trivalent phosphorus.
• (Item A3) The composition according to any one of the preceding items, wherein the organic phosphorus compound is phosphine substituted with an alkyl, cycloalkyl or aryl.
• the organophosphorus compound is derived from tributylphosphine, trioctylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, cyclohexyldiphenylphosphine, 1,2-bis (diphenylphosphine) ethane, and tricyclohexylphosphine.
• (Item A4b) The composition according to any one of the above items, wherein the organic phosphorus compound is triphenylphosphine.
• the metal-based component is a metal, a metal oxide, a metal carbide, a metal sulfide, or a combination thereof.
• the metal comprises silver, copper, gold, aluminum, zinc, nickel, tin, and / or iron.
• the composition according to any one of the above items, wherein the metal is silver.
• the metal oxide is one or more of oxides selected from the group consisting of alumina, tin oxide, indium oxide, zinc oxide, indium-tin oxide, and antimony-tin oxide.
• the composition according to any one of the preceding paragraphs which is a combination.
• the metal carbide is one or a combination of two or more carbides selected from the group consisting of tungsten carbide, titanium carbide, molybdenum carbide, tantalum carbide, niobium carbide, vanadium carbide, and zirconium carbide.
• the composition according to any one of the preceding paragraphs (Item A9) The composition according to any one of the preceding items, wherein the metallic component is particles having a particle size of 1 ⁇ m to 100 ⁇ m.
• the polymer matrix in the conductive polymer is a (meth) acrylic polymer, a urethane polymer, an olefin polymer, an epoxy polymer, or a styrene-butadiene polymer, any one of the preceding items.
• the composition according to. (Item A10b) The composition according to any one of the above items, wherein the polymer matrix in the conductive polymer is a (meth) acrylic polymer.
• the monomer component of the polymer matrix is the formula (1). It is a compound represented by, and in the formula, R 1 is a hydrogen atom or a methyl group and R 2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted non-aryl heterocycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.
• composition according to any one of the preceding paragraphs The composition according to any one of the preceding paragraphs.
• (Item A12b) The composition according to any one of the above items, wherein R 1 is a hydrogen atom.
• (Section A12E) R 2 is ethyl, A composition according to any one of the above items.
• (Item A14) The sintering accelerator according to any one of the preceding items, which comprises one or more of the characteristics described in the preceding item.
• (Item A15) A conductive material containing a polymer matrix, a metal, and an organic phosphorus compound.
• (Item A16) The conductive material according to any one of the preceding items, wherein the organic phosphorus compound contains trivalent phosphorus.
• the organophosphorus compound is derived from tributylphosphine, trioctylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, cyclohexyldiphenylphosphine, 1,2-bis (diphenylphosphine) ethane, and tricyclohexylphosphine.
• the conductive material according to any one of the above items which is one kind of phosphine or a combination of two or more kinds selected from the above group.
• the conductive material according to any one of the above items, wherein the organic phosphorus compound is triphenylphosphine.
• (Item A20b) The conductive material according to any one of the above items, wherein the polymer matrix is a (meth) acrylic polymer.
• (Item A21a) The conductive material according to any one of the preceding items, wherein the polymer matrix is a homopolymer containing one kind of monomer component or a copolymer containing two or three kinds of monomer components.
• (Item A21b) The conductive material according to any one of the above items, wherein the polymer matrix is a homopolymer.
• the monomer component of the polymer matrix is the formula (1).
• R 1 is a hydrogen atom or a methyl group and R 2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted non-aryl heterocycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.
• the conductive material according to any one of the preceding items. (Item A22b) The conductive material according to any one of the above items, wherein R 1 is a hydrogen atom.
• (Item A26b) A method for improving the conductivity of a conductive polymer containing a metal, wherein the method heats a polymer matrix and a mixture containing the metal and an organic phosphorus compound to heat the conductive polymer containing the metal. Including the process of producing Method.
• (Item A27) The method according to any one of the preceding items, wherein the heating temperature is 80 ° C. to 150 ° C.
• (Item A28) The method according to any one of the preceding items, wherein the heating temperature is 100 ° C. to 140 ° C.
• (Item A29) The method according to any one of the preceding items, wherein the heating time is 10 to 50 minutes.
• conductivity improvers are provided, and by using these, it is possible to provide a technique capable of improving the conductivity.
• conductivity is used in the usual sense in the art and means the property of conducting electricity, and the amount of physical properties thereof is called “conductivity”, and is used for a certain object (also called a conductor). It is defined as the reciprocal of resistivity (specific resistivity, also called volume resistivity in the resin field).
• the conductivity is measured as follows. Specifically, unless otherwise specified, a measurement target (for example, a film) is cut out into a length of 0.5 cm, a width of 2.00 cm, and a thickness of 0.2 cm, and a four-terminal measurement method (for example, Loresta GP [Mitsubishi Chemical]. Analytech] can be used, but the value measured by is not limited to this).
• the term "conductive material" refers to any material having conductivity.
• the conductive material has a resistance of 1.0 ⁇ 10 -1 ⁇ ⁇ cm or less, usually 1.0 ⁇ 10 ⁇ 2 ⁇ ⁇ cm or less, preferably 1.0 ⁇ 10 -3 ⁇ ⁇ cm or less. It is intended for those with a rate, but is not limited to this.
• the conductive material contains a conductive component that imparts conductivity.
• the conductive material is usually composed of a base material and a conductive component.
• Phosphine as used herein is a trivalent phosphorus compound represented by R 3 P, wherein each R is independently hydrogen or optionally substituted, any alkyl, cycloalkyl, aryl , Non-aryl heterocycloalkyl, heteroaryl and the like.
• organicphosphorus compound is used in the usual sense in the art and is a general term for organic compounds containing phosphorus, such as those in which a phosphorus atom is directly bonded to a carbon atom and a phosphoric acid ester. Some are bonded, and organic compounds containing a carbon-phosphorus bond are generally used.
• organic phosphorus compound a compound containing trivalent phosphorus is typically used, and examples thereof include, but are not limited to, phosphine substituted with alkyl, cycloalkyl or aryl, and examples thereof include tributylphosphine and tri.
• One or more phosphines selected from the group consisting of octylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, cyclohexyldiphenylphosphine, 1,2-bis (diphenylphosphine) ethane, and tricyclohexylphosphine. Combinations of, especially triphosphine and the like can be used.
• improving conductivity means that when a component of the present disclosure is added to a conductive component or a conductive material, the conductivity is significantly increased as compared with that before the addition, for example.
• Conductivity at least about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80% , About 85%, about 90%, about 95%, about 99% improvement, which can also be expressed by a decrease in volume resistivity.
• the volume resistivity is about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, and about, as compared with the comparison target. 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70% , About 75%, about 80%, about 85%, about 90%, about 95%, about 99% reduction.
• the term "lowering the sintering temperature” means the same or smaller when the components of the present disclosure are added to the conductive component or the conductive material, even when heated at a lower temperature than when not added. It means that the volume resistivity can be achieved.
• the sintering temperature is at least about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15. %, About 20%, About 25%, About 30%, About 35%, About 40%, About 45%, About 50%, About 55%, About 60%, About 65%, About 70%, About 75%, It means to reduce by about 80%, about 85%, about 90%, about 95%, and about 99%.
• the base material is also referred to as a "matrix” and refers to a basic part of the structure of a conductive material.
• Various polymers can be used as the base material.
• the base material may be referred to as a "polymer matrix".
• the polymer matrix may be a homopolymer containing one kind of monomer component or a copolymer containing two or three kinds of monomer components, and a (meth) acrylic polymer or the like can be used.
• the monomer component of the polymer matrix is the formula (1).
• R 1 is a hydrogen atom or a methyl group
• R 2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted compound. It may be a compound which is a non-aryl heterocycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.
• the "metal-based component” is a component containing a metal atom as a component thereof in some form, and in addition to a metal component such as a metal, a component derived from a metal (for example, a metal oxide, a metal carbide, etc.) It is a concept that includes metal sulfide, etc.) or a combination thereof.
• the "metal component” includes a metal or an alloy.
• the metal may be silver, copper, gold, aluminum, zinc, nickel, tin, and / or iron.
• metal oxide examples include alumina, tin oxide, indium oxide, zinc oxide, indium-tin oxide, and antimony-tin oxide.
• metal carbide examples include tungsten carbide, titanium carbide, molybdenum carbide, tantalum carbide, niobium carbide, vanadium carbide, zirconium carbide and the like.
• the "particle size” or “particle size” of the metal-based component is used interchangeably, means an average particle size d50, and can be measured by a commercially available laser diffraction type particle size distribution measuring device or the like. it can.
• the particle size is also applied to the case of a shape that is not spherical, and if it is other than spherical, it means the particle size when converted to spherical.
• the shape other than the spherical shape may be any shape such as a reptile shape or a needle shape.
• the term "conductive polymer” includes, among the polymers, those having conductivity and those having conductivity as a whole when mixed with other components, preferably having a resistivity of 1. 0 x 10 -3 ⁇ ⁇ cm or less.
• a typical example of a conductive polymer is a mixture of a polymer matrix and a metallic component.
• the conductive polymer is sometimes referred to as a conductive polymer composition.
• the "(meth) acrylic monomer” is a monomer containing an acrylic group and / or a methacrylic group, and examples thereof include acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, and acrylic acid amide. Examples thereof include methacrylic acid amide.
• (meth) acrylic means “acrylic” or “methacryl”
• (meth) acrylate means “acrylate” or “methacrylate”.
• a typical example is that obtained by reacting a polyol with diisocyanate.
• Urethane-based polymers may also be referred to herein as “urethane-based resins” or “urethane resins.”
• the "olefin polymer” is a polymer produced by polymerizing a hydrocarbon monomer (typically an alkene) having one or more double bonds. Specific examples include polyethylene, polypropylene, polystyrene and the like. Olefin polymers may also be referred to herein as “olefinic resins” or “olefinic resins.”
• epoxy polymer refers to a thermosetting resin that can be cured by forming a cross-linked network with epoxy groups remaining in the polymer.
• Epoxy-based polymers include prepolymers before cross-linking networking and resins obtained by thermosetting a mixture of prepolymer and curing agent. Epoxy polymers may also be referred to herein as "epoxy resins" or "epoxy resins.”
• the "styrene-butadiene polymer” is a copolymer produced by copolymerizing a styrene-based monomer and a butadiene-based monomer.
• the styrene-butadiene polymer may be referred to as a "styrene-butadiene resin” or a “styrene-butadiene resin” in the present specification.
• substituted number means the maximum number of hydrogens that can be substituted when hydrogen of a certain group is substituted with a substituent, provided that the resulting group is chemically stable. To do.
• alkyl group refers to a monovalent group produced by the loss of one hydrogen atom from an aliphatic hydrocarbon (alkane) such as methane, ethane, or propane, and is generally C n H 2n + 1- . Represented (where n is a positive integer).
• alkyl group can be straight or branched.
• Examples of the alkyl (C 1-4 alkyl) group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and a sec-butyl group.
• Examples of the alkyl (C 1 to 6 alkyl) group having 1 to 6 carbon atoms include a C 1 to 4 alkyl group, an n-pentyl group, an isoamyl group, an n-hexyl group, an isohexyl group and the like. Is not limited to such examples.
• Examples of the alkyl (C 1 to 10 alkyl) group having 1 to 10 carbon atoms include a C 1 to 6 alkyl group, an n-octyl group, an n-nonyl group, an isononyl group, a branched nonyl group, and an n-decanyl group.
• Examples thereof include an isodecyl group, but the present disclosure is not limited to such examples.
• Examples of the alkyl (C 1-18 alkyl) group having 1 to 18 carbon atoms e.g., C 1 ⁇ 10 alkyl group, undecyl group, lauryl group, tridecyl group, myristyl group, pentadecyl group, palmityl group, heptadecyl group, stearyl group , Isostearyl groups and the like, but the present disclosure is not limited to such examples.
• alkenyl group refers to a monovalent group formed by the loss of one hydrogen atom from an aliphatic hydrocarbon (alkene) containing at least one double bond such as ethene, propene, or butene. good, generally represented by C m H 2m-1 (where, m is an integer of 2 or more).
• alkenyl group can be straight or branched. Examples of the alkenyl group having 2 to 6 carbon atoms include an ethenyl group, a 1-propenyl group, a 2-propenyl group, a butenyl group, a pentenyl group, a hexenyl group and the like, but the present disclosure is limited to such examples.
• alkenyl group having 2 to 10 carbon atoms examples include an alkenyl group having 2 to 6 carbon atoms, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group and the like, but the present disclosure is limited to such examples. It's not a thing.
• alkoxy group refers to a monovalent group formed by the loss of the hydrogen atom of the hydroxy group of alcohols, and is generally represented by C n H 2n + 1 O- (where n is 1 or more). Is an integer of).
• alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a tert-butyloxy group, a sec-butyloxy group and an n-. Examples thereof include a pentyloxy group, an isoamyloxy group, an n-hexyloxy group, an isohexyloxy group and the like, but the present disclosure is not limited to such examples.
• haloalkyl group refers to an alkyl group in which one or more hydrogen atoms on the alkyl group are substituted with halogen atoms.
• perhaloalkyl refers to an alkyl group in which all hydrogen atoms on the alkyl group are substituted with halogen atoms.
• Examples of the haloalkyl group having 1 to 6 carbon atoms include a trifluoromethyl group, a trifluoroethyl group (2,2,2-trifluoroethyl group, etc.), a perfluoroethyl group, and a trifluoro group.
• n-propyl group tetrafluoropropyl group (2,2,3,3-tetrafluoropropyl group, etc.)
• perfluoro n-propyl group trifluoroisopropyl group, perfluoroisopropyl group, trifluoro n-butyl group, perfluoro n- Butyl group, trifluoroisobutyl group, perfluoroisobutyl group, trifluorotert-butyl group, perfluorotert-butyl group, trifluoron-pentyl group, octafluoropentyl group (2,2,3,3,4,4,5) , 5-Octafluoropentyl group, etc.), perfluoro n-pentyl group, trifluoro n-hexyl group, perfluoro n-hexyl group, etc., but the present disclosure is not limited to such examples.
• Examples of the haloalkyl group having 1 to 8 carbon atoms include C 1-6 haloalkyl group, undecafluoro n-heptyl group, perfluoro n-heptyl group, and tridecafluorooctyl group (3,3, 4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group, etc.), perfluoron-octyl group, etc., but the present disclosure is limited to such examples. It is not limited.
• cycloalkyl group means a monocyclic or polycyclic saturated hydrocarbon group, and includes those having a crosslinked structure.
• C 3-12 cycloalkyl group means a cyclic alkyl group having 3 to 12 carbon atoms.
• Specific examples of the C 6-12 cycloalkyl group include a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, an isobornyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group and the like.
• the present disclosure is not limited to such examples.
• C 5-12 cycloalkyl group examples include a cyclopentyl group, a C 6-12 cycloalkyl group, and the like, but the present disclosure is not limited to these examples.
• Specific examples of the C 3-12 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a C 5-12 cycloalkyl group and the like.
• Preferably, "C 6-12 cycloalkyl group" is mentioned, but the present disclosure is not limited to such an example.
• cycloalkenyl group means a monocyclic or polycyclic unsaturated hydrocarbon group containing a double bond, and includes those having a crosslinked structure. Examples thereof include those in which one or more of the carbon-carbon bonds of the "cycloalkyl group” are double bonds.
• C 3-12 cycloalkenyl group means a cyclic alkenyl group having 3 to 12 carbon atoms.
• C 6-12 cycloalkenyl group examples thereof include a 1-cyclohexenyl group, a 2-cyclohexenyl group, a 3-cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclononenyl group and the like in the case of "C 6-12 cycloalkenyl group”. Be done.
• C 3-12 cycloalkyl group a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a C 6-12 cycloalkenyl group and the like can be mentioned.
• C 6-12 cycloalkenyl group is mentioned, but the present disclosure is not limited to such an example.
• non-aryl heterocycloalkyl and the “non-aryl heterocycle” are cyclic compounds having 1 to 3 atoms of the same type or different types selected from nitrogen atom, oxygen atom and sulfur atom in the ring. Means a group, which may contain one or more unsaturated bonds but is free of aromatic groups.
• "3 to 8-membered non-aryl heterocycloalkyl” means a non-aryl heterocycloalkyl having 3 to 8 ring-constituting atoms.
• non-aryl heterocycloalkyl examples include an oxylanyl group, an oxetanyl group, a pyranyl group, a pyrrolidinyl group, an imidazolidinyl group, a piperidinyl group, a morpholinyl group, a thiomorpholinyl group, a hexamethyleneiminyl group, a thiazolidinyl group and a tetrahydrofuranyl group.
• Examples thereof include a tetrahydropyridinyl group, a tetrahydropyranyl group, a 1,3-dioxolanyl group, a 1,3-dioxanyl group, a 1,4-dioxanyl group, etc., but the present disclosure is not limited to such examples. Absent.
• the group also includes a heterocyclic group having a crosslinked structure.
• aryl group refers to a group formed by the detachment of one hydrogen atom bonded to the ring of an aromatic hydrocarbon.
• a phenyl group from the benzene C 6 H 5 -
• tolyl from toluene
• xylyl from xylene
• naphthalene naphthyl group C 10 H 8 -
• C 6-14 aryl group means an aromatic hydrocarbon group having a carbon number of 6 to 14.
• C 6 ⁇ 14 aryl group for example, phenyl, 1-naphthyl, 2-naphthyl group, azulenyl group, acenaphthenyl group, acenaphthyl group, an anthryl group, fluorenyl group, phenalenyl group, phenanthryl group and the like Can be mentioned.
• C 6 ⁇ 18 aryl group for example, C 6 ⁇ 14 aryl group, a benzo [a] anthryl group, benzo [a] fluorenyl group, benzo [c] phenanthryl group, a chrysenyl group, fluoranthenyl Examples thereof include a group, a pyrenyl group, a tetrasenyl group, a triphenylenyl group and the like.
• the arylthio group refers to an aryl-S-group.
• a phenyl-S-group (phenylthio group) and the like can be mentioned, but the present disclosure is not limited to such an example.
• heteroaryl group means a monocyclic or polycyclic heteroatom-containing aromatic group, which is the same or heterologous hetero selected from nitrogen, sulfur and oxygen atoms. Contains one or more atoms (eg 1 to 4).
• heteroaryl group means a heteroaryl group having 5 to 18 ring-constituting atoms.
• Halo heteroaryl group refers to one or more hydrogens on a ring-constituting atom substituted with halogen.
• heteroaryl group examples include, for example, a pyrrolyl group, a thienyl group, a benzothienyl group, a benzofuranyl group, a benzoxazolyl group, a benzothiazolyl group, a frill group, an oxazolyl group, a thiazolyl group, an isooxazolyl group and an isothiazolyl group.
• substituted refers to the replacement of one or more hydrogen radicals in a given structure by radicals of a particular substituent. It is recognized that the phrase “may be replaced” is used interchangeably with the phrase “non-replacement or replacement”.
• C 1 ⁇ 10 alkyl optionally substituted C 6 ⁇ also be 18 aryl group group
• unsubstituted C 6 ⁇ 18 aryl group or a C 1 ⁇ 10 C 6 ⁇ substituted with an alkyl group It is synonymous with " 18 aryl group”.
• the number of substituents in a group defined by using “substituent” or “may be substituted” is not particularly limited as long as it can be substituted, and may be one or more. is there. Unless otherwise indicated, the description of each group also applies when the group is part of another group or a substituent.
• the number of carbon atoms in the definition of “substituent” may be expressed as, for example, “C 1-6 ". Specifically, the notation "C 1-6 alkyl” is synonymous with an alkyl group having 1 to 6 carbon atoms.
• a substituent that does not specifically specify the term "substituted” or “may be substituted” means a "unsubstituted” substituent.
• the "polymer” means a compound formed by polymerizing a plurality of monomers.
• the monomer is the “starting material (material)” and the polymer is the product (final product).
• a "homopolymer” is a compound formed by polymerizing only one type of monomer
• a “copolymer” is a compound formed by polymerizing two or more types of monomers. Is.
• the copolymer of monomer A means a copolymer in which one of the contained monomers is monomer A.
• (meth) acrylate means acrylate or methacrylate, and acrylate and methacrylate may be used alone or in combination.
• (Meta) acryloyloxy means acryloyloxy or methacryloyloxy, and acryloyloxy and methacryloyloxy may be used alone or in combination.
• (Meta) acrylic acid means acrylic acid or methacrylic acid, and acrylic acid and methacrylic acid may be used alone or in combination.
• (meth) acrylic polymer and “(meth) acrylic polymer” refer to homopolymers or copolymers such as (meth) acrylic acid or (meth) acrylate or salts or derivatives thereof.
• the "monomer” means a compound obtained by polymerizing two or more of them to form a polymer.
• the monomers of the present disclosure include (meth) acrylic monomers, ethylene-based monomers, styrene-based monomers, butadiene-based monomers, urethane-based monomers, amide-based monomers, ester-based monomers, ether-based monomers, imide-based monomers, and amide-.
• firing refers to a process of molding a raw material powder, heating it, shrinking and densifying it, and obtaining a sintered body having a certain shape and strength.
• sintering refers to a phenomenon in which raw material powder is baked and hardened at a high temperature, and although gaps are observed between the particles of the raw material powder, sintering is performed in a high temperature environment (temperature lower than the melting point). When this happens, the contact area between the particles increases, the gaps decrease, and the particles harden. The remaining gap is called a "void” or "vacancy”.
• the "sintering accelerator” refers to a substance that lowers the temperature required to achieve sintering by interacting with a metallic component as compared with before its addition.
• the "kit” usually refers to a unit in which parts to be provided (for example, coating component, conductive component, solvent, instruction manual, etc.) are provided by dividing into two or more sections.
• the form of this kit is preferred when the purpose is to provide a composition that should not be mixed and provided for stability and the like, but is preferably mixed and used immediately before use.
• Such a kit preferably describes how to use the provided parts (eg, conductive components, coating components) or how to treat the reagents or waste liquid after use. Or it is advantageous to have instructions.
• the kit may usually include instructions and the like that describe how to use the solvent and the like.
• the conductive material provided in the present disclosure includes any conductive component available in the art.
• the conductive material of the present disclosure is characterized in that the conductivity is improved by containing a composition (also referred to as a conductivity improver) for improving the conductivity provided in the present disclosure.
• the conductive material of the present disclosure may typically contain other substrates of conductive components.
• composition (conductivity improver) for improving the conductivity of the conductive polymer provided in the present disclosure contains an organic phosphorus compound.
• the conductive component that can be targeted by the conductivity improver of the present disclosure may be any substance as long as it is a substance that promotes adsorption and diffusion, and a typical component includes any metal-based component.
• a typical component includes any metal-based component.
• the conductive component that can be targeted by the conductivity improver of the present disclosure is preferably a metal component.
• a metal component I do not want to be bound by the theory, but in the case of metal components, if there are molecules in the system that interact with the metal components, the molecules will be adsorbed on the metal surface and the amount of metal that can interact with the adsorbed part will be. It is also considered that the dissociation of the fine particles increases the amount of metal fine particles present in the system, and the number of contacts increases, so that the conductivity is improved.
• silver, copper, gold, aluminum, zinc, nickel, tin, iron and the like are targeted, and even more preferably silver is targeted.
• the polymer matrix of the present disclosure can be prepared by heating a monomer and / or by irradiating the monomer with ultraviolet rays of a specific illuminance to polymerize the monomer. .. Such ultraviolet irradiation can be arbitrarily set and carried out by those skilled in the art.
• a drying operation for removing the solvent which is a complicated operation, is not required, and the workability is excellent.
• ultraviolet rays refer to electromagnetic waves having a shorter wavelength than visible light and a longer wavelength than X-rays.
• the short wavelength end of visible light at the upper limit is 400 nm, and ultraviolet light can be defined as an electromagnetic wave having a wavelength lower than this.
• the lower limit of the wavelength of ultraviolet rays is about 10 nm, and it is understood that electromagnetic waves having a wavelength longer than this fall into the category of ultraviolet rays.
• the wavelength of the ultraviolet rays used in the present disclosure may be any wavelength, and an appropriate wavelength can be selected according to the intended purpose.
• any wavelength may be used as long as it can exert an initial effect on the monomer.
• it is of a wavelength that can be illuminated by the light source used in the examples or test examples.
• a light source of about 150 nm to 400 nm is used, preferably 300 nm to 400 nm.
• the preferred illuminance of ultraviolet light used in this disclosure depends on the starting material.
• the ultraviolet irradiation device is not particularly limited, and for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a black light lamp, a UV electrodeless lamp, a short arc lamp, an LED, etc. Can be mentioned.
• a polymerization initiator When polymerizing the monomer, it is preferable to use a polymerization initiator.
• the polymerization initiator include a thermal polymerization initiator, a photopolymerization initiator, a redox polymerization initiator, an ATRP (atomic transfer radical polymerization) initiator, an ICAR ATRP initiator, an ARGET ATRP initiator, and a RAFT (reversible addition-cleavage).
• ATRP atomic transfer radical polymerization
• ICAR ATRP initiator atomic transfer radical polymerization
• ARGET ATRP initiator an ARGET ATRP initiator
• RAFT reversible addition-cleavage
• Examples thereof include a chain transfer polymerization) agent, an NMP (nitroxide-mediated polymerization) agent, and a polymer polymerization initiator.
• These polymerization initiators may be used alone or in combination of two or more.
• a photopolymerization initiator is preferable from the viewpoint of not leaving a
• photopolymerization initiator examples include 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,1'.
• the amount of the photopolymerization initiator is usually preferably about 0.01 part by weight to about 20 parts by weight per 100 parts by weight of all the monomers.
• thermal polymerization initiator examples include azobisisobutyronitrile (AIBN), 2,2'-azobis (methyl isobutyrate), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2.
• Azo-based polymerization initiators such as'-azobis (2-methylbutyronitrile) and 1,1'-azobis (cyclohexane-1-carbonitrile), peroxides such as benzoyl peroxide, potassium persulfate, and ammonium persulfate. Examples thereof include a polymerization initiator, but the present disclosure is not limited to such examples. These polymerization initiators may be used alone or in combination of two or more.
• the amount of the thermal polymerization initiator is usually preferably about 0.01 part by weight to about 20 parts by weight per 100 parts by weight of all the monomers.
• the resulting composite material may contain air bubbles. Since such bubbles can be the starting point of fracture, it is predicted that the impact absorption capacity can be improved while the properties such as the extensibility of the composite material may be deteriorated.
• the bubbles contained in the composite material are not limited to those derived from the polymerization initiator, and the resin or the like contains bubbles, such as those obtained by adding a foaming agent and those obtained by removing the solvent. It may be a bubble obtained by a known method capable of this.
• redox polymerization initiators such as hydrogen peroxide and iron (II) salt, persulfate and sodium hydrogen sulfite, and ATRP using alkyl halides under a metal catalyst.
• RAFT reversible addition-cleavage chain transfer polymerization
• NMP nitrogen-mediated polymerization
• Polydimethylsiloxane unit-containing polymer azo polymerization initiator polyethylene glycol unit-containing polymer azo polymerization initiator, and other polymer polymerization initiators, but the present disclosure is not limited to these examples. .. These polymerization initiators may be used alone or in combination of two or more.
• a chain transfer agent When polymerizing the monomer, a chain transfer agent may be used to adjust the molecular weight. Chain transfer agents can usually be used by mixing with monomers. Examples of the chain transfer agent include 2- (dodecylthiocarbonothio oil thio) -2-methylpropionic acid, 2- (dodecylthiocarbonoti oil thio) propionate, and methyl 2- (dodecylthio carbonothio oil thio)-.
• the atmosphere for polymerizing the monomer is not particularly limited and may be the atmosphere or an inert gas such as nitrogen gas or argon gas.
• the temperature at which the monomer is polymerized is not particularly limited, and is usually preferably about 5 to 100 ° C.
• the time required to polymerize the monomer varies depending on the polymerization conditions and cannot be unconditionally determined. Therefore, it is arbitrary, but it is usually about 1 to 20 hours.
• the polymerization reaction can be arbitrarily terminated when the amount of the remaining monomer is 20% by mass or less.
• the amount of the remaining monomer can be measured by using, for example, gel permeation chromatography (GPC).
• a polymer matrix can be obtained by bulk polymerization of the monomers as described above.
• the monomer is polymerized in the absence of a cross-linking agent. In another embodiment, the monomer is polymerized in the presence of a cross-linking agent.
• the polymer matrix is thermally polymerized or photopolymerized. In another embodiment, the polymer matrix is thermally polymerized. In another embodiment, the polymer matrix is photopolymerized.
• Examples of the method for polymerizing the monomer include a massive polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and the like, but the present disclosure is not limited to these examples.
• a massive polymerization method and a solution polymerization method are preferable.
• the polymerization of the monomer can be carried out by a method such as a radical polymerization method, a living radical polymerization method, an anion polymerization method, a cationic polymerization method, an addition polymerization method, a polycondensation method, or a catalytic polymerization method.
• the monomer when the monomer is polymerized by a solution polymerization method, for example, the monomer can be polymerized by dissolving the monomer in a solvent and adding a polymerization initiator to the solution while stirring the obtained solution.
• the monomer can be polymerized by dissolving the initiator in a solvent and adding the monomer to the solution while stirring the obtained solution.
• the solvent is preferably an organic solvent that is compatible with the monomer.
• the homopolymers or copolymers contained in the conductive materials of the present disclosure use peroxide-based initiators (for example, benzoyl peroxide and azobisisobutyronitrile, and their analogs) as polymerization initiators. May be polymerized by.
• peroxide-based initiators for example, benzoyl peroxide and azobisisobutyronitrile, and their analogs
• the amount of the polymerization initiator is usually preferably about 0.01 part by weight to about 20 parts by weight per 100 parts by weight of all the monomers.
• electron beam polymerization is performed by irradiating the monomer with an electron beam.
• the monomer can be polymerized by irradiation with only an electron beam.
• the electron beam is irradiated in the presence of a photopolymerization initiator in one embodiment and in the absence of a photopolymerization initiator in another embodiment. Both embodiments are within the scope of the present disclosure.
• the polymerization reaction temperature and atmosphere when polymerizing the monomer are not particularly limited. Generally, the polymerization reaction temperature is about 50 ° C. to about 120 ° C.
• the atmosphere during the polymerization reaction is preferably an inert gas atmosphere such as nitrogen gas.
• the polymerization reaction time of the monomer varies depending on the polymerization reaction temperature and the like and cannot be unconditionally determined, but is usually about 3 to 20 hours.
• the polymer (or polymer matrix) contained in the conductive material of the present disclosure is required by mixing two or more specific monomers under appropriate polymerization conditions. It can be produced by polymerizing with an appropriate additive such as a polymerization initiator. Then, the conductive material of the present disclosure can be produced by mixing the conductive component and any other component with this polymer matrix and heating the polymer matrix.
• the polymer will be described in detail below with details such as individual components and specific production conditions.
• the present disclosure relates to a method of producing a homopolymer containing one monomer component or a copolymer containing two to three monomer components as a polymer matrix.
• the monomer component of the polymer matrix is of formula (1).
• R 1 is a hydrogen atom or a methyl group, and is a compound represented by.
• R 2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted non-aryl heterocycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. ..
• the polymerization of the monomer is carried out according to a polymerization method selected from the group consisting of a massive polymerization method, a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method.
• a polymerization method selected from the group consisting of a massive polymerization method, a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method.
• the monomers of the present disclosure can be polymerized by chain polymerization, step-growth polymerization, or living polymerization.
• the monomer component used in the present disclosure may be commercially available from a manufacturer exemplified in Examples or Test Examples, and is prepared according to a method well known to those skilled in the art. You may.
• the polymer matrix of the present disclosure is one step by exposure-polymerizing a monomer (including one or more kinds of monomers) in the presence of a polymerization initiator. Obtained at.
• the polymer matrix of the present disclosure can be produced by irradiating one type of (meth) acrylic monomer with ultraviolet rays in the presence of a polymerization initiator.
• a polymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
• This step is usually carried out at room temperature for about 2 hours, but is not limited to this, and may take 0.5 to 3 hours, 0.5 hours to 24 hours or more.
• the polymer matrix of the present disclosure obtained by polymerizing a monomer is dissolved in a solvent to produce a resin solution.
• a solvent examples include heptane, octane, undecane, limonene, 3-methoxy-3-methyl-1-butanol, octanol, and 2-ethyl-1-hexanol.
• the conductive material is prepared by mixing the resin solution obtained in (3-3) with a conductive component and, if necessary, a dispersant, and the obtained mixture is used. Obtained by heating.
• a person skilled in the art can produce a conductive material by using any method known in the art as described in the present specification and using other methods.
• the conductive material of the present disclosure is obtained by mixing one or more specific monomers and polymerizing them under appropriate polymerization conditions using appropriate additives such as a polymerization initiator as necessary. , Can be manufactured. The individual components and specific manufacturing conditions will be described in detail below.
• the essential conductive component in the present disclosure is a metal-based component (including a conductive whisker such as zinc oxide and potassium titanate, and a conductive metal oxide such as titanium oxide), preferably a metal component, and more.
• metal particles such as copper, gold, nickel, tin, aluminum, zinc, iron and silver.
• natural graphite such as scaly graphite, graphite such as artificial graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, etc. are used together with the metallic component.
• Carbon-based materials such as carbon black, graphite, carbon nanotubes, and fullerene; conductive fibers such as carbon fibers and metal fibers; carbon fluoride; organic conductive materials such as polyphenylene derivatives may be used.
• each of the essential conductive components may be used alone, or two or more of these conductive components may be used in combination, including at least one essential conductive component.
• the solid content of the conductive component in the total solid content of the polymer matrix and the conductive component cannot be unconditionally determined because it differs depending on the type of the conductive component and the like, but it is usually excellent in workability and moldability, and also. From the viewpoint of obtaining a conductive film having excellent flexibility and extensibility, it is preferably 1% by mass or more, and from the viewpoint of obtaining a conductive film having excellent workability and moldability and excellent flexibility and extensibility. It is preferably 100% by mass or less.
• Examples of carbon nanotubes include single-wall carbon nanotubes having a hollow cylindrical structure in which one sheet of graphite (graphene sheet) is rolled into a cylinder, and multi-walls having a structure in which a plurality of single-wall carbon nanotubes having different diameters are concentrically laminated.
• Examples thereof include carbon nanotubes, single-wall carbon nanotubes manufactured by the super-growth method, carbon nanocones having a conical and closed end of the single-wall carbon nanotubes, and carbon nanotubes containing fullerenes inside. Is not limited to such examples.
• Each of these carbon nanotubes may be used alone, or two or more types may be used in combination.
• multi-wall carbon nanotubes are preferable.
• the length of the carbon nanotubes is preferably 0.1 to 1000 ⁇ m, more preferably 1 to 500 ⁇ m, and further, from the viewpoint of obtaining a conductive film having excellent workability and moldability and excellent flexibility and extensibility. It is preferably 1 to 90 ⁇ m.
• the diameter of the carbon nanotubes is preferably 10 to 50 nm, more preferably 10 to 20 nm, from the viewpoint of obtaining a conductive film having excellent workability and moldability, as well as excellent flexibility and extensibility.
• the solid content of the carbon nanotubes in the total solid content of the polymer matrix and the carbon nanotubes is preferably 1% by mass from the viewpoint of obtaining a conductive film having excellent workability and moldability as well as excellent flexibility and extensibility.
• the above is more preferably 1.5% by mass or more, still more preferably 2% by mass or more, and is preferably 25 from the viewpoint of obtaining a conductive film having excellent workability and moldability and excellent flexibility and extensibility. It is mass% or less, more preferably 20 mass% or less, further preferably 15 mass% or less, and even more preferably 3.5 to 10 mass%.
• the conductive polymer of the present disclosure is used in, for example, sensors, wirings, electrodes, substrates, power generating elements, speakers, microphones, noise cancellers, transducers, artificial muscles, small pumps, medical instruments and the like used in actuators, industrial robots and the like. It can be suitably used as a conductive film that can be suitably used and as a raw material for the conductive film.
• the present disclosure relates to conductivity improving applications.
• the present disclosure provides a composition for improving the conductivity of a conductive polymer containing a metallic component, which contains an organic phosphorus compound.
• the organophosphorus compound comprises trivalent phosphorus.
• the organophosphorus compound is phosphine substituted with alkyl, cycloalkyl or aryl.
• the organophosphorus compounds are tributylphosphine, trioctylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, cyclohexyldiphenylphosphine, 1,2-bis (diphenylphosphino) ethane, and tricyclohexyl.
• tributylphosphine trioctylphosphine
• triphenylphosphine tri (o-tolyl) phosphine
• cyclohexyldiphenylphosphine 1,2-bis (diphenylphosphino) ethane
• tricyclohexyl 1,2-bis (diphenylphosphino) ethane
• the organophosphorus compound is triphenylphosphine.
• the metal-based component is a metal, a metal oxide, a metal carbide, a metal sulfide, or a combination thereof.
• the metal comprises silver, copper, gold, aluminum, zinc, tin, nickel, and / or iron.
• the metal is silver.
• the metal oxide is one or two oxides selected from the group consisting of alumina, tin oxide, indium oxide, zinc oxide, indium-tin oxide, and antimony-tin oxide. The above combination.
• the metal carbide is one or more combinations of carbides selected from the group consisting of tungsten carbide, titanium carbide, molybdenum carbide, tantalum carbide, niobium carbide, vanadium carbide, and zirconium carbide. is there.
• the metal-based component is a particle having a particle diameter of 1 ⁇ m to 100 ⁇ m.
• the metallic component is preferably a particle having a particle diameter of 90 ⁇ m or less, 80 ⁇ m or less, 70 ⁇ m or less, 60 ⁇ m or less, 50 ⁇ m or less, 40 ⁇ m or less, 30 ⁇ m or less, 20 ⁇ m or less, 10 ⁇ m or less, 5 ⁇ m or less, and 0.
• the metal-based component is more preferably particles having a particle size of 1 ⁇ m to 50 ⁇ m, further preferably 1 ⁇ m to 10 ⁇ m, and even more preferably 1 ⁇ m to 10 ⁇ m.
• the shape of the particles is not particularly limited, and examples thereof include spherical, scaly, and needle-shaped shapes.
• the polymer matrix in the conductive polymer is a (meth) acrylic polymer, a urethane polymer, an olefin polymer, or an epoxy polymer.
• the polymer matrix in the conductive polymer is a (meth) acrylic polymer, a urethane polymer, an olefin polymer, an epoxy polymer, or a styrene-butadiene polymer.
• the polymer matrix in the conductive polymer is a (meth) acrylic polymer.
• the polymer matrix in the conductive polymer is a homopolymer containing one monomer component or a copolymer containing two to three monomer components.
• the polymer matrix in the conductive polymer is a homopolymer.
• the monomer component of the polymer matrix is of formula (1).
• R 1 is a hydrogen atom or a methyl group
• R 2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted non-substituted compound.
• R 1 is a hydrogen atom. In another embodiment, R 1 is a methyl group.
• R 2 is a hydrogen atom, or a substituted or unsubstituted alkyl group.
• R 2 is a hydrogen atom, or a substituted or unsubstituted C 1-6 alkyl group.
• R 2 is ethyl
• the present disclosure provides sintering accelerators for metallic components, including organophosphorus compounds.
• the present disclosure provides sintering accelerators for metallic components, including triarylphosphine.
• sintering accelerator any embodiment described in the present specification or a combination thereof can be utilized, and any of the embodiments described in the section (Use for improving conductivity) in the present specification.
• One or a combination of a plurality of embodiments of the above can be applied.
• metallic components eg, silver particles
• organic molecules eg, triphenylphosphine
• the sintering accelerator of the present disclosure may be used for the above-mentioned firing, such as when manufacturing a molded product by powder metallurgy or manufacturing a sintered alloy.
• the present disclosure provides a conductive material comprising the polymer matrix of the present disclosure, a metal, and an organophosphorus compound.
• the heating temperature is lower.
• the mixture of silver microparticles and acrylic copolymer required heat treatment at 180 ° C., but the resin composition and silver particles were changed by adding a triphenylphosphine solution to the mixture of polymer matrix and metal. It is possible to perform heat treatment at a lower temperature than the conventional one without doing so.
• any embodiment described in the present specification or a combination thereof can be utilized, and any embodiment described in the section (use for improving conductivity) in the present specification. Can be applied as one or a combination of two or more.
• the organophosphorus compound comprises trivalent phosphorus.
• the organophosphorus compound is phosphine substituted with alkyl, cycloalkyl or aryl.
• the organophosphorus compounds are tributylphosphine, trioctylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, cyclohexyldiphenylphosphine, 1,2-bis (diphenylphosphino) ethane, and tricyclohexyl.
• phosphine or a combination of two or more types selected from the group consisting of phosphine.
• the organophosphorus compound is triphenylphosphine.
• the metal comprises silver, copper, gold, aluminum, zinc, tin, nickel, and / or iron.
• the metal is silver. I don't want to be bound by theory, because silver has excellent conductivity and resistance.
• the metal is a particle having a particle size of 1 ⁇ m to 100 ⁇ m.
• the polymer matrix is an acrylic polymer, a urethane polymer, an olefin polymer, or an epoxy polymer.
• the polymer matrix is an acrylic polymer, a urethane polymer, an olefin polymer, an epoxy polymer, or a styrene-butadiene polymer.
• the polymer matrix is a (meth) acrylic polymer or a styrene-butadiene polymer. In one embodiment, the polymer matrix is a (meth) acrylic polymer. In one embodiment, the polymer matrix is a styrene-butadiene polymer.
• the polymer matrix is a homopolymer containing one monomer component or a copolymer containing two to three monomer components.
• the polymer matrix is a homopolymer.
• the monomer component of the polymer matrix is of formula (1).
• R 1 is a hydrogen atom or a methyl group
• R 2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted non-substituted compound.
• R 1 is a hydrogen atom. In another embodiment, R 1 is a methyl group.
• R 2 is a hydrogen atom, or a substituted or unsubstituted alkyl group.
• R 2 is a hydrogen atom, or a substituted or unsubstituted C 1-6 alkyl group.
• R 2 is ethyl
• the conductive material further comprises a dispersant.
• the dispersant is 2- (2-butoxyethoxy) ethanol.
• the present disclosure provides a method for producing the conductive materials and sintering accelerators of the present disclosure.
• the present disclosure provides a method for producing a conductive material, which comprises a step of heating a mixture containing a polymer matrix, a metal and an organophosphorus compound to produce a conductive material.
• the method comprises heating a mixture of the polymer matrix with the metal and an organophosphorus compound to produce a conductive polymer containing the metal.
• any embodiment described in the present specification or a combination thereof can be utilized, and any embodiment described in the section (Use for improving conductivity) in the present specification. Can be applied as one or a combination of two or more.
• the heating temperature is 80 ° C. to 150 ° C., preferably 100 ° C. to 140 ° C.
• the heating time is 10 to 50 minutes.
• the method comprises adding a dispersant to the mixture prior to heating.
• Test examples are described below. The handling of organisms used in the following test examples complied with the standards set by the regulatory agency, if necessary. Specifically, as the reagents, the products described in Examples or Test Examples were used, but equivalent products of other manufacturers (Sigma-Aldrich, etc.) can be substituted.
• An acrylic resin solution was obtained by dissolving the obtained polymer (10.00 g) in toluene (90.00 g).
• Triphenylphosphine (5.00 g) was dissolved in tetrahydrofuran (5.00 g) to obtain a phosphine solution.
• the obtained conductive material precursor was applied as a release film to a release polyethylene terephthalate film (manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name Separator SP-PET PET-01-Bu) to form a coating film.
• a release polyethylene terephthalate film manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name Separator SP-PET PET-01-Bu
• the coating film was heated in an oven at 120 ° C. for 30 minutes to obtain a conductive film having a thickness of about 30 ⁇ m.
• the obtained conductive film was cut into a length of 0.5 cm and a width of 2.00 cm, and measured by a 4-terminal method using Loresta GP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.).
• the conductive film obtained above was cut out to a length of 0.5 cm and a width of 2.00 cm, and before stretching with a digital multimeter [trade name PC773 manufactured by Sanwa Denki Keiki Co., Ltd.] in which the distance between electrodes was fixed at 1.00 cm.
• the resistance value ( ⁇ A) was measured.
• Test Example 2 A conductive film was prepared in the same manner as in Test Example 1 except that the amount of the triphenylphosphine solution added was changed as shown in Table 1, and the change in resistance value was measured in the same manner as in Test Example 1.
• ⁇ Test Example 4> A cyclohexyldiphenylphosphine solution was prepared in the same manner as in Test Example 1 except that cyclohexyldiphenylphosphine was used instead of triphenylphosphine.
• a conductive film was prepared in the same manner as in Test Example 1 except that this cyclohexyldiphenylphosphine solution was used instead of the triphenylphosphine solution, and the change in resistance value was measured in the same manner as in Test Example 1.
• Test Example 5 A conductive film was prepared in the same manner as in Test Example 1 except that the amount of the silver filler added was changed as shown in Table 2, and the change in resistance value was measured in the same manner as in Test Example 1.
• Test Example 8> A conductive film was prepared in the same manner as in Test Example 1 except that the temperature of the heat treatment was changed to 150 ° C., and the change in resistance value was measured in the same manner as in Test Example 1.
• a resin solution was obtained by dissolving polycycloolefin (40.00 g, manufactured by Zeon Corporation, trade name: Zeonoa) in toluene (60.00 g). Using this resin solution, a conductive film having the composition shown in Table 2 was prepared in the same manner as in each of the above test examples, and the change in resistance value was measured in the same manner as in Test Example 1.
• ⁇ Test Example 12> A conductive film was prepared in the same manner as in Test Example 11 except that the amount of the triphenylphosphine solution added was changed as shown in Table 2, and the change in resistance value was measured in the same manner as in Test Example 1.
• the frequency is high in the range of 5 ⁇ m to 10 ⁇ m and ⁇ 1 ⁇ m in the added system, and about 3 to 5 ⁇ m in the non-added system. Frequent frequency was observed in the range (data not shown).
• the conductivity improver of the present disclosure it is possible to provide an efficient conductive material, and it can be used in industries that require a conductive material.
• the sintering accelerator of the present disclosure can be used to lower the sintering temperature of metal-based components, and can be used in industries that require sintering of metal-based components.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Physics & Mathematics (AREA)
• Dispersion Chemistry (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Conductive Materials (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=74569290

Family Applications (1)

Country Status (3)

Citations (2)

Family Cites Families (5)

• 2020
  • 2020-08-07 WO PCT/JP2020/030366 patent/WO2021029359A1/ja not_active Ceased
  • 2020-08-07 TW TW109126832A patent/TW202112792A/zh unknown
  • 2020-08-07 JP JP2021539272A patent/JP7719715B2/ja active Active

Patent Citations (2)

Also Published As

Similar Documents

Legal Events