WO2021029362A1 - Novel firing temperature reducing agent for conductive material - Google Patents

Novel firing temperature reducing agent for conductive material Download PDF

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WO2021029362A1
WO2021029362A1 PCT/JP2020/030369 JP2020030369W WO2021029362A1 WO 2021029362 A1 WO2021029362 A1 WO 2021029362A1 JP 2020030369 W JP2020030369 W JP 2020030369W WO 2021029362 A1 WO2021029362 A1 WO 2021029362A1
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substituted
unsubstituted
hydrogen atom
meth
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慎一朗 岡本
亮平 池田
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大阪有機化学工業株式会社
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Publication of WO2021029362A1 publication Critical patent/WO2021029362A1/en

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D303/00Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02Compounds containing oxirane rings
    • C07D303/12Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/16Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D305/00Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/04Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D305/06Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10Esters
    • C08F20/26Esters containing oxygen in addition to the carboxy oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/26Esters containing oxygen in addition to the carboxy oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04Homopolymers or copolymers of esters
    • C08L33/14Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00Apparatus or processes specially adapted for manufacturing conductors or cables

Definitions

  • the present disclosure relates to a new conductive material firing temperature lowering agent, a new conductivity improving agent, and related technologies. More specifically, the present disclosure relates to a composition for lowering the firing temperature of the conductive material and improving the conductivity of the conductive material, which comprises the compound represented by the formula (4) described in the specification.
  • the present disclosure provides a conductive material containing a desired combination of conductive components and a base material.
  • the disclosure provides, for example:
  • a composition for lowering the firing temperature of a conductive material which comprises the compound represented by.
  • 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.
  • n is an integer of 0 or 1, Composition.
  • composition according to any one of the preceding items, wherein n 0 and the compound represented by the formula (4) has one or two or more vinyloxy groups.
  • the conductive material contains a homopolymer or copolymer of a compound represented by the formula (4) and a conductive component.
  • the conductive material comprises a homopolymer or copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing ring and a conductive component.
  • the copolymer is a copolymer of a compound represented by the formula (4) and a second (meth) acrylic monomer.
  • R 2 is an alkyl group or a cycloalkyl group which may be substituted with an oxygen-containing group, and the oxygen-containing group is a hydroxy, hydroxyalkyl, vinyloxyalkyl, alkoxy, oxylan ring or oxetane ring.
  • R 1 is a hydrogen atom or a methyl group.
  • R 2 is hydroxy, alkoxy, oxirane ring and an alkyl group substituted by a substituent from one selected from the group consisting of oxetane ring to substitutable number, The composition according to any one of the preceding paragraphs.
  • the alkyl (meth) acrylate substituted with the oxygen-containing group is the formula (1).
  • R 1 is a hydrogen atom or a methyl group and R 2 is alkoxy, oxirane ring and an alkyl group which is substituted with up substitutable number from 1 selected from the group consisting of oxetane ring, The composition according to any one of the preceding paragraphs.
  • the alkyl (meth) acrylate substituted with the oxygen-containing ring is the formula (1).
  • R 1 is a hydrogen atom or a methyl group and R 2 is an alkyl group substituted with one or more oxylan or oxetane rings, The composition according to any one of the preceding paragraphs.
  • R 1 is a hydrogen atom or a methyl group.
  • the second (meth) acrylic monomer has the formula (2).
  • R 3 is a hydrogen atom or a methyl group and R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkyl are alkoxy-substituted, The composition according to any one of the preceding paragraphs.
  • R 4 is an unsubstituted alkyl group having 2-10 carbon atoms, preceding composition according to any one of claims.
  • (Section A6c) R 4 is an unsubstituted alkyl group having 11 or more carbon atoms, the preceding composition according to any one of claims.
  • (Section A6d) R 4 is an unsubstituted alkyl group having 13 or more carbon atoms, the preceding composition according to any one of claims.
  • Section A6E R 4 is an unsubstituted alkyl group having 18 or more carbon atoms, the preceding composition according to any one of claims.
  • the compound represented by the formula (4) of (Item A7a) is 4-hydroxybutyl vinyl ether, 2-methoxyethyl acrylate, (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate.
  • the alkyl (meth) acrylate substituted with the oxygen-containing group is 2-methoxyethyl acrylate, (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate.
  • (Item A7c) Any one of the preceding items, wherein the alkyl (meth) acrylate substituted with the oxygen-containing ring is (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate.
  • the composition according to. (Item A7d) The composition according to any one of the preceding items, wherein the compound represented by the formula (4) is 4-hydroxybutyl vinyl ether.
  • (Item A8) The composition according to any one of the preceding items, wherein the second (meth) acrylic monomer is ethyl acrylate, stearyl acrylate, isostearyl acrylate or lauryl acrylate.
  • 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.
  • n is an integer of 0 or 1, Conductive material.
  • the compound represented by the formula (4) is a conductive material which is an alkyl (meth) acrylate substituted with an oxygen-containing group.
  • the compound represented by the formula (4) is a conductive material which is an alkyl (meth) acrylate substituted with an oxygen-containing ring.
  • a conductive material in which n 0 and R 2 is an alkyl group or a cycloalkyl group which may be substituted with an oxygen-containing group.
  • (Item A11a) Equation (4) A method for producing a copolymer of a compound represented by the above and a conductive material containing a conductive component. A step of obtaining a copolymer by polymerizing a compound represented by the formula (4) and a polymerizable monomer. Including the steps of mixing the copolymer and the conductive components to obtain a mixture, and heating the mixture to produce a conductive material.
  • 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.
  • n is an integer of 0 or 1
  • Method. (Item A11b) The method according to any one of the preceding items, wherein the compound represented by the above formula (4) is an alkyl (meth) acrylate substituted with an oxygen-containing group.
  • 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.
  • n is an integer of 0 or 1 and
  • the second (meth) acrylic monomer has the formula (2).
  • R 3 is a hydrogen atom or a methyl group and R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkyl are alkoxy-substituted, Copolymer.
  • the compound represented by the formula (4) is the formula (1).
  • An alkyl (meth) acrylate substituted with an oxygen-containing group represented by R 1 is a hydrogen atom or a methyl group and R 2 is an alkyl group substituted with one or more oxygen-containing groups, The copolymer according to any one of the preceding paragraphs.
  • the compound represented by the formula (4) is the formula (1).
  • An alkyl (meth) acrylate substituted with an oxygen-containing ring, represented by R 1 is a hydrogen atom or a methyl group and R 2 is an alkyl group substituted with one or more oxylan or oxetane rings, The copolymer according to any one of the preceding paragraphs.
  • (Section A13e) R 4 is an unsubstituted alkyl group having 2 to 10 carbon atoms, the copolymer according to any one of the preceding claim.
  • (Section A13f) R 4 is an unsubstituted alkyl group having 11 or more carbon atoms, the copolymer according to any one of the preceding claim.
  • R 4 is an unsubstituted alkyl group having 13 or more carbon atoms, the copolymer according to any one of the preceding claim.
  • (Section A13h) R 4 is an unsubstituted alkyl group having 18 or more carbon atoms, the copolymer according to any one of the preceding claim.
  • (Item A15a) A composition for use as a matrix in a conductive material containing a conductive component, which comprises a copolymer of a compound represented by the formula (4) according to any one of the preceding items.
  • (Item A15b) A composition for use as a matrix in a conductive material containing a conductive component, which comprises a copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing group according to any one of the preceding items.
  • (Item A15c) A composition for use as a matrix in a conductive material containing a conductive component, which comprises a copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing ring according to any one of the preceding items.
  • 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.
  • n is an integer of 0 or 1, blend.
  • the alkyl (meth) acrylate substituted with the oxygen-containing group has the formula (1).
  • R 1 is a hydrogen atom or a methyl group and
  • R 2 is an alkyl group substituted with one to a substitutable number of substituents selected from the group consisting of alkoxy, oxylan ring and oxetane ring.
  • the second (meth) acrylic monomer has the formula (2).
  • R 3 is a hydrogen atom or a methyl group and R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkyl are alkoxy-substituted, The mixture according to any one of the preceding paragraphs.
  • the alkyl (meth) acrylate substituted with the oxygen-containing ring has the formula (1).
  • R 1 is a hydrogen atom or a methyl group and R 2 is an alkyl group substituted with one or more oxylan or oxetane rings, The mixture according to any one of the preceding paragraphs.
  • R 4 is an unsubstituted alkyl group having 2 to 10 carbon atoms, the copolymer according to any one of the preceding claim.
  • (Section A17h) R 4 is an unsubstituted alkyl group having 11 or more carbon atoms, the preceding mixture according to any one of claims.
  • (Section A17i) R 4 is an unsubstituted alkyl group having 13 or more carbon atoms, the preceding mixture according to any one of claims.
  • (Section A17j) R 4 is an unsubstituted alkyl group having 18 or more carbon atoms, the preceding mixture according to any one of claims.
  • the disclosure also provides, for example:
  • a composition for lowering the firing temperature of a conductive material which comprises an alkyl (meth) acrylate substituted with an oxygen-containing ring.
  • the conductive material contains a copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing ring and a conductive component.
  • the copolymer is a copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing ring and a second (meth) acrylic monomer.
  • the alkyl (meth) acrylate substituted with the oxygen-containing ring is the formula (1).
  • R 1 is a hydrogen atom or a methyl group and R 2 is an alkyl group substituted with one or more oxylan or oxetane rings,
  • the composition according to any one of the above items. (Item 6)
  • the second (meth) acrylic monomer has the formula (2).
  • R 3 is a hydrogen atom or a methyl group and R 4 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,
  • R 4 is not an alkyl group substituted with an oxygen-containing ring, The composition according to any one of the above items.
  • (Section 6a) R 4 is an unsubstituted alkyl group having 11 or more carbon atoms, A composition according to any one of the above items.
  • R 4 is an unsubstituted alkyl group having 13 or more carbon atoms, A composition according to any one of the above items.
  • (Section 6c) R 4 is an unsubstituted alkyl group having 18 or more carbon atoms, A composition according to any one of the above items.
  • (Item 7) In any one of the above items, the alkyl (meth) acrylate substituted with the oxygen-containing ring is (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate. The composition described.
  • (Item 8) The composition according to any one of the above items, wherein the second (meth) acrylic monomer is isostearyl acrylate or lauryl acrylate.
  • (Item 9) A conductive material containing a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring and a conductive component.
  • (Item 10) The conductive material according to any one of the above items, which comprises one or more of the features described in the above item.
  • (Item 11) A method for producing a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring and a conductive material containing a conductive component.
  • a step of obtaining a copolymer by polymerizing an alkyl (meth) acrylate substituted with the oxygen-containing ring and a polymerizable monomer comprising the steps of mixing the copolymer and a conductive component to obtain a mixture and heating the mixture to produce a conductive material.
  • the alkyl (meth) acrylate substituted with the oxygen-containing ring has the formula (1).
  • R 1 is a hydrogen atom or a methyl group and R 2 is an alkyl group substituted with one or more oxylan or oxetane rings.
  • the second (meth) acrylic monomer has the formula (2).
  • R 3 is a hydrogen atom or a methyl group and R 4 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,
  • R 4 is not an alkyl group substituted with an oxygen-containing ring, Copolymer.
  • R 4 is an unsubstituted alkyl group having 11 or more carbon atoms, the copolymer according to any one of the above items.
  • (Section 13b) R 4 is an unsubstituted alkyl group having 13 or more carbon atoms, the copolymer according to any one of the above items.
  • (Section 13c) R 4 is an unsubstituted alkyl group having 18 or more carbon atoms, the copolymer according to any one of the above items.
  • Item 14 The copolymer according to any one of the above items, which comprises one or more of the characteristics described in the above item.
  • (Item 15) A composition for use as a matrix in a conductive material containing a conductive component, which comprises a copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing ring according to any one of the above items.
  • (Item 16) The composition according to any one of the above items, which comprises one or more of the characteristics described in the above item.
  • (Item 17) A copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring and a second (meth) acrylic monomer, and a mixture of metals.
  • (Item 18) The mixture according to any one of the above items, wherein the metal contains silver, copper, gold, aluminum, zinc, nickel, tin, and / or iron.
  • the alkyl (meth) acrylate substituted with the oxygen-containing ring has the formula (1).
  • R 1 is a hydrogen atom or a methyl group and R 2 is an alkyl group substituted with one or more oxylan or oxetane rings.
  • the second (meth) acrylic monomer has the formula (2).
  • R 3 is a hydrogen atom or a methyl group and R 4 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,
  • R 4 is not an alkyl group substituted with an oxygen-containing ring, The mixture according to any one of the above items.
  • R 4 is an unsubstituted alkyl group having 11 or more carbon atoms, mixtures of any one of the above items.
  • R 4 is an unsubstituted alkyl group having 13 or more carbon atoms, mixtures of any one of the above items.
  • a conductive material firing temperature lowering agent and a conductivity improving agent 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.
  • the term "improving conductivity” means that when the component of the present disclosure is added to a conductive component or a conductive material, the conductivity is significantly increased as compared with the case where the component is not added.
  • the conductivity 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%.
  • 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 firing temperature” means the same or smaller volume when the components of the present disclosure are added to a conductive component or a conductive material and heated at a lower temperature than when not added. It means that the resistivity can be achieved.
  • the firing 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%, about It means to reduce by 80%, about 85%, about 90%, about 95%, and about 99%.
  • the conductive material is often heat-treated for the purpose of removing the solvent contained therein.
  • the temperature of the heat treatment is low, it is preferable because the conductive material itself and the material coated with the conductive material are less likely to be damaged.
  • the conductive component is a metal-based component described later, it is often necessary to perform a heat treatment to sinter the particles of the metal-based component in order to make the conductive material exhibit conductivity. Therefore, if the particles can be sintered with each other even if the firing temperature is lowered, it is preferable because the conductive material itself and the material coated with the conductive material are less likely to be damaged.
  • 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 is a polymer
  • the base material may be referred to as a polymer matrix.
  • the "conductive component” means any component that imparts conductivity.
  • the conductive component include, but are not limited to, any metal component, a metal oxide, a metal component such as a metal carbide, a conductive carbon component, a conductive organic compound, a conductive polymer, and the like. ..
  • 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.).
  • the "metal component” includes a metal or an alloy.
  • the "conductive carbon-based component” means a conductive material containing carbon.
  • Specific examples include natural graphite such as scaly graphite, graphite such as artificial graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black and other carbon black, graphene, and carbon nanotubes.
  • Carbon-based materials such as graphene; carbon fibers; carbon fluoride and the like can be mentioned, but are not limited thereto.
  • Metal carbides are not included in the conductive carbon-based components.
  • the "conductive carbon-based component” may also be referred to as a "carbon-based component".
  • 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”.
  • the (meth) acrylic monomer also has formula (2).
  • R 3 is a hydrogen atom or a methyl group
  • R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkoxy-substituted alkyl.
  • the (meth) acrylic monomer also has formula (2).
  • R 3 is a hydrogen atom or a methyl group
  • R 4 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
  • R 4 is not an alkyl group substituted with an oxygen-containing ring.
  • alkyl (meth) acrylate substituted with an oxygen-containing ring is the formula (1).
  • substituted number refers to the maximum number of hydrogens that can be substituted when hydrogen on a group is substituted with a substituent, provided that the resulting group is chemically stable. means.
  • 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.
  • Examples of the haloalkyl group having 1 to 8 carbon atoms include a C 1-6 haloalkyl group, an undecafluoro n-heptyl group, a perfluoro n-heptyl group, and a 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 hexamethyleneiminal 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 these examples. Absent.
  • the group also includes those having a crosslinked structure.
  • oxygen-containing group means a group having a carbon atom and an oxygen atom (for example, 1 to 5, 1 to 4, or 1 to 3) as constituent atoms, and the group is 1 It may contain one or more unsaturated bonds and may not contain carbon atoms, but it does not contain aromatic groups.
  • oxygen-containing group include a hydroxy group, an alkoxy group (for example, methoxy group, ethoxy group, etc.), an alkenyloxy group (for example, vinyloxy group, propenyloxy group, etc.), an oxylanyl group, an oxetanyl group, and a tetrahydrofuranyl.
  • alkenyloxyalkyl-cycloalkyl-alkyl eg 4- (vinyloxymethyl) cyclohexane-1-yl, etc.
  • oxygen-containing ring and “oxygen-containing cyclic group” mean a cyclic group having a carbon atom and 1 to 3 oxygen atoms as ring-constituting atoms, and the group may be one or more. May contain unsaturated bonds, but does not contain aromatic groups.
  • the “3 to 8-membered oxygen-containing ring” means an oxygen-containing ring having 3 to 8 ring-constituting atoms.
  • oxygen-containing ring examples include an oxylanyl group, a tetrahydrofuranyl group, an oxetanyl group, a 1,3-dioxolanyl group, a 1,3-dioxanyl group, a 1,4-dioxanyl group, and the like. It is not limited to.
  • the group also includes those 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.
  • alkyl group substituted with an oxygen-containing group refers to an alkyl group in which one hydrogen atom on the alkyl group is substituted with an oxygen-containing group, and (2) on the same carbon of the alkyl group.
  • the oxygen-containing group of the alkyl group substituted with the oxygen-containing group may be unsubstituted or substituted with a C1 to 6 alkyl group and / or a vinyloxy group.
  • the "cycloalkyl group substituted with an oxygen-containing group” is the same as the alkyl group in which one hydrogen atom on the cycloalkyl group is substituted with an oxygen-containing group, and (2) the cycloalkyl group.
  • the oxygen-containing group of the cycloalkyl group substituted with the oxygen-containing group may be unsubstituted or substituted with a C1 to 6 alkyl group and / or a vinyloxy group.
  • Examples of cycloalkyl groups substituted with oxygen-containing groups include 4- (vinyloxymethyl) cyclohexyl, 4- (hydroxymethyl) cyclohexyl and the like, but the present disclosure is not limited to such examples. Absent.
  • alkyl group substituted with an oxygen-containing ring refers to (1) an alkyl group in which one hydrogen atom on the alkyl group is substituted with an oxygen-containing ring, and (2) the same alkyl group.
  • the oxygen-containing ring of the alkyl group substituted with the oxygen-containing ring may be unsubstituted or substituted with a C 1 to 6 alkyl group.
  • alkyl groups substituted with an oxygen-containing ring examples include 2,3-epoxypropyl, (3-ethyloxetane-3-yl) methyl, tetrahydrofurfuryl, (2-ethyl-2-methyl-1,3-).
  • Examples thereof include dioxolane-4-yl) methyl, (5-ethyl-1,3-dioxane-5-yl) methyl, and the like, but the present disclosure is not limited to such examples.
  • 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 containing a monomer component” means a copolymer produced by polymerizing the monomer component.
  • 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, urethane-based monomers, amide-based monomers, ester-based monomers, ether-based monomers, imide-based monomers, amide-imide-based monomers, and carbonate-based monomers.
  • Examples include 4-hydroxybutyl vinyl ether (HBVE), 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEVGV), n-propyl vinyl ether (NPVE), isopropyl vinyl ether (IPVE), and n-butyl vinyl ether.
  • NBVE isobutyl vinyl ether
  • IBVE isobutyl vinyl ether
  • 2-EHVE 2-ethylhexyl vinyl ether
  • CHVE 1,4-cyclohexanedimethanol monovinyl ether
  • BDVE 1,4-butanediol divinyl ether
  • TEGDVE Triethylene glycol divinyl ether
  • DEGDVE diethylene glycol divinyl ether
  • CHDVE 1,4-cyclohexanedimethanol divinyl ether
  • 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 "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 firing temperature for obtaining the conductive material is lowered by containing the composition (also referred to as a firing temperature lowering agent) for lowering the firing temperature provided in the present disclosure. is there.
  • the conductive material of the present disclosure may typically contain other substrates of conductive components.
  • the composition (calcination temperature lowering agent) for lowering the firing temperature of the conductive material provided in the present disclosure is the formula (4). Includes compounds represented by.
  • 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-aryl heterocycloalkyl group.
  • R 2 is an alkyl or cycloalkyl group that may be substituted with an oxygen-containing group.
  • R 2 is an alkyl group substituted with an oxygen-containing group.
  • R 2 is an alkyl group substituted with an oxygen-containing ring.
  • the compound represented by the formula (4) is an alkyl (meth) acrylate substituted with an oxygen-containing group.
  • the compound represented by the formula (4) is an alkyl (meth) acrylate substituted with an oxygen-containing ring.
  • n 0 and the compound represented by the formula (4) has one or two or more vinyloxy groups.
  • the composition (calcination temperature lowering agent) comprises an alkyl (meth) acrylate substituted with an oxygen-containing group. In one embodiment, the composition (calcination temperature lowering agent) also comprises an alkyl (meth) acrylate substituted with an oxygen-containing ring. In one embodiment, the composition (calcination temperature lowering agent) comprises a compound having n of 0 and represented by the formula (4). In one embodiment, the composition (calcination temperature lowering agent) comprises a compound represented by the formula (4) in which n is 0 and R 1 is a hydrogen atom.
  • an example of an alkyl (meth) acrylate substituted with an oxygen-containing ring provided in the present disclosure is of formula (1). Regardless of the type of oxygen-containing ring contained, the form of the alkyl group (carbon number, branched / linear state, etc.), methacrylic, acrylic, etc., all of them lower the firing temperature.
  • the conductive material comprises a homopolymer or copolymer of a compound represented by the formula (4) and a conductive component.
  • the conductive material comprises a homopolymer or copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing group and a conductive component.
  • the conductive material comprises a homopolymer or copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing ring and a conductive component.
  • the copolymer is a copolymer of a compound represented by the formula (4) and a second (meth) acrylic monomer.
  • the copolymer is a copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing group and a second (meth) acrylic monomer.
  • the copolymer is a copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing ring and a second (meth) acrylic monomer.
  • R 2 is an alkyl or cycloalkyl group optionally substituted with an oxygen-containing group, wherein the oxygen-containing group is a hydroxy, hydroxyalkyl, vinyloxyalkyl, alkoxy, oxylan ring or oxetane.
  • the oxygen-containing group is an alkoxy, oxylan ring or oxetane ring.
  • the oxygen-containing ring is an oxylan ring or an oxetane ring.
  • the oxygen-containing group is hydroxy or alkoxy.
  • R 2 is an alkyl group, a cycloalkyl group, or an alkylcycloalkylalkyl group that may be substituted with vinyloxy or hydroxy, or-(CH 2 CH 2 O) y- R 7 .
  • R 7 is hydrogen or vinyl, and y is an integer of 1 or more.
  • R 1 is a hydrogen atom or a methyl group and R 2 is substituted with one to a substitutable substituent selected from the group consisting of hydroxy, alkoxy, oxylan and oxetane rings. Alkoxy group.
  • the alkyl (meth) acrylate substituted with the oxygen-containing group is the formula (1).
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is an alkyl group substituted with one to a substitutable number selected from the group consisting of an alkoxy, an oxylan ring and an oxetane ring. Is.
  • the alkyl (meth) acrylate substituted with the oxygen-containing ring is the formula (1).
  • R 1 is a hydrogen atom or a methyl group and R 2 is an alkyl group substituted with one or more oxylan or oxetane rings.
  • R 1 is a hydrogen atom.
  • the second (meth) acrylic monomer is of formula (2).
  • R 3 is a hydrogen atom or a methyl group and R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkoxy-substituted alkyl.
  • the compound represented by formula (4) is 4-hydroxybutyl vinyl ether, 2-methoxyethyl acrylate, (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate. is there.
  • the alkyl (meth) acrylate substituted with the oxygen-containing group is 2-methoxyethyl acrylate, (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate.
  • the alkyl (meth) acrylate substituted with the oxygen-containing ring is (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate.
  • the compound represented by the formula (4) is 4-hydroxybutyl vinyl ether.
  • the second (meth) acrylic monomer is ethyl acrylate, stearyl acrylate, isostearyl acrylate or lauryl acrylate.
  • the compound represented by formula (4) is (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate, said second (meth) acrylic monomer.
  • the compound represented by formula (4) is (3-ethyloxetane-3-yl) methyl acrylate and the second (meth) acrylic monomer is isostearyl acrylate.
  • the compound represented by the formula (4) is 2,3-epoxypropyl methacrylate, and the second (meth) acrylic monomer is an isostearyl acrylate.
  • the compound represented by the formula (4) is 4-hydroxybutyl vinyl ether or 2-methoxyethyl acrylate, and the second (meth) acrylic monomer is ethyl acrylate. In one preferred embodiment, the compound represented by the formula (4) is 2-methoxyethyl acrylate, and the second (meth) acrylic monomer is ethyl acrylate. In one preferred embodiment, the compound represented by formula (4) is 4-hydroxybutyl vinyl ether and the second (meth) acrylic monomer is ethyl acrylate.
  • the basic usage of the firing temperature lowering agent is as follows.
  • the conductive material that can be targeted by the firing temperature lowering agent of the present disclosure is a material containing an arbitrary conductive component and a polymer matrix, preferably any conductive component contains a metal-based component, and more preferably any conductive component. It contains a metal component.
  • 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 emitted by the light source used in the 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.
  • copolymers contained in the conductive materials of the present disclosure are polymerized by using peroxide-based initiators (eg, benzoyl peroxide and azobisisobutyronitrile, and their analogs) as polymerization initiators. You may.
  • peroxide-based initiators eg, 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 equation (4). It relates to a method for producing a copolymer of a compound represented by the above and a second (meth) acrylic monomer.
  • 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-aryl heterocycloalkyl group, a substituted or An unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, where n is an integer of 0 or 1.
  • the second (meth) acrylic monomer has the formula (2).
  • R 3 is a hydrogen atom or a methyl group
  • R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkoxy-substituted alkyl.
  • the disclosure relates to a method of making a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring and a second (meth) acrylic monomer.
  • the alkyl (meth) acrylate substituted with the oxygen-containing ring has the formula (1).
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is an alkyl group substituted with one or more oxylan or oxetane rings.
  • the second (meth) acrylic monomer has the formula (2).
  • R 3 is a hydrogen atom or a methyl group
  • R 4 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
  • R 4 is not an alkyl group substituted with an oxygen-containing ring.
  • 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.
  • alkyl fluorinated (meth) acrylate and (meth) acrylic monomer used in the present disclosure may be commercially available from a manufacturer exemplified in Examples. It may be prepared according to a method well known to those skilled in the art.
  • the polymer matrix of the present disclosure is obtained in one step by exposure-polymerizing a monomer (including a plurality of types of monomers) in the presence of a polymerization initiator. ..
  • the polymer matrix of the present disclosure is prepared by irradiating one (meth) acrylic monomer and an alkyl (meth) acrylate substituted with an oxygen-containing ring with ultraviolet light in the presence of a polymerization initiator. be able to.
  • Preferred examples of the 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, or 0.5 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, limonene and the like.
  • 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.
  • Examples of conductive components include natural graphite such as scaly graphite, graphite such as artificial graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black and other carbon black, graphene, carbon nanotubes, and fullerene.
  • Carbon-based materials such as; conductive fibers such as carbon fiber and metal fiber; carbon fluoride; powder of metal particles such as copper, gold, nickel, tin, aluminum, zinc, iron and silver; zinc oxide, potassium titanate, etc.
  • Examples thereof include conductive whiskers; conductive metal oxides such as titanium oxide; organic conductive materials such as polyphenylene derivatives, but the present disclosure is not limited to these examples.
  • Each of these conductive components may be used alone, or two or more types may be used in combination.
  • these conductive components carbon nanotubes, carbon black, graphene and metal particles are preferable, and carbon nanotubes and carbon are preferable from the viewpoint of obtaining a conductive film having excellent workability and moldability as well as excellent flexibility and extensibility. Black, graphene and silver particles are more preferred.
  • 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 material of the present disclosure is suitable for, for example, sensors, wirings, electrodes, substrates, power generation 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 used in the above and as a raw material of the conductive film.
  • the present disclosure relates to a firing temperature lowering application.
  • the present disclosure is a composition for lowering the calcination temperature for producing a conductive material (calcination temperature lowering agent) containing an alkyl (meth) acrylate substituted with an oxygen-containing ring.
  • a composition for lowering the calcination temperature for producing a conductive material (calcination temperature lowering agent) containing an alkyl (meth) acrylate substituted with an oxygen-containing ring.
  • the calcination temperature lowering agent of the present disclosure is incorporated and used as part of a polymer matrix.
  • the conductive material of the present disclosure comprises a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring and a conductive component.
  • the alkyl (meth) acrylate substituted with the oxygen-containing ring can be included as a copolymer to lower the calcination temperature for producing the conductive material.
  • the copolymer used in the present disclosure is a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing group and a second (meth) acrylic monomer.
  • the copolymer used in the present disclosure is a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring and a second (meth) acrylic monomer.
  • the copolymers used in the present disclosure are represented by formula (4), where n is 0, R 1 is a hydrogen atom, and R 2 is an alkyl substituted with an oxygen-containing group. It is advantageous that the compound is a copolymer of a second (meth) acrylic monomer.
  • the alkyl (meth) acrylate substituted with the oxygen-containing ring is of formula (1).
  • R 1 is a hydrogen atom or a methyl group and R 2 is an alkyl group substituted with one or more oxylan or oxetane rings.
  • the second (meth) acrylic monomer is of formula (2).
  • R 3 is a hydrogen atom or a methyl group and
  • R 4 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,
  • R 4 is not an alkyl group substituted with an oxygen-containing ring.
  • R 4 is an unsubstituted alkyl group having 11 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 24 carbon atoms.
  • R 4 is an unsubstituted alkyl group having 13 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 24 carbon atoms.
  • R 4 is an unsubstituted alkyl group having 18 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 24 carbon atoms.
  • R 4 is an unsubstituted alkyl group having 2 to 10 carbon atoms.
  • the alkyl (meth) acrylate substituted with the oxygen-containing ring is (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate.
  • the second (meth) acrylic monomer is isostearyl acrylate or lauryl acrylate.
  • the present disclosure provides a conductive material with improved conductivity.
  • the present disclosure provides a conductive material comprising a copolymer of an alkyl fluorinated (meth) acrylate and a conductive component.
  • a conductive material comprising a copolymer of an alkyl fluorinated (meth) acrylate and a conductive component.
  • 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 present disclosure also provides a method for producing the conductive material and the firing temperature lowering agent of the present disclosure.
  • the present disclosure provides a method for producing a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring and a conductive material containing a conductive component.
  • a step of obtaining a copolymer by polymerizing an alkyl (meth) acrylate substituted with the oxygen-containing ring and a polymerizable monomer a step of mixing the copolymer and a conductive component to obtain a mixture, and a step of obtaining the mixture. It includes a step of heating to produce a conductive material.
  • any embodiment described in the present specification or a combination thereof can be utilized, and any embodiment described in the section (Baking temperature lowering use) in the present specification. Can be applied as one or a combination of two or more.
  • the following conditions are typically preferable: under atmospheric pressure. 5 ° C to 100 ° C.
  • the following conditions are typically preferable: stirring by a planetary mixing stirrer at room temperature under atmospheric pressure.
  • the following conditions are typically preferable: 120 ° C. to 150 ° C. under atmospheric pressure.
  • the present disclosure is expressed in equation (4).
  • the second (meth) acrylic monomer has the formula (2).
  • R 3 is a hydrogen atom or a methyl group
  • R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkyl are alkoxy-substituted, Provide copolymers. This copolymer is used, for example, as a matrix of conductive materials.
  • the alkyl (meth) acrylate substituted with the oxygen-containing group is of formula (1).
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is an alkyl group substituted with one or more oxygen-containing groups.
  • equation (4) In the compound represented by, R 1 is a hydrogen atom and R 2 is an alkyl group, a cycloalkyl group, or an alkylcycloalkylalkyl group, which may be substituted with vinyloxy or hydroxy, or-(CH 2 CH). 2 O) y- R 7 , where R 7 is hydrogen or vinyl, y is an integer greater than or equal to 1, and n is 0.
  • the present disclosure also provides a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring and a second (meth) acrylic monomer, wherein the alkyl (meth) acrylate substituted with the oxygen-containing group is of the formula ( 1) Represented by, R 1 is a hydrogen atom or a methyl group, R 2 is an alkyl group substituted with one or more oxylan or oxetane rings.
  • the second (meth) acrylic monomer has the formula (2).
  • R 3 is a hydrogen atom or a methyl group
  • R 4 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
  • R 4 is not an alkyl group substituted with an oxygen-containing ring.
  • This copolymer is used, for example, as a matrix of conductive materials.
  • R 4 is an unsubstituted alkyl group having 11 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 24 carbon atoms.
  • R 4 is an unsubstituted alkyl group having 13 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 24 carbon atoms.
  • R 4 is an unsubstituted alkyl group having 18 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 24 carbon atoms.
  • R 4 is an unsubstituted alkyl group having 2 to 10 carbon atoms.
  • the present disclosure provides matrix applications.
  • the present disclosure is a composition for use as a matrix in a conductive material containing a conductive component, comprising a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring represented by formula (1).
  • I will provide a.
  • the present disclosure also provides a mixture.
  • the present disclosure provides a mixture as a substance (ie, a composition comprising a copolymer and a metallic component).
  • the disclosure provides a copolymer of a compound represented by formula (4) with a (second) (meth) acrylic monomer and a mixture of metals.
  • the "second" (meth) acrylic monomer means a monomer as a companion to the compound represented by the (first) formula (4) of the copolymer.
  • the mixture is a copolymer and metal mixture of an alkyl (meth) acrylate (monomer) substituted with an oxygen-containing group and a (second) (meth) acrylic monomer.
  • R 1 is a hydrogen atom and R 2 is an alkyl group, a cycloalkyl group, or an alkylcycloalkylalkyl group, which may be substituted with vinyloxy or hydroxy, or-(. CH 2 CH 2 O) y- R 7 , where R 7 is hydrogen or vinyl, y is an integer greater than or equal to 1, and n is 0, and the compound represented by the formula (4) (second).
  • a mixture of a copolymer with a (meth) acrylic monomer and a metal is a mixture of a copolymer with a (meth) acrylic monomer and a metal.
  • the present disclosure also provides a copolymer of an alkyl (meth) acrylate (monomer) substituted with an oxygen-containing ring and a (second) (meth) acrylic monomer and a mixture of metals.
  • the "second" (meth) acrylic monomer means a monomer as a companion to the alkyl (meth) acrylate monomer substituted with the (first) oxygen-containing ring of the copolymer.
  • 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 alkyl (meth) acrylate substituted with an oxygen-containing group is of formula (1).
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is alkoxy, oxirane ring and an alkyl group substituted by a substituent from one selected from the group consisting of oxetane ring to substitutable number.
  • the second (meth) acrylic monomer has the formula (2).
  • R 3 is a hydrogen atom or a methyl group
  • R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkoxy-substituted alkyl.
  • the alkyl (meth) acrylate substituted with the oxygen-containing ring is of formula (1).
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is an alkyl group substituted with one or more oxylan or oxetane rings.
  • the second (meth) acrylic monomer has the formula (2).
  • R 3 is a hydrogen atom or a methyl group
  • R 4 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
  • R 4 is not an alkyl group substituted with an oxygen-containing ring.
  • R 4 is an unsubstituted alkyl group having 11 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 24 carbon atoms.
  • R 4 is an unsubstituted alkyl group having 13 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 24 carbon atoms.
  • R 4 is an unsubstituted alkyl group having 18 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 24 carbon atoms.
  • R 4 is an unsubstituted alkyl group having 2 to 10 carbon atoms.
  • Example 1 Preparation of polymer matrix
  • a polymer matrix was prepared.
  • Example a Isostearyl acrylate (ISTA, 9.50 g) as monomer A, (3-ethyloxetane-3-yl) methyl acrylate (4.00 g, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name OXE-10) as monomer C, and A monomer component containing a polymerization initiator was obtained by mixing 2,4,6-trimethylbenzoyldiphenylphosphine oxide (0.14 g, manufactured by BASF, trade name Irgacure (registered trademark) TPO) as a polymerization initiator. ..
  • Example b to d Comparative Example 1
  • a polymer was obtained in the same manner as in Example a except that the ratio of the monomer A and the monomer C was changed as shown in Table 1.
  • a monomer component containing a polymerization initiator was obtained by mixing 6-trimethylbenzoyldiphenylphosphine oxide (0.14 g, manufactured by BASF, trade name Irgacure (registered trademark) TPO).
  • Example 2 Preparation of conductive film
  • a conductive film was prepared.
  • 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
  • Example 3 Measurement of volume resistivity
  • the conductive film obtained in Example 2 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).
  • Example 4 Confirmation of resistance value change
  • the change in resistance value was confirmed.
  • 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.
  • the conductive material improver of the present disclosure can be used to provide an efficient conductive material, which can be used in industries that require a conductive material.

Abstract

The present disclosure provides a composition for improving the conductivity of a conductive component or conductive material, the composition comprising the compound represented by formula (4). The present disclosure further provides a conductive material comprising a conductive component and a polymer of the compound, and a method for producing the conductive material. The present disclosure further provides a use for the polymer of the compound as a matrix.

Description

新規導電材焼成温度低下剤New conductive material firing temperature lowering agent
 本開示は、新規導電材焼成温度低下剤および新規導電率向上剤、ならびに関連技術に関する。より特定すると、本開示は、明細書中に記載の式(4)により表される化合物を含む、導電材焼成温度低下および導電材の導電率を向上させるための組成物等に関する。 The present disclosure relates to a new conductive material firing temperature lowering agent, a new conductivity improving agent, and related technologies. More specifically, the present disclosure relates to a composition for lowering the firing temperature of the conductive material and improving the conductivity of the conductive material, which comprises the compound represented by the formula (4) described in the specification.
 導電材や導電体については、種々の改良がなされてきている。しかし、現在提供されている導電材は、特定の組合せの導電成分と基材とを含むものに限定されているのが現状である。 Various improvements have been made to conductive materials and conductors. However, at present, the conductive materials currently provided are limited to those containing a specific combination of conductive components and a base material.
特開2019-102719号公報Japanese Unexamined Patent Publication No. 2019-102719 国際公開第2015/099049号International Publication No. 2015/099049 国際公開第2019/039511号International Publication No. 2019/039511 国際公開第2017/163615号International Publication No. 2017/1663615 特開2017-183207号公報JP-A-2017-183207
 本開示は、所望の組合せの導電成分と基材とを含む導電材を提供する。 The present disclosure provides a conductive material containing a desired combination of conductive components and a base material.
 本開示は、例えば、以下を提供する。 The disclosure provides, for example:
(項A1a)式(4)
Figure JPOXMLDOC01-appb-C000008
により表される化合物を含む、導電材の焼成温度を低下させるための組成物であって、
は、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であり、
nは、0または1の整数である、
組成物。
(項A1b)Rが、酸素含有基で置換されていてもよいアルキル基またはシクロアルキル基である、先行する項に記載の組成物。
(項A1c)Rが、酸素含有基で置換されたアルキル基である、先行する項のいずれか一項に記載の組成物。
(項A1d)Rが、酸素含有環で置換されたアルキル基である、先行する項のいずれか一項に記載の組成物。
(項A1e)式(4)により表される化合物が、酸素含有基で置換されたアルキル(メタ)アクリレートである、先行する項のいずれか一項に記載の組成物。
(項A1f)式(4)により表される化合物が、酸素含有環で置換されたアルキル(メタ)アクリレートである、先行する項のいずれか一項に記載の組成物。
(項A1g)n=0であり、式(4)により表される化合物が1個もしくは2個またはそれより多くのビニルオキシ基を有する、先行する項のいずれか一項に記載の組成物。
(項A2a)前記導電材が、式(4)により表される化合物のホモポリマーもしくはコポリマーおよび導電成分を含む、先行する項のいずれか一項に記載の組成物。
(項A2b)前記導電材が、前記酸素含有基で置換されたアルキル(メタ)アクリレートのホモポリマーもしくはコポリマーおよび導電成分を含む、先行する項のいずれか一項に記載の組成物。
(項A2c)前記導電材が、前記酸素含有環で置換されたアルキル(メタ)アクリレートのホモポリマーもしくはコポリマーおよび導電成分を含む、先行する項のいずれか一項に記載の組成物。
(項A3a)前記コポリマーが、式(4)により表される化合物と、第2の(メタ)アクリルモノマーとのコポリマーである、先行する項のいずれか一項に記載の組成物。
(項A3b)前記コポリマーが、前記酸素含有基で置換されたアルキル(メタ)アクリレートと、第2の(メタ)アクリルモノマーとのコポリマーである、先行する項のいずれか一項に記載の組成物。
(項A3c)前記コポリマーが、前記酸素含有環で置換されたアルキル(メタ)アクリレートと、第2の(メタ)アクリルモノマーとのコポリマーである、先行する項のいずれか一項に記載の組成物。
(項A4a)Rが、酸素含有基で置換されていてもよいアルキル基またはシクロアルキル基であり、前記酸素含有基が、ヒドロキシ、ヒドロキシアルキル、ビニルオキシアルキル、アルコキシ、オキシラン環もしくはオキセタン環、または-(CHCHO)-Rであり、Rが水素またはビニルであり、yが1から5の整数である、先行する項のいずれか一項に記載の組成物。
(項A4b)前記酸素含有基が、アルコキシ、オキシラン環またはオキセタン環である、先行する項のいずれか一項に記載の組成物。
(項A4c)前記酸素含有環が、オキシラン環またはオキセタン環である、先行する項のいずれか一項に記載の組成物。
(項A4d)前記酸素含有基が、ヒドロキシまたはアルコキシである、先行する項のいずれか一項に記載の組成物。
(項A4e)Rが、ビニルオキシもしくはヒドロキシで置換されていてもよいアルキル基、シクロアルキル基、もしくはアルキルシクロアルキルアルキル基、または
-(CHCHO)-Rであり、Rが水素またはビニルであり、yが1以上の整数である、
先行する項のいずれか一項に記載の組成物。
(項A5a)Rは、水素原子またはメチル基であり、
は、ヒドロキシ、アルコキシ、オキシラン環およびオキセタン環からなる群より選択される1個から置換可能数までの置換基で置換されたアルキル基である、
先行する項のいずれか一項に記載の組成物。
(項A5b)前記酸素含有基で置換されたアルキル(メタ)アクリレートが、式(1)
Figure JPOXMLDOC01-appb-C000009
によって表され、
は、水素原子またはメチル基であり、
は、アルコキシ、オキシラン環およびオキセタン環からなる群より選択される1個から置換可能数までの置換基で置換されたアルキル基である、
先行する項のいずれか一項に記載の組成物。
(項A5c)前記酸素含有環で置換されたアルキル(メタ)アクリレートが、式(1)
Figure JPOXMLDOC01-appb-C000010
によって表され、
は、水素原子またはメチル基であり、
は、1個またはそれより多くのオキシラン環またはオキセタン環で置換されたアルキル基である、
先行する項のいずれか一項に記載の組成物。
(項A5d)Rは、水素原子またはメチル基であり、
が、
ビニルオキシもしくはヒドロキシで置換されていてもよいアルキル基、シクロアルキル基、もしくはアルキルシクロアルキルアルキル基、または
-(CHCHO)-Rであり、Rが水素またはビニルであり、yが1から5の整数である、
n=0である、
先行する項のいずれか一項に記載の組成物。
(項A5e)n=0のとき、Rは水素原子である、先行する項のいずれか一項に記載の組成物。
(項A6a)前記第2の(メタ)アクリルモノマーは、式(2)
Figure JPOXMLDOC01-appb-C000011
によって表され、
は、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは、酸素含有環で置換されたアルキル基でも、アルコキシ置換されたアルキルでもない、
先行する項のいずれか一項に記載の組成物。
(項A6b)Rが2~10個の炭素原子を有する非置換アルキル基である、先行する項のいずれか一項に記載の組成物。
(項A6c)Rが11個またはそれより多くの炭素原子を有する非置換アルキル基である、先行する項のいずれか一項に記載の組成物。
(項A6d)Rが13個またはそれより多くの炭素原子を有する非置換アルキル基である、先行する項のいずれか一項に記載の組成物。
(項A6e)Rが18個またはそれより多くの炭素原子を有する非置換アルキル基である、先行する項のいずれか一項に記載の組成物。
(項A7a)式(4)により表される化合物が、4-ヒドロキシブチルビニルエーテル、2-メトキシエチルアクリレート、(3-エチルオキセタン-3-イル)メチルアクリレートまたは2,3-エポキシプロピルメタクリレートである、先行する項のいずれか一項に記載の組成物。
(項A7b)前記酸素含有基で置換されたアルキル(メタ)アクリレートが、2-メトキシエチルアクリレート、(3-エチルオキセタン-3-イル)メチルアクリレートまたは2,3-エポキシプロピルメタクリレートである、先行する項のいずれか一項に記載の組成物。
(項A7c)前記酸素含有環で置換されたアルキル(メタ)アクリレートが、(3-エチルオキセタン-3-イル)メチルアクリレートまたは2,3-エポキシプロピルメタクリレートである、先行する項のいずれか一項に記載の組成物。
(項A7d)式(4)により表される化合物が、4-ヒドロキシブチルビニルエーテルである、先行する項のいずれか一項に記載の組成物。
(項A8)前記第2の(メタ)アクリルモノマーが、エチルアクリレート、ステアリルアクリレート、イソステアリルアクリレートまたはラウリルアクリレートである、先行する項のいずれか一項に記載の組成物。
(項A9a)式(4)
Figure JPOXMLDOC01-appb-C000012
により表される化合物のコポリマーおよび導電成分を含む、導電材であって、
は、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であり、
nは、0または1の整数である、
導電材。
(項A9b)式(4)により表される化合物は、酸素含有基で置換されたアルキル(メタ)アクリレートである、導電材。
(項A9c)式(4)により表される化合物は、酸素含有環で置換されたアルキル(メタ)アクリレートである、導電材。
(項A9d)n=0であり、Rが、酸素含有基で置換されていてもよいアルキル基またはシクロアルキル基である、導電材。
(項A10)先行する項に記載の1つまたは複数の特徴を含む、先行する項のいずれか一項に記載の導電材。
(項A11a)式(4)
Figure JPOXMLDOC01-appb-C000013
により表される化合物のコポリマーおよび導電成分を含む導電材を製造する方法であって、前記方法は、
前記式(4)により表される化合物および重合性モノマーを重合することによりコポリマーを得る工程、
該コポリマーおよび導電成分を混合して、混合物を得る工程、および
該混合物を加熱して導電材を生成する工程
を包含し、
は、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であり、
nは、0または1の整数である、
方法。
(項A11b)前記式(4)により表される化合物は、酸素含有基で置換されたアルキル(メタ)アクリレートである、先行する項のいずれか一項に記載の方法。
(項A11c)前記式(4)により表される化合物は、酸素含有環で置換されたアルキル(メタ)アクリレートである、先行する項のいずれか一項に記載の方法。
(項A11d)n=0であり、Rが、酸素含有基で置換されていてもよいアルキル基またはシクロアルキル基である、先行する項のいずれか一項に記載の方法。
(項A12)先行する項に記載の1つまたは複数の特徴を含む、先行する項のいずれか一項に記載の方法。
(項A13a)式(4)
Figure JPOXMLDOC01-appb-C000014
により表される化合物と第2の(メタ)アクリルモノマーとのコポリマーであって、
は、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であり、
nは、0または1の整数であり、
該第2の(メタ)アクリルモノマーは、式(2)
Figure JPOXMLDOC01-appb-C000015
によって表され、
は、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは、酸素含有環で置換されたアルキル基でも、アルコキシ置換されたアルキルでもない、
コポリマー。
(項A13b)式(4)により表される化合物は、式(1)
Figure JPOXMLDOC01-appb-C000016
によって表される、酸素含有基で置換されたアルキル(メタ)アクリレートであり、
は、水素原子またはメチル基であり、
は、1個またはそれより多くの酸素含有基で置換されたアルキル基である、
先行する項のいずれか一項に記載のコポリマー。
(項A13c)式(4)により表される化合物は、式(1)
Figure JPOXMLDOC01-appb-C000017
によって表される、酸素含有環で置換されたアルキル(メタ)アクリレートであり、
は、水素原子またはメチル基であり、
は、1個またはそれより多くのオキシラン環またはオキセタン環で置換されたアルキル基である、
先行する項のいずれか一項に記載のコポリマー。
(項A13d)n=0であり、Rが、酸素含有基で置換されていてもよいアルキル基またはシクロアルキル基である、先行する項のいずれか一項に記載のコポリマー。
(項A13e)Rが2~10個の炭素原子を有する非置換アルキル基である、先行する項のいずれか一項に記載のコポリマー。
(項A13f)Rが11個またはそれより多くの炭素原子を有する非置換アルキル基である、先行する項のいずれか一項に記載のコポリマー。
(項A13g)Rが13個またはそれより多くの炭素原子を有する非置換アルキル基である、先行する項のいずれか一項に記載のコポリマー。
(項A13h)Rが18個またはそれより多くの炭素原子を有する非置換アルキル基である、先行する項のいずれか一項に記載のコポリマー。
(項A14)先行する項に記載の1つまたは複数の特徴を含む、先行する項のいずれか一項に記載のコポリマー。
(項A15a)先行する項のいずれか一項に記載の式(4)により表される化合物のコポリマーを含む、導電成分を含む導電材中のマトリクスとして使用するための組成物。
(項A15b)先行する項のいずれか一項に記載の酸素含有基で置換されたアルキル(メタ)アクリレートのコポリマーを含む、導電成分を含む導電材中のマトリクスとして使用するための組成物。
(項A15c)先行する項のいずれか一項に記載の酸素含有環で置換されたアルキル(メタ)アクリレートのコポリマーを含む、導電成分を含む導電材中のマトリクスとして使用するための組成物。
(項A15d)n=0であり、Rが、酸素含有基で置換されていてもよいアルキル基またはシクロアルキル基である、先行する項のいずれか一項に記載の式(4)により表される化合物のコポリマーを含む、導電成分を含む導電材中のマトリクスとして使用するための組成物。
(項A16)先行する項に記載の1つまたは複数の特徴を含む、先行する項のいずれか一項に記載の組成物。
(項A17a)式(4)
Figure JPOXMLDOC01-appb-C000018
により表される化合物と第2の(メタ)アクリルモノマーとのコポリマーおよび
金属
の混合物であって、
は、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であり、
nは、0または1の整数である、
混合物。
(項A17b)式(4)により表される化合物は、酸素含有基で置換されたアルキル(メタ)アクリレートである、先行する項のいずれか一項に記載の混合物。
(項A17c)式(4)により表される化合物は、酸素含有環で置換されたアルキル(メタ)アクリレートである、先行する項のいずれか一項に記載の混合物。
(項A17d)前記酸素含有基で置換されたアルキル(メタ)アクリレートは、式(1)
Figure JPOXMLDOC01-appb-C000019
によって表され、
は、水素原子またはメチル基であり、
は、アルコキシ、オキシラン環およびオキセタン環からなる群より選択される1個から置換可能数までの置換基で置換されたアルキル基であり、
前記第2の(メタ)アクリルモノマーは、式(2)
Figure JPOXMLDOC01-appb-C000020
によって表され、
は、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは、酸素含有環で置換されたアルキル基でも、アルコキシ置換されたアルキルでもない、
先行する項のいずれか一項に記載の混合物。
(項A17e)前記酸素含有環で置換されたアルキル(メタ)アクリレートは、式(1)
Figure JPOXMLDOC01-appb-C000021
によって表され、
は、水素原子またはメチル基であり、
は、1個またはそれより多くのオキシラン環またはオキセタン環で置換されたアルキル基である、
先行する項のいずれか一項に記載の混合物。
(項A17f)Rが、酸素含有基で置換されていてもよいアルキル基またはシクロアルキル基であり、n=0である、先行する項のいずれか一項に記載の混合物。
(項A17g)Rが2~10個の炭素原子を有する非置換アルキル基である、先行する項のいずれか一項に記載のコポリマー。
(項A17h)Rが11個またはそれより多くの炭素原子を有する非置換アルキル基である、先行する項のいずれか一項に記載の混合物。
(項A17i)Rが13個またはそれより多くの炭素原子を有する非置換アルキル基である、先行する項のいずれか一項に記載の混合物。
(項A17j)Rが18個またはそれより多くの炭素原子を有する非置換アルキル基である、先行する項のいずれか一項に記載の混合物。
(項A18a)前記金属が、銀、銅、金、アルミニウム、亜鉛、ニッケル、錫、および/または鉄を含む、先行する項のいずれか一項に記載の混合物。
(項A18b)前記金属が銀である、先行する項のいずれか一項に記載の混合物。
(項A19)先行する項に記載の1つまたは複数の特徴を含む、先行する項のいずれか一項に記載の混合物。
(Item A1a) Equation (4)
Figure JPOXMLDOC01-appb-C000008
A composition for lowering the firing temperature of a conductive material, which comprises the compound represented by.
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. ,
n is an integer of 0 or 1,
Composition.
(Item A1b) The composition according to the preceding item, wherein R 2 is an alkyl group or a cycloalkyl group which may be substituted with an oxygen-containing group.
(Item A1c) The composition according to any one of the preceding items, wherein R 2 is an alkyl group substituted with an oxygen-containing group.
(Section A1d) R 2 is an alkyl group substituted with an oxygen-containing rings, the preceding composition according to any one of claims.
(Item A1e) The composition according to any one of the preceding items, wherein the compound represented by the formula (4) is an alkyl (meth) acrylate substituted with an oxygen-containing group.
(Item A1f) The composition according to any one of the preceding items, wherein the compound represented by the formula (4) is an alkyl (meth) acrylate substituted with an oxygen-containing ring.
(Item A1g) The composition according to any one of the preceding items, wherein n = 0 and the compound represented by the formula (4) has one or two or more vinyloxy groups.
(Item A2a) The composition according to any one of the preceding items, wherein the conductive material contains a homopolymer or copolymer of a compound represented by the formula (4) and a conductive component.
(Item A2b) The composition according to any one of the preceding items, wherein the conductive material contains a homopolymer or copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing group and a conductive component.
(Item A2c) The composition according to any one of the preceding items, wherein the conductive material comprises a homopolymer or copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing ring and a conductive component.
(Item A3a) The composition according to any one of the preceding items, wherein the copolymer is a copolymer of a compound represented by the formula (4) and a second (meth) acrylic monomer.
(Item A3b) The composition according to any one of the preceding items, wherein the copolymer is a copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing group and a second (meth) acrylic monomer. ..
(Item A3c) The composition according to any one of the preceding items, wherein the copolymer is a copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing ring and a second (meth) acrylic monomer. ..
(Item A4a) R 2 is an alkyl group or a cycloalkyl group which may be substituted with an oxygen-containing group, and the oxygen-containing group is a hydroxy, hydroxyalkyl, vinyloxyalkyl, alkoxy, oxylan ring or oxetane ring. Or-(CH 2 CH 2 O) y- R 7 , where R 7 is hydrogen or vinyl and y is an integer of 1 to 5, according to any one of the preceding paragraphs.
(Item A4b) The composition according to any one of the preceding items, wherein the oxygen-containing group is an alkoxy, an oxylan ring or an oxetane ring.
(Item A4c) The composition according to any one of the preceding items, wherein the oxygen-containing ring is an oxylan ring or an oxetane ring.
(Item A4d) The composition according to any one of the preceding items, wherein the oxygen-containing group is hydroxy or alkoxy.
(Item A4e) R 2 is an alkyl group, a cycloalkyl group, or an alkylcycloalkylalkyl group which may be substituted with vinyloxy or hydroxy, or-(CH 2 CH 2 O) y- R 7 , and R 7 Is hydrogen or vinyl and y is an integer greater than or equal to 1.
The composition according to any one of the preceding paragraphs.
(Item A5a) R 1 is a hydrogen atom or a methyl group.
R 2 is hydroxy, alkoxy, oxirane ring and an alkyl group substituted by a substituent from one selected from the group consisting of oxetane ring to substitutable number,
The composition according to any one of the preceding paragraphs.
(Item A5b) The alkyl (meth) acrylate substituted with the oxygen-containing group is the formula (1).
Figure JPOXMLDOC01-appb-C000009
Represented by
R 1 is a hydrogen atom or a methyl group and
R 2 is alkoxy, oxirane ring and an alkyl group which is substituted with up substitutable number from 1 selected from the group consisting of oxetane ring,
The composition according to any one of the preceding paragraphs.
(Item A5c) The alkyl (meth) acrylate substituted with the oxygen-containing ring is the formula (1).
Figure JPOXMLDOC01-appb-C000010
Represented by
R 1 is a hydrogen atom or a methyl group and
R 2 is an alkyl group substituted with one or more oxylan or oxetane rings,
The composition according to any one of the preceding paragraphs.
(Item A5d) R 1 is a hydrogen atom or a methyl group.
R 2
Alkyl group, cycloalkyl group, or alkylcycloalkylalkyl group which may be substituted with vinyloxy or hydroxy, or-(CH 2 CH 2 O) y- R 7 , where R 7 is hydrogen or vinyl, y Is an integer from 1 to 5,
n = 0,
The composition according to any one of the preceding paragraphs.
(Item A5e) The composition according to any one of the preceding items, wherein R 1 is a hydrogen atom when n = 0.
(Item A6a) The second (meth) acrylic monomer has the formula (2).
Figure JPOXMLDOC01-appb-C000011
Represented by
R 3 is a hydrogen atom or a methyl group and
R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkyl are alkoxy-substituted,
The composition according to any one of the preceding paragraphs.
(Section A6b) R 4 is an unsubstituted alkyl group having 2-10 carbon atoms, preceding composition according to any one of claims.
(Section A6c) R 4 is an unsubstituted alkyl group having 11 or more carbon atoms, the preceding composition according to any one of claims.
(Section A6d) R 4 is an unsubstituted alkyl group having 13 or more carbon atoms, the preceding composition according to any one of claims.
(Section A6E) R 4 is an unsubstituted alkyl group having 18 or more carbon atoms, the preceding composition according to any one of claims.
The compound represented by the formula (4) of (Item A7a) is 4-hydroxybutyl vinyl ether, 2-methoxyethyl acrylate, (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate. The composition according to any one of the preceding paragraphs.
(Item A7b) The alkyl (meth) acrylate substituted with the oxygen-containing group is 2-methoxyethyl acrylate, (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate. The composition according to any one of the items.
(Item A7c) Any one of the preceding items, wherein the alkyl (meth) acrylate substituted with the oxygen-containing ring is (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate. The composition according to.
(Item A7d) The composition according to any one of the preceding items, wherein the compound represented by the formula (4) is 4-hydroxybutyl vinyl ether.
(Item A8) The composition according to any one of the preceding items, wherein the second (meth) acrylic monomer is ethyl acrylate, stearyl acrylate, isostearyl acrylate or lauryl acrylate.
(Item A9a) Equation (4)
Figure JPOXMLDOC01-appb-C000012
A conductive material containing a copolymer of the compound represented by and a conductive component.
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. ,
n is an integer of 0 or 1,
Conductive material.
(Item A9b) The compound represented by the formula (4) is a conductive material which is an alkyl (meth) acrylate substituted with an oxygen-containing group.
(Item A9c) The compound represented by the formula (4) is a conductive material which is an alkyl (meth) acrylate substituted with an oxygen-containing ring.
(Item A9d) A conductive material in which n = 0 and R 2 is an alkyl group or a cycloalkyl group which may be substituted with an oxygen-containing group.
(Item A10) The conductive material according to any one of the preceding items, which comprises one or more of the features described in the preceding item.
(Item A11a) Equation (4)
Figure JPOXMLDOC01-appb-C000013
A method for producing a copolymer of a compound represented by the above and a conductive material containing a conductive component.
A step of obtaining a copolymer by polymerizing a compound represented by the formula (4) and a polymerizable monomer.
Including the steps of mixing the copolymer and the conductive components to obtain a mixture, and heating the mixture to produce a conductive material.
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. ,
n is an integer of 0 or 1,
Method.
(Item A11b) The method according to any one of the preceding items, wherein the compound represented by the above formula (4) is an alkyl (meth) acrylate substituted with an oxygen-containing group.
(Item A11c) The method according to any one of the preceding items, wherein the compound represented by the above formula (4) is an alkyl (meth) acrylate substituted with an oxygen-containing ring.
(Section A11d) is n = 0, R 2 is an oxygen-containing optionally substituted alkyl group or a cycloalkyl group with a group A method according to any one of the preceding claim.
(Item A12) The method according to any one of the preceding items, which comprises one or more of the features described in the preceding item.
(Item A13a) Equation (4)
Figure JPOXMLDOC01-appb-C000014
It is a copolymer of a compound represented by and a second (meth) acrylic monomer.
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. ,
n is an integer of 0 or 1 and
The second (meth) acrylic monomer has the formula (2).
Figure JPOXMLDOC01-appb-C000015
Represented by
R 3 is a hydrogen atom or a methyl group and
R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkyl are alkoxy-substituted,
Copolymer.
(Item A13b) The compound represented by the formula (4) is the formula (1).
Figure JPOXMLDOC01-appb-C000016
An alkyl (meth) acrylate substituted with an oxygen-containing group, represented by
R 1 is a hydrogen atom or a methyl group and
R 2 is an alkyl group substituted with one or more oxygen-containing groups,
The copolymer according to any one of the preceding paragraphs.
(Item A13c) The compound represented by the formula (4) is the formula (1).
Figure JPOXMLDOC01-appb-C000017
An alkyl (meth) acrylate substituted with an oxygen-containing ring, represented by
R 1 is a hydrogen atom or a methyl group and
R 2 is an alkyl group substituted with one or more oxylan or oxetane rings,
The copolymer according to any one of the preceding paragraphs.
(Section A13d) is n = 0, R 2 is substituted with an oxygen-containing group is also an alkyl group or a cycloalkyl group, preceding copolymer according to any one of claims.
(Section A13e) R 4 is an unsubstituted alkyl group having 2 to 10 carbon atoms, the copolymer according to any one of the preceding claim.
(Section A13f) R 4 is an unsubstituted alkyl group having 11 or more carbon atoms, the copolymer according to any one of the preceding claim.
(Section A13g) R 4 is an unsubstituted alkyl group having 13 or more carbon atoms, the copolymer according to any one of the preceding claim.
(Section A13h) R 4 is an unsubstituted alkyl group having 18 or more carbon atoms, the copolymer according to any one of the preceding claim.
(Item A14) The copolymer according to any one of the preceding items, which comprises one or more of the features described in the preceding item.
(Item A15a) A composition for use as a matrix in a conductive material containing a conductive component, which comprises a copolymer of a compound represented by the formula (4) according to any one of the preceding items.
(Item A15b) A composition for use as a matrix in a conductive material containing a conductive component, which comprises a copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing group according to any one of the preceding items.
(Item A15c) A composition for use as a matrix in a conductive material containing a conductive component, which comprises a copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing ring according to any one of the preceding items.
(Section A15d) is n = 0, Table R 2 is an oxygen-containing optionally substituted alkyl group or a cycloalkyl group with a group, the formula (4) according to any one of the preceding claim A composition for use as a matrix in a conductive material containing a conductive component, which comprises a copolymer of the compound to be used.
(Item A16) The composition according to any one of the preceding items, which comprises one or more of the features described in the preceding item.
(Item A17a) Equation (4)
Figure JPOXMLDOC01-appb-C000018
A copolymer of a compound represented by and a second (meth) acrylic monomer and a mixture of metals.
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. ,
n is an integer of 0 or 1,
blend.
(Item A17b) The mixture represented by any one of the preceding items, wherein the compound represented by the formula (4) is an alkyl (meth) acrylate substituted with an oxygen-containing group.
(Item A17c) The mixture represented by any one of the preceding items, wherein the compound represented by the formula (4) is an alkyl (meth) acrylate substituted with an oxygen-containing ring.
(Item A17d) The alkyl (meth) acrylate substituted with the oxygen-containing group has the formula (1).
Figure JPOXMLDOC01-appb-C000019
Represented by
R 1 is a hydrogen atom or a methyl group and
R 2 is an alkyl group substituted with one to a substitutable number of substituents selected from the group consisting of alkoxy, oxylan ring and oxetane ring.
The second (meth) acrylic monomer has the formula (2).
Figure JPOXMLDOC01-appb-C000020
Represented by
R 3 is a hydrogen atom or a methyl group and
R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkyl are alkoxy-substituted,
The mixture according to any one of the preceding paragraphs.
(Item A17e) The alkyl (meth) acrylate substituted with the oxygen-containing ring has the formula (1).
Figure JPOXMLDOC01-appb-C000021
Represented by
R 1 is a hydrogen atom or a methyl group and
R 2 is an alkyl group substituted with one or more oxylan or oxetane rings,
The mixture according to any one of the preceding paragraphs.
(Section A17f) R 2 is substituted with an oxygen-containing group is also an alkyl group or a cycloalkyl group, a n = 0, the preceding mixture according to any one of claims.
(Section A17g) R 4 is an unsubstituted alkyl group having 2 to 10 carbon atoms, the copolymer according to any one of the preceding claim.
(Section A17h) R 4 is an unsubstituted alkyl group having 11 or more carbon atoms, the preceding mixture according to any one of claims.
(Section A17i) R 4 is an unsubstituted alkyl group having 13 or more carbon atoms, the preceding mixture according to any one of claims.
(Section A17j) R 4 is an unsubstituted alkyl group having 18 or more carbon atoms, the preceding mixture according to any one of claims.
(Item A18a) The mixture according to any one of the preceding items, wherein the metal comprises silver, copper, gold, aluminum, zinc, nickel, tin, and / or iron.
(Item A18b) The mixture according to any one of the preceding items, wherein the metal is silver.
(Item A19) The mixture according to any one of the preceding items, which comprises one or more of the features described in the preceding item.
 本開示はまた、例えば、以下を提供する。 The disclosure also provides, for example:
(項1)酸素含有環で置換されたアルキル(メタ)アクリレートを含む、導電材の焼成温度を低下させるための組成物。
(項2)前記導電材が、前記酸素含有環で置換されたアルキル(メタ)アクリレートのコポリマーおよび導電成分を含む、上記項に記載の組成物。
(項3)前記コポリマーが、前記酸素含有環で置換されたアルキル(メタ)アクリレートと、第2の(メタ)アクリルモノマーとのコポリマーである、上記項のいずれか一項に記載の組成物。
(項4)前記酸素含有環が、オキシラン環またはオキセタン環である、上記項のいずれか一項に記載の組成物。
(項5)前記酸素含有環で置換されたアルキル(メタ)アクリレートが、式(1)
Figure JPOXMLDOC01-appb-C000022
によって表され、
は、水素原子またはメチル基であり、
は、1個またはそれより多くのオキシラン環またはオキセタン環で置換されたアルキル基である、
上記項のいずれか一項に記載の組成物。
(項6)前記第2の(メタ)アクリルモノマーは、式(2)
Figure JPOXMLDOC01-appb-C000023
によって表され、
は、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは酸素含有環で置換されたアルキル基ではない、
上記項のいずれか一項に記載の組成物。
(項6a)Rが11個またはそれより多くの炭素原子を有する非置換アルキル基である、上記項のいずれか一項に記載の組成物。
(項6b)Rが13個またはそれより多くの炭素原子を有する非置換アルキル基である、上記項のいずれか一項に記載の組成物。
(項6c)Rが18個またはそれより多くの炭素原子を有する非置換アルキル基である、上記項のいずれか一項に記載の組成物。
(項7)前記酸素含有環で置換されたアルキル(メタ)アクリレートが、(3-エチルオキセタン-3-イル)メチルアクリレートまたは2,3-エポキシプロピルメタクリレートである、上記項のいずれか一項に記載の組成物。
(項8)前記第2の(メタ)アクリルモノマーが、イソステアリルアクリレートまたはラウリルアクリレートである、上記項のいずれか一項に記載の組成物。
(項9)酸素含有環で置換されたアルキル(メタ)アクリレートのコポリマーおよび導電成分を含む、導電材。
(項10)上記項に記載の1つまたは複数の特徴を含む、上記項のいずれか一項に記載の導電材。
(項11)酸素含有環で置換されたアルキル(メタ)アクリレートのコポリマーおよび導電成分を含む導電材を製造する方法であって、
前記酸素含有環で置換されたアルキル(メタ)アクリレートおよび重合性モノマーを重合することによりコポリマーを得る工程、
該コポリマーおよび導電成分を混合して、混合物を得る工程、および
該混合物を加熱して導電材を生成する工程
を包含する、方法。
(項12)上記項に記載の1つまたは複数の特徴を含む、上記項のいずれか一項に記載の方法。
(項13)酸素含有環で置換されたアルキル(メタ)アクリレートと第2の(メタ)アクリルモノマーとのコポリマーであって、
該酸素含有環で置換されたアルキル(メタ)アクリレートは、式(1)
Figure JPOXMLDOC01-appb-C000024
によって表され、
は、水素原子またはメチル基であり、
は、1個またはそれより多くのオキシラン環またはオキセタン環で置換されたアルキル基であり、
該第2の(メタ)アクリルモノマーは、式(2)
Figure JPOXMLDOC01-appb-C000025
によって表され、
は、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは酸素含有環で置換されたアルキル基ではない、
コポリマー。
(項13a)Rが11個またはそれより多くの炭素原子を有する非置換アルキル基である、上記項のいずれか一項に記載のコポリマー。
(項13b)Rが13個またはそれより多くの炭素原子を有する非置換アルキル基である、上記項のいずれか一項に記載のコポリマー。
(項13c)Rが18個またはそれより多くの炭素原子を有する非置換アルキル基である、上記項のいずれか一項に記載のコポリマー。
(項14)上記項に記載の1つまたは複数の特徴を含む、上記項のいずれか一項に記載のコポリマー。
(項15)上記項のいずれか一項に記載の酸素含有環で置換されたアルキル(メタ)アクリレートのコポリマーを含む、導電成分を含む導電材中のマトリクスとして使用するための組成物。
(項16)上記項に記載の1つまたは複数の特徴を含む、上記項のいずれか一項に記載の組成物。
(項17)酸素含有環で置換されたアルキル(メタ)アクリレートと第2の(メタ)アクリルモノマーとのコポリマーおよび
金属
の混合物。
(項18)前記金属が、銀、銅、金、アルミニウム、亜鉛、ニッケル、錫、および/または鉄を含む、上記項のいずれか一項に記載の混合物。
(項18a)前記金属が銀である、上記項のいずれか一項に記載の混合物。
(項19)前記酸素含有環で置換されたアルキル(メタ)アクリレートは、式(1)
Figure JPOXMLDOC01-appb-C000026
によって表され、
は、水素原子またはメチル基であり、
は、1個またはそれより多くのオキシラン環またはオキセタン環で置換されたアルキル基であり、
前記第2の(メタ)アクリルモノマーは、式(2)
Figure JPOXMLDOC01-appb-C000027
によって表され、
は、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは酸素含有環で置換されたアルキル基ではない、
上記項のいずれか一項に記載の混合物。
(項19a)Rが11個またはそれより多くの炭素原子を有する非置換アルキル基である、上記項のいずれか一項に記載の混合物。
(項19b)Rが13個またはそれより多くの炭素原子を有する非置換アルキル基である、上記項のいずれか一項に記載の混合物。
(項19c)Rが18個またはそれより多くの炭素原子を有する非置換アルキル基である、上記項のいずれか一項に記載の混合物。
(項20)上記項に記載の1つまたは複数の特徴を含む、上記項のいずれか一項に記載の混合物。
(Item 1) A composition for lowering the firing temperature of a conductive material, which comprises an alkyl (meth) acrylate substituted with an oxygen-containing ring.
(Item 2) The composition according to the above item, wherein the conductive material contains a copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing ring and a conductive component.
(Item 3) The composition according to any one of the above items, wherein the copolymer is a copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing ring and a second (meth) acrylic monomer.
(Item 4) The composition according to any one of the above items, wherein the oxygen-containing ring is an oxylan ring or an oxetane ring.
(Item 5) The alkyl (meth) acrylate substituted with the oxygen-containing ring is the formula (1).
Figure JPOXMLDOC01-appb-C000022
Represented by
R 1 is a hydrogen atom or a methyl group and
R 2 is an alkyl group substituted with one or more oxylan or oxetane rings,
The composition according to any one of the above items.
(Item 6) The second (meth) acrylic monomer has the formula (2).
Figure JPOXMLDOC01-appb-C000023
Represented by
R 3 is a hydrogen atom or a methyl group and
R 4 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, However, R 4 is not an alkyl group substituted with an oxygen-containing ring,
The composition according to any one of the above items.
(Section 6a) R 4 is an unsubstituted alkyl group having 11 or more carbon atoms, A composition according to any one of the above items.
(Section 6b) R 4 is an unsubstituted alkyl group having 13 or more carbon atoms, A composition according to any one of the above items.
(Section 6c) R 4 is an unsubstituted alkyl group having 18 or more carbon atoms, A composition according to any one of the above items.
(Item 7) In any one of the above items, the alkyl (meth) acrylate substituted with the oxygen-containing ring is (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate. The composition described.
(Item 8) The composition according to any one of the above items, wherein the second (meth) acrylic monomer is isostearyl acrylate or lauryl acrylate.
(Item 9) A conductive material containing a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring and a conductive component.
(Item 10) The conductive material according to any one of the above items, which comprises one or more of the features described in the above item.
(Item 11) A method for producing a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring and a conductive material containing a conductive component.
A step of obtaining a copolymer by polymerizing an alkyl (meth) acrylate substituted with the oxygen-containing ring and a polymerizable monomer.
A method comprising the steps of mixing the copolymer and a conductive component to obtain a mixture and heating the mixture to produce a conductive material.
(Item 12) The method according to any one of the above items, which comprises one or more of the features described in the above item.
(Item 13) A copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring and a second (meth) acrylic monomer.
The alkyl (meth) acrylate substituted with the oxygen-containing ring has the formula (1).
Figure JPOXMLDOC01-appb-C000024
Represented by
R 1 is a hydrogen atom or a methyl group and
R 2 is an alkyl group substituted with one or more oxylan or oxetane rings.
The second (meth) acrylic monomer has the formula (2).
Figure JPOXMLDOC01-appb-C000025
Represented by
R 3 is a hydrogen atom or a methyl group and
R 4 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, However, R 4 is not an alkyl group substituted with an oxygen-containing ring,
Copolymer.
(Section 13a) R 4 is an unsubstituted alkyl group having 11 or more carbon atoms, the copolymer according to any one of the above items.
(Section 13b) R 4 is an unsubstituted alkyl group having 13 or more carbon atoms, the copolymer according to any one of the above items.
(Section 13c) R 4 is an unsubstituted alkyl group having 18 or more carbon atoms, the copolymer according to any one of the above items.
(Item 14) The copolymer according to any one of the above items, which comprises one or more of the characteristics described in the above item.
(Item 15) A composition for use as a matrix in a conductive material containing a conductive component, which comprises a copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing ring according to any one of the above items.
(Item 16) The composition according to any one of the above items, which comprises one or more of the characteristics described in the above item.
(Item 17) A copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring and a second (meth) acrylic monomer, and a mixture of metals.
(Item 18) The mixture 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 mixture according to any one of the above items, wherein the metal is silver.
(Item 19) The alkyl (meth) acrylate substituted with the oxygen-containing ring has the formula (1).
Figure JPOXMLDOC01-appb-C000026
Represented by
R 1 is a hydrogen atom or a methyl group and
R 2 is an alkyl group substituted with one or more oxylan or oxetane rings.
The second (meth) acrylic monomer has the formula (2).
Figure JPOXMLDOC01-appb-C000027
Represented by
R 3 is a hydrogen atom or a methyl group and
R 4 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, However, R 4 is not an alkyl group substituted with an oxygen-containing ring,
The mixture according to any one of the above items.
(Section 19a) R 4 is an unsubstituted alkyl group having 11 or more carbon atoms, mixtures of any one of the above items.
(Section 19b) R 4 is an unsubstituted alkyl group having 13 or more carbon atoms, mixtures of any one of the above items.
(Section 19c) R 4 is an unsubstituted alkyl group having 18 or more carbon atoms, mixtures of any one of the above items.
(Item 20) The mixture according to any one of the above items, which comprises one or more of the characteristics described in the above item.
 本開示において、上記1または複数の特徴は、明示された組み合わせに加え、さらに組み合わせて提供されうることが意図される。本開示のなおさらなる実施形態および利点は、必要に応じて以下の詳細な説明を読んで理解すれば、当業者に認識される。 In the present disclosure, it is intended that the above one or more features may be provided in a further combination in addition to the specified combinations. Further embodiments and advantages of the present disclosure will be appreciated by those skilled in the art upon reading and understanding the following detailed description as necessary.
 本開示により、導電材焼成温度低下剤および導電性向上剤が提供され、これらを用いることで、導電性を向上させることができる技術を提供することができる。 According to the present disclosure, a conductive material firing temperature lowering agent and a conductivity improving agent are provided, and by using these, it is possible to provide a technique capable of improving the conductivity.
 以下、本開示を最良の形態を示しながら説明する。本明細書の全体にわたり、単数形の表現は、特に言及しない限り、その複数形の概念をも含むことが理解されるべきである。従って、単数形の冠詞(例えば、英語の場合は「a」、「an」、「the」など)は、特に言及しない限り、その複数形の概念をも含むことが理解されるべきである。また、本明細書において使用される用語は、特に言及しない限り、当該分野で通常用いられる意味で用いられることが理解されるべきである。したがって、他に定義されない限り、本明細書中で使用されるすべての専門用語および科学技術用語は、本開示の属する分野の当業者によって一般的に理解されるのと同じ意味を有する。矛盾する場合、本明細書(定義を含めて)が優先する。 Hereinafter, the present disclosure will be described while showing the best form. Throughout the specification, it should be understood that the singular representation also includes its plural concept, unless otherwise stated. Therefore, it should be understood that singular articles (eg, "a", "an", "the", etc. in English) also include the concept of their plural, unless otherwise noted. It should also be understood that the terms used herein are used in the meaning commonly used in the art unless otherwise noted. Thus, unless otherwise defined, all terminology and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this disclosure belongs. In case of conflict, this specification (including definitions) takes precedence.
 以下に本明細書において特に使用される用語の定義および/または基本的技術内容を適宜説明する。 The definitions of terms and / or basic technical contents particularly used in this specification will be described below as appropriate.
 (用語の定義)
 本明細書において、「導電性」とは、当該分野における通常の意味で使用され、電気を通す性質を意味し、その物性量を「導電率」といい、ある対象(導体ともよばれる)についての抵抗率(比抵抗、樹脂分野では体積抵抗率ともよばれる)の逆数として定義される。本明細書では、導電率(または抵抗率)は、以下のようにして測定する。具体的には、特に断らない限り、測定対象(例えば、フィルム等)を縦0.5cm×横2.00cm×厚さ0.2cmに切り出して、4端子測定法(例えば、ロレスタGP〔三菱化学アナリテック社製〕を用いることができるが、これに限定されない。)により測定された値を採用する。
(Definition of terms)
In the present specification, "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). In the present specification, the conductivity (or resistivity) 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).
 本明細書において、「導電材」とは、導電性を有する任意の材料を指す。本明細書では、導電材は、1.0×10-1Ω・cm以下、通常、1.0×10-2Ω・cm以下、好ましくは1.0×10-3Ω・cm以下の抵抗率を有するものを対象とするが、これに限定されない。導電材は、導電性を付与する導電成分を含む。代表的には、導電材は、通常基材と導電成分とを含んで構成される。 As used herein, the term "conductive material" refers to any material having conductivity. In the present specification, the conductive material has a resistance of 1.0 × 10 -1 Ω · cm or less, usually 1.0 × 10 −2 Ω · cm or less, preferably 1.0 × 10 -3 Ω · 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. Typically, the conductive material is usually composed of a base material and a conductive component.
 本明細書において「導電率を向上」とは、本開示の成分を導電成分または導電材に加えたときに、加えていない場合と比較して導電率が有意に増加していることをいい、例えば、導電率を少なくとも、約1%、約2%、約3%、約4%、約5%、約6%、約7%、約8%、約9%、約10%、約15%、約20%、約25%、約30%、約35%、約40%、約45%、約50%、約55%、約60%、約65%、約70%、約75%、約80%、約85%、約90%、約95%、約99%向上させることをいい、体積抵抗率の低下によっても表現することができる。例えば、比較対象と比べて、体積抵抗率が、約1%、約2%、約3%、約4%、約5%、約6%、約7%、約8%、約9%、約10%、約15%、約20%、約25%、約30%、約35%、約40%、約45%、約50%、約55%、約60%、約65%、約70%、約75%、約80%、約85%、約90%、約95%、約99%低下させることをいう。 As used herein, the term "improving conductivity" means that when the component of the present disclosure is added to a conductive component or a conductive material, the conductivity is significantly increased as compared with the case where the component is not added. For example, the conductivity 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%, about It means an improvement of 80%, about 85%, about 90%, about 95%, about 99%, and can also be expressed by a decrease in volume resistivity. For example, 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.
 本明細書において「焼成温度を低下」とは、本開示の成分を導電成分または導電材に加えたときに、加えていない場合と比較して低い温度で加熱した場合でも同じまたはそれより小さい体積抵抗率を達成できることをいう。例えば、焼成温度を少なくとも、約1%、約2%、約3%、約4%、約5%、約6%、約7%、約8%、約9%、約10%、約15%、約20%、約25%、約30%、約35%、約40%、約45%、約50%、約55%、約60%、約65%、約70%、約75%、約80%、約85%、約90%、約95%、約99%低下させることをいう。導電材は、含まれる溶媒を除去することなどを目的として、加熱処理される場合が多い。加熱処理の温度が低ければ、導電材自体や導電材が塗布された材料などへのダメージを与えにくいので好ましい。また、導電成分が後述する金属系成分の場合、導電材に導電性を発現させるためには、加熱処理を行い、金属系成分の粒子同士を焼結させる必要がある場合が多い。したがって、焼成温度を低下させても粒子同士を焼結させることができれば、導電材自体や導電材が塗布された材料などへのダメージを与えにくいので好ましい。 As used herein, the term "lowering the firing temperature" means the same or smaller volume when the components of the present disclosure are added to a conductive component or a conductive material and heated at a lower temperature than when not added. It means that the resistivity can be achieved. For example, the firing 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%, about It means to reduce by 80%, about 85%, about 90%, about 95%, and about 99%. The conductive material is often heat-treated for the purpose of removing the solvent contained therein. When the temperature of the heat treatment is low, it is preferable because the conductive material itself and the material coated with the conductive material are less likely to be damaged. Further, when the conductive component is a metal-based component described later, it is often necessary to perform a heat treatment to sinter the particles of the metal-based component in order to make the conductive material exhibit conductivity. Therefore, if the particles can be sintered with each other even if the firing temperature is lowered, it is preferable because the conductive material itself and the material coated with the conductive material are less likely to be damaged.
 本明細書において「基材」とは、マトリクスとも称し、導電材の構造の基礎的な部分を指す。基材としては、各種ポリマーを使用することができる。基材がポリマーである場合、基材をポリマーマトリクスと呼ぶ場合がある。 In the present specification, 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. When the base material is a polymer, the base material may be referred to as a polymer matrix.
 本明細書において、「導電成分」とは、導電性を付与する任意の成分を意味する。導電成分としては、例えば、任意の金属成分、金属酸化物、金属炭化物等の金属系成分、導電性炭素系成分、導電性有機化合物、導電性ポリマー等を挙げることができるが、これらに限定されない。 In the present specification, the "conductive component" means any component that imparts conductivity. Examples of the conductive component include, but are not limited to, any metal component, a metal oxide, a metal component such as a metal carbide, a conductive carbon component, a conductive organic compound, a conductive polymer, and the like. ..
 本明細書において「金属系成分」とは、金属原子をその構成要素として何らかの形式で含む成分であり、金属等の金属成分の他、金属に由来する成分(例えば、金属酸化物、金属炭化物、金属硫化物等)を包含する概念である。 In the present specification, 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.).
 本明細書において「金属成分」とは、金属または合金を含む。 In the present specification, the "metal component" includes a metal or an alloy.
 本明細書において「導電性炭素系成分」とは、炭素を含有する導電性材料を意味する。その具体的な例としては、鱗片状黒鉛などの天然黒鉛、人造黒鉛などのグラファイト、アセチレンブラック、ケッチェンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、サーマルブラックなどのカーボンブラック、グラフェン、カーボンナノチューブ、フラーレンなどの炭素系材料;炭素繊維;フッ化カーボンなどを挙げることができるが、これらに限定されない。金属炭化物は、導電性炭素系成分に含まれない。「導電性炭素系成分」は、「炭素系成分」と称する場合もある。 In the present specification, the "conductive carbon-based component" means a conductive material containing carbon. Specific examples include natural graphite such as scaly graphite, graphite such as artificial graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black and other carbon black, graphene, and carbon nanotubes. Carbon-based materials such as graphene; carbon fibers; carbon fluoride and the like can be mentioned, but are not limited thereto. Metal carbides are not included in the conductive carbon-based components. The "conductive carbon-based component" may also be referred to as a "carbon-based component".
 本明細書において「(メタ)アクリルモノマー」とは、アクリル基および/またはメタクリル基を含むモノマーであり、その例としては、アクリル酸、メタクリル酸、アクリル酸エステル、メタクリル酸エステル、アクリル酸アミド、メタクリル酸アミド等が挙げられる。 In the present specification, 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.
 本明細書において、「(メタ)アクリル」は、「アクリル」または「メタクリル」を意味し、「(メタ)アクリレート」は「アクリレート」または「メタクリレート」を意味する。 In the present specification, "(meth) acrylic" means "acrylic" or "methacryl", and "(meth) acrylate" means "acrylate" or "methacrylate".
 例えば、(メタ)アクリルモノマーはまた、式(2)
Figure JPOXMLDOC01-appb-C000028
によって表され、式中、Rは、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは、酸素含有環で置換されたアルキル基でも、アルコキシ置換されたアルキルでもない。
For example, the (meth) acrylic monomer also has formula (2).
Figure JPOXMLDOC01-appb-C000028
Represented by, in the formula, R 3 is a hydrogen atom or a methyl group,
R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkoxy-substituted alkyl.
 例えば、(メタ)アクリルモノマーはまた、式(2)
Figure JPOXMLDOC01-appb-C000029
によって表され、式中、Rは、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは酸素含有環で置換されたアルキル基ではない。
For example, the (meth) acrylic monomer also has formula (2).
Figure JPOXMLDOC01-appb-C000029
Represented by, in the formula, R 3 is a hydrogen atom or a methyl group,
R 4 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, However, R 4 is not an alkyl group substituted with an oxygen-containing ring.
 本明細書において「酸素含有環で置換されたアルキル(メタ)アクリレート」の代表的な一例は、式(1)
Figure JPOXMLDOC01-appb-C000030
によって表される(メタ)アクリレートであり、式中、Rは、水素原子またはメチル基であり、Rは、1個またはそれより多くのオキシラン環またはオキセタン環で置換されたアルキル基である。
In the present specification, a typical example of "alkyl (meth) acrylate substituted with an oxygen-containing ring" is the formula (1).
Figure JPOXMLDOC01-appb-C000030
Is a (meth) acrylate represented by, in which R 1 is a hydrogen atom or a methyl group and R 2 is an alkyl group substituted with one or more oxylan or oxetane rings. ..
 本明細書において、「置換可能な数」とは、ある基上の水素を置換基で置換する場合に、生じる基が化学的に安定であることを条件として、置換可能な水素の最大数を意味する。 As used herein, the term "substitutable number" refers to the maximum number of hydrogens that can be substituted when hydrogen on a group is substituted with a substituent, provided that the resulting group is chemically stable. means.
 本明細書において「アルキル基」とは、メタン、エタン、プロパンのような脂肪族炭化水素(アルカン)から水素原子が一つ失われて生ずる1価の基をいい、一般にC2n+1-で表される(ここで、nは正の整数である)。アルキル基は、直鎖または分枝鎖であり得る。炭素数1~4のアルキル(C1~4アルキル)基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基、sec-ブチル基などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。炭素数1~6のアルキル(C1~6アルキル)基としては、例えば、C1~4アルキル基、n-ペンチル基、イソアミル基、n-ヘキシル基、イソヘキシル基などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。炭素数1~10のアルキル(C1~10アルキル)基としては、例えば、C1~6アルキル基、n-オクチル基、n-ノニル基、イソノニル基、分岐型ノニル基、n-デカニル基、イソデシル基などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。炭素数1~18のアルキル(C1~18アルキル)基としては、例えば、C1~10アルキル基、ウンデシル基、ラウリル基、トリデシル基、ミリスチル基、ペンタデシル基、パルミチル基、ヘプタデシル基、ステアリル基、イソステアリル基などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。 As used herein, the term "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). The 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. However, the present disclosure is not limited to such examples. 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.
 本明細書において「アルケニル基」とは、エテン、プロペン、ブテンのような二重結合を少なくとも一つ含有する脂肪族炭化水素(アルケン)から水素原子が一つ失われて生ずる1価の基をいい、一般にC2m-1で表される(ここで、mは2以上の整数である)。アルケニル基は、直鎖または分枝鎖であり得る。炭素数2~6のアルケニル基としては、例えば、エテニル基、1-プロペニル基、2-プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。炭素数2~10のアルケニル基としては、例えば、炭素数2~6のアルケニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。 As used herein, the term "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). The 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. It's not something. Examples of the alkenyl group having 2 to 10 carbon atoms 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.
 本明細書において「アルコキシ基」とは、アルコール類のヒドロキシ基の水素原子が失われて生ずる1価の基をいい、一般にC2n+1O-で表される(ここで、nは1以上の整数である)。炭素数1~6のアルコキシ基としては、例えば、メトキシ基、エトキシ基、n-プロピルオキシ基、イソプロピルオキシ基、n-ブチルオキシ基、イソブチルオキシ基、tert-ブチルオキシ基、sec-ブチルオキシ基、n-ペンチルオキシ基、イソアミルオキシ基、n-ヘキシルオキシ基、イソヘキシルオキシ基などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。 As used herein, the term "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). Examples of the 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.
 本明細書において「ハロアルキル基」とは、上記アルキル基上の1個もしくは複数個の水素原子がハロゲン原子で置換されているアルキル基をいう。また、「ペルハロアルキル」は、上記アルキル基上の全ての水素原子がハロゲン原子で置換されているアルキル基をいう。炭素数1~6のハロアルキル基(C1-6ハロアルキル基)としては、例えば、トリフルオロメチル基、トリフルオロエチル基(2,2,2-トリフルオロエチル基など)、ペルフルオロエチル基、トリフルオロn-プロピル基、テトラフルオロプロピル基(2,2,3,3-テトラフルオロプロピル基など)、ペルフルオロn-プロピル基、トリフルオロイソプロピル基、ペルフルオロイソプロピル基、トリフルオロn-ブチル基、ペルフルオロn-ブチル基、トリフルオロイソブチル基、ペルフルオロイソブチル基、トリフルオロtert-ブチル基、ペルフルオロtert-ブチル基、トリフルオロn-ペンチル基、オクタフルオロペンチル基(2,2,3,3,4,4,5,5-オクタフルオロペンチル基など)、ペルフルオロn-ペンチル基、トリフルオロn-ヘキシル基、ペルフルオロn-ヘキシル基などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。炭素数1~8のハロアルキル基(C1-8ハロアルキル基)としては、C1-6ハロアルキル基、ウンデカフルオロn-ヘプチル基、ペルフルオロn-ヘプチル基、トリデカフルオロオクチル基(3,3,4,4,5,5,6,6,7,7,8,8,8-トリデカフルオロオクチル基など)、ペルフルオロn-オクチル基、などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。 As used herein, the term "haloalkyl group" refers to an alkyl group in which one or more hydrogen atoms on the alkyl group are substituted with halogen atoms. Further, "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 (C 1-6 haloalkyl group) 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.), perfluoron-propyl group, trifluoroisopropyl group, perfluoroisopropyl group, trifluoron-butyl group, perfluoron- Butyl group, trifluoroisobutyl group, perfluoroisobutyl group, trifluorotert-butyl group, perfluorotert-butyl group, trifluoron-pentyl group, octafluoropentyl group (2,2,3,3,4,5) , 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 (C 1-8 haloalkyl group) include a C 1-6 haloalkyl group, an undecafluoro n-heptyl group, a perfluoro n-heptyl group, and a 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.
 本明細書において「シクロアルキル基」とは、単環又は多環式飽和炭化水素基を意味し、架橋された構造のものも含まれる。例えば、「C3-12シクロアルキル基」とは炭素原子数が3~12の環状アルキル基を意味する。C6-12シクロアルキル基の具体例としては、シクロへキシル基、シクロヘプチル基、シクロオクチル基、アダマンチル基、イソボルニル基、2-メチル-2-アダマンチル基、2-エチル-2-アダマンチル基などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。C5-12シクロアルキル基の具体例としては、シクロペンチル基、C6-12シクロアルキル基などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。C3-12シクロアルキル基の具体例としては、シクロプロピル基、シクロブチル基、C5-12シクロアルキル基などが挙げられる。好ましくは、「C6-12シクロアルキル基」が挙げられるが、本開示は、かかる例示のみに限定されるものではない。 As used herein, the term "cycloalkyl group" means a monocyclic or polycyclic saturated hydrocarbon group, and includes those having a crosslinked structure. For example, "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. However, the present disclosure is not limited to such examples. Specific examples of the C 5-12 cycloalkyl group 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.
 本明細書において「シクロアルケニル基」とは、二重結合を含む単環又は多環式不飽和炭化水素基を意味し、架橋された構造のものも含まれる。上記「シクロアルキル基」の炭素間結合の1つ以上が二重結合になったものが挙げられる。例えば、「C3-12シクロアルケニル基」とは炭素原子数が3~12の環状アルケニル基を意味する。具体例として、「C6-12シクロアルケニル基」の場合には、1-シクロへキセニル基、2-シクロへキセニル基、3-シクロへキセニル基、シクロヘプテニル基、シクロオクテニル基、シクロノネニル基等が挙げられる。「C3-12シクロアルキル基」の場合には、シクロプロペニル基、シクロブテニル基、シクロペンテニル基、C6-12シクロアルケニル基等が挙げられる。好ましくは、「C6-12シクロアルケニル基」が挙げられるが、本開示は、かかる例示のみに限定されるものではない。 As used herein, the term "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. For example, "C 3-12 cycloalkenyl group" means a cyclic alkenyl group having 3 to 12 carbon atoms. Specific 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. In the case of "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. Preferably, "C 6-12 cycloalkenyl group" is mentioned, but the present disclosure is not limited to such an example.
 本明細書において「非アリールヘテロシクロアルキル」および「非アリールヘテロ環」とは、その環内に窒素原子、酸素原子および硫黄原子から選択される同種または異種の原子を1~3個有する環式基を意味し、該基は、1つまたは複数の不飽和結合を含んでいてもよいが、芳香族基を含まない。例えば、「3~8員非アリールヘテロシクロアルキル」とは、環構成原子数が3~8個の非アリールヘテロシクロアルキルを意味する。「非アリールヘテロシクロアルキル」の具体例としては、オキシラニル基、オキセタニル基、ピラニル基、ピロリジニル基、イミダゾリジニル基、ピペリジニル基、モルホリニル基、チオモルホリニル基、ヘキサメチレンイミニル基、チアゾリジニル基、テトラヒドロフラニル基、テトラヒドロピリジニル基、テトラヒドロピラニル基、1,3-ジオキソラニル基、1,3-ジオキサニル基、1,4-ジオキサニル基などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。尚、該基には架橋構造を有するものも含まれる。 In the present specification, the "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. For example, "3 to 8-membered non-aryl heterocycloalkyl" means a non-aryl heterocycloalkyl having 3 to 8 ring-constituting atoms. Specific examples of the "non-aryl heterocycloalkyl" 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 hexamethyleneiminal 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 these examples. Absent. The group also includes those having a crosslinked structure.
 本明細書において「酸素含有基」は、構成原子として炭素原子および酸素原子(例えば、1~5個、1~4個、または1~3個)を有する基を意味し、該基は、1つまたは複数の不飽和結合を含んでいてもよく、炭素原子を含まなくてもよいが、芳香族基を含まない。「酸素含有基」の具体例としては、ヒドロキシ基、アルコキシ基(例えば、メトキシ基、エトキシ基など)、アルケニルオキシ基(例えば、ビニルオキシ基、プロペニルオキシ基など)、オキシラニル基、オキセタニル基、テトラヒドロフラニル基、アルケニルオキシアルキル-シクロアルキル-アルキル(例えば、4-(ビニルオキシメチル)シクロヘキサン-1-イルなど)、-(OCHCH-OH、-(OCHCH-OCH=CH(ここで、xは1~4の整数である)などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。 As used herein, the term "oxygen-containing group" means a group having a carbon atom and an oxygen atom (for example, 1 to 5, 1 to 4, or 1 to 3) as constituent atoms, and the group is 1 It may contain one or more unsaturated bonds and may not contain carbon atoms, but it does not contain aromatic groups. Specific examples of the "oxygen-containing group" include a hydroxy group, an alkoxy group (for example, methoxy group, ethoxy group, etc.), an alkenyloxy group (for example, vinyloxy group, propenyloxy group, etc.), an oxylanyl group, an oxetanyl group, and a tetrahydrofuranyl. Group, alkenyloxyalkyl-cycloalkyl-alkyl (eg 4- (vinyloxymethyl) cyclohexane-1-yl, etc.),-(OCH 2 CH 2 ) x- OH,-(OCH 2 CH 2 ) x -OCH = CH 2 (where x is an integer of 1 to 4) and the like can be mentioned, but the present disclosure is not limited to such an example.
 本明細書において「酸素含有環」および「酸素含有環式基」は、環構成原子として炭素原子および1~3個の酸素原子を有する環式基を意味し、該基は、1つまたは複数の不飽和結合を含んでいてもよいが、芳香族基を含まない。例えば、「3~8員酸素含有環」とは、環構成原子数が3~8個の酸素含有環を意味する。「酸素含有環」は、オキシラニル基、テトラヒドロフラニル基、オキセタニル基、1,3-ジオキソラニル基、1,3-ジオキサニル基、1,4-ジオキサニル基などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。尚、該基には架橋構造を有するものも含まれる。 In the present specification, the "oxygen-containing ring" and "oxygen-containing cyclic group" mean a cyclic group having a carbon atom and 1 to 3 oxygen atoms as ring-constituting atoms, and the group may be one or more. May contain unsaturated bonds, but does not contain aromatic groups. For example, the “3 to 8-membered oxygen-containing ring” means an oxygen-containing ring having 3 to 8 ring-constituting atoms. Examples of the "oxygen-containing ring" include an oxylanyl group, a tetrahydrofuranyl group, an oxetanyl group, a 1,3-dioxolanyl group, a 1,3-dioxanyl group, a 1,4-dioxanyl group, and the like. It is not limited to. The group also includes those having a crosslinked structure.
 本明細書において「アリール基」は、芳香族炭化水素の環に結合する水素原子が1個離脱して生ずる基をいう。例えば、ベンゼンからはフェニル基(C-)、トルエンからはトリル基(CH-)、キシレンからはキシリル基((CH-)、ナフタレンからはナフチル基(C10-)が誘導される。「C6~14アリール基」は、炭素数が6~14の芳香族炭化水素基を意味する。「C6~14アリール基」の具体例としては、例えば、フェニル基、1-ナフチル基、2-ナフチル基、アズレニル基、アセナフテニル基、アセナフチル基、アントリル基、フルオレニル基、フェナレニル基、フェナントリル基等が挙げられる。「C6~18アリール基」の具体例としては、例えば、C6~14アリール基、ベンゾ[a]アントリル基、ベンゾ[a]フルオレニル基、ベンゾ[c]フェナントリル基、クリセニル基、フルオランテニル基、ピレニル基、テトラセニル基、トリフェニレニル基などが挙げられる。アリールチオ基とは、アリール-S-基をいう。例えば、フェニル-S-基(フェニルチオ基)などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。 As used herein, the term "aryl group" refers to a group formed by the detachment of one hydrogen atom bonded to the ring of an aromatic hydrocarbon. For example, a phenyl group from the benzene (C 6 H 5 -), tolyl from toluene (CH 3 C 6 H 4 - ), xylyl from xylene ((CH 3) 2 C 6 H 3 -), naphthalene naphthyl group (C 10 H 8 -) is derived. "C 6-14 aryl group" means an aromatic hydrocarbon group having a carbon number of 6 to 14. Specific examples of the "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. Specific examples of the "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. For example, a phenyl-S- group (phenylthio group) and the like can be mentioned, but the present disclosure is not limited to such an example.
 本明細書において「ヘテロアリール基」は、単環式もしくは多環式のヘテロ原子含有芳香族基を意味し、該基は、窒素原子、硫黄原子および酸素原子から選択される同種または異種のヘテロ原子を1個以上(例えば1~4個)含む。例えば、「5~18員ヘテロアリール基」は、環構成原子数が5~18個のヘテロアリール基を意味する。「ハロヘテロアリール基」は、環構成原子上の1個または複数個の水素がハロゲンで置換されているものを指す。「ヘテロアリール基」の具体例としては、例えば、ピロリル基、チエニル基、ベンゾチエニル基、ベンゾフラニル基、ベンゾオキサゾリル基、ベンゾチアゾリル基、フリル基、オキサゾリル基、チアゾリル基、イソオキサゾリル基、イソチアゾリル基、ベンゾイソオキサゾリル基、ベンゾイソチアゾリル基、イミダゾリル基、ピラゾリル基、ピリジル基、ピラジル基、ピリミジル基、ピリダジル基、キノリル基、イソキノリル基、トリアゾリル基、トリアジニル基、テトラゾリル基、インドリル基、イミダゾ[1,2-a]ピリジル基、ピラゾロ[1,5-a]ピリジル基、[1,2,4]トリアゾロ[1,5-a]ピリジル基、ベンゾイミダゾリル基、キノキサリル基、シンノリル基、キナゾリル基、インダゾリル基、ナフチリジル基、キノリノリル基、イソキノリノリル基等が挙げられるが、本開示は、かかる例示のみに限定されるものではない。 As used herein, the term "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). For example, "5- to 18-membered 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. Specific examples of the "heteroaryl group" 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. Benzoisooxazolyl group, benzoisothiazolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazil group, pyrimidyl group, pyridadyl group, quinolyl group, isoquinolyl group, triazolyl group, triazinyl group, tetrazolyl group, indolyl group, imidazole group [1,2-a] pyridyl group, pyrazolo [1,5-a] pyridyl group, [1,2,4] triazolo [1,5-a] pyridyl group, benzoimidazolyl group, quinoxalyl group, synnolyl group, quinazolyl group , Indazolyl group, naphthylidyl group, quinolinolyl group, isoquinolinolyl group and the like, but the present disclosure is not limited to such examples.
 通常、用語「置換(されている)」は、特定の置換基のラジカルによる、所与の構造における1つ以上の水素ラジカルとの置き換えのことを指す。句「置換されていてもよい」は、句「非置換または置換(の)」と互換的に使用されることが認識される。例えば、「C1~10アルキル基で置換されていてもよいC6~18アリール基」は、「非置換C6~18アリール基、またはC1~10アルキル基で置換されているC6~18アリール基」と同義である。本明細書において、「置換(されている)」または「置換されていてもよい」を用いて定義される基における置換基の数は、置換可能であれば特に制限はなく、1または複数である。また、特に指示した場合を除き、各々の基の説明はその基が他の基の一部分または置換基である場合にも該当する。「置換基」の定義における炭素原子の数を、例えば、「C1-6」等と表記する場合もある。具体的には、「C1-6アルキル」なる表記は、炭素数1から6のアルキル基と同義である。また、本明細書において、「置換(されている)」または「置換されていてもよい」なる用語を特に明示していない置換基については、「非置換」の置換基を意味する。 Usually, the term "substituent" 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". For example, "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". In the present specification, 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. Further, in the present specification, a substituent that does not specifically specify the term "substituted" or "may be substituted" means a "unsubstituted" substituent.
 本明細書において「酸素含有基で置換されたアルキル基」は、上記アルキル基上の1個の水素原子が酸素含有基で置換されているアルキル基、および(2)アルキル基の同一炭素上の2個の水素原子が置換されて、該炭素を環原子として含む酸素含有環を形成している、アルキル基をいう。酸素含有基で置換されたアルキル基の酸素含有基は、非置換であってもよく、C1~6アルキル基および/またはビニルオキシ基で置換されていてもよい。酸素含有基で置換されたアルキル基の例としては、2-メトキシエチル、2-ヒドロキシエチル、3-ヒドロキシプロピル、3-(ビニルオキシ)プロピル、4-ヒドロキシブチル、4-(ビニルオキシ)ブチル、2,3-エポキシプロピル、(3-エチルオキセタン-3-イル)メチル、テトラヒドロフルフリル、(2-エチル-2-メチル-1,3-ジオキソラン-4-イル)メチル、[4-(ビニルオキシメチル)シクロヘキシル]メチル、[4-(ヒドロキシメチル)シクロヘキシル]メチル、-(CHCHO)-H、-(CHCHO)-CH=CH(ここで、xは1~5の整数である)等が挙げられるが、本開示は、かかる例示のみに限定されるものではない。 In the present specification, the "alkyl group substituted with an oxygen-containing group" refers to an alkyl group in which one hydrogen atom on the alkyl group is substituted with an oxygen-containing group, and (2) on the same carbon of the alkyl group. An alkyl group in which two hydrogen atoms are substituted to form an oxygen-containing ring containing the carbon as a ring atom. The oxygen-containing group of the alkyl group substituted with the oxygen-containing group may be unsubstituted or substituted with a C1 to 6 alkyl group and / or a vinyloxy group. Examples of alkyl groups substituted with oxygen-containing groups include 2-methoxyethyl, 2-hydroxyethyl, 3-hydroxypropyl, 3- (vinyloxy) propyl, 4-hydroxybutyl, 4- (vinyloxy) butyl, 2, 3-Epoxypropyl, (3-ethyloxetane-3-yl) methyl, tetrahydrofurfuryl, (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl, [4- (vinyloxymethyl) Cyclohexyl] methyl, [4- (hydroxymethyl) cyclohexyl] methyl,-(CH 2 CH 2 O) x- H,-(CH 2 CH 2 O) x -CH = CH 2 (where x is 1-5 (It is an integer of), etc., but the present disclosure is not limited to such an example.
 本明細書において「酸素含有基で置換されたシクロアルキル基」は、上記シクロアルキル基上の1個の水素原子が酸素含有基で置換されているアルキル基、および(2)シクロアルキル基の同一炭素上の2個の水素原子が置換されて、該炭素を環原子として含む酸素含有環を形成している、シクロアルキル基をいう。酸素含有基で置換されたシクロアルキル基の酸素含有基は、非置換であってもよく、C1~6アルキル基および/またはビニルオキシ基で置換されていてもよい。酸素含有基で置換されたシクロアルキル基の例としては、4-(ビニルオキシメチル)シクロヘキシル、4-(ヒドロキシメチル)シクロヘキシル等が挙げられるが、本開示は、かかる例示のみに限定されるものではない。 In the present specification, the "cycloalkyl group substituted with an oxygen-containing group" is the same as the alkyl group in which one hydrogen atom on the cycloalkyl group is substituted with an oxygen-containing group, and (2) the cycloalkyl group. A cycloalkyl group in which two hydrogen atoms on a carbon are substituted to form an oxygen-containing ring containing the carbon as a ring atom. The oxygen-containing group of the cycloalkyl group substituted with the oxygen-containing group may be unsubstituted or substituted with a C1 to 6 alkyl group and / or a vinyloxy group. Examples of cycloalkyl groups substituted with oxygen-containing groups include 4- (vinyloxymethyl) cyclohexyl, 4- (hydroxymethyl) cyclohexyl and the like, but the present disclosure is not limited to such examples. Absent.
 本明細書において「酸素含有環で置換されたアルキル基」は、(1)上記アルキル基上の1個の水素原子が酸素含有環で置換されているアルキル基、および(2)アルキル基の同一炭素上の2個の水素原子が置換されて、該炭素を環原子として含む酸素含有環を形成している、アルキル基をいう。酸素含有環で置換されたアルキル基の酸素含有環は、非置換であってもよく、C1~6アルキル基で置換されていてもよい。酸素含有環で置換されたアルキル基の例としては、2,3-エポキシプロピル、(3-エチルオキセタン-3-イル)メチル、テトラヒドロフルフリル、(2-エチル-2-メチル-1,3-ジオキソラン-4-イル)メチル、(5-エチル-1,3-ジオキサン-5-イル)メチル等が挙げられるが、本開示は、かかる例示のみに限定されるものではない。 In the present specification, the "alkyl group substituted with an oxygen-containing ring" refers to (1) an alkyl group in which one hydrogen atom on the alkyl group is substituted with an oxygen-containing ring, and (2) the same alkyl group. An alkyl group in which two hydrogen atoms on a carbon are substituted to form an oxygen-containing ring containing the carbon as a ring atom. The oxygen-containing ring of the alkyl group substituted with the oxygen-containing ring may be unsubstituted or substituted with a C 1 to 6 alkyl group. Examples of alkyl groups substituted with an oxygen-containing ring include 2,3-epoxypropyl, (3-ethyloxetane-3-yl) methyl, tetrahydrofurfuryl, (2-ethyl-2-methyl-1,3-). Examples thereof include dioxolane-4-yl) methyl, (5-ethyl-1,3-dioxane-5-yl) methyl, and the like, but the present disclosure is not limited to such examples.
 本明細書において、「ポリマー」とは、複数のモノマーが重合することによってできた化合物をいう。この場合、モノマーは「出発物質(材料)」であり、ポリマーは生成物(最終生成物)である。 In the present specification, the "polymer" means a compound formed by polymerizing a plurality of monomers. In this case, the monomer is the "starting material (material)" and the polymer is the product (final product).
 本明細書において、「ホモポリマー」とは、1種のみのモノマーが重合することによってできた化合物であり、「コポリマー」とは、2種もしくは2種超のモノマーが重合することによってできた化合物である。 As used herein, a "homopolymer" is a compound formed by polymerizing only one type of monomer, and a "copolymer" is a compound formed by polymerizing two or more types of monomers. Is.
 本明細書において、「モノマー成分を含むコポリマー」とは、当該モノマー成分を重合して生成されるコポリマーをいう。 In the present specification, the "copolymer containing a monomer component" means a copolymer produced by polymerizing the monomer component.
 本明細書において、モノマーAのコポリマーとは、含まれるモノマーの一種がモノマーAであるコポリマーを意味する。 In the present specification, the copolymer of monomer A means a copolymer in which one of the contained monomers is monomer A.
 本明細書において、「(メタ)アクリレート」は、アクリレートまたはメタクリレートを意味し、アクリレートおよびメタクリレートは、それぞれ単独で用いてもよく、併用してもよい。「(メタ)アクリロイルオキシ」は、アクリロイルオキシまたはメタクリロイルオキシを意味し、アクリロイルオキシおよびメタクリロイルオキシは、それぞれ単独で用いてもよく、併用してもよい。「(メタ)アクリル酸」は、アクリル酸またはメタクリル酸を意味し、アクリル酸およびメタクリル酸は、それぞれ単独で用いてもよく、併用してもよい。 In the present specification, "(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.
 本明細書において、「(メタ)アクリルポリマー」および「(メタ)アクリル系ポリマー」は、(メタ)アクリル酸もしくは(メタ)アクリレートまたはその塩もしくは誘導体などのホモポリマーまたはコポリマーをいう。 In the present specification, "(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.
 本明細書において、「モノマー」とは、それが2個以上重合してポリマーを生ずる化合物をいう。本開示のモノマーの例としては、(メタ)アクリル系モノマー、エチレン系モノマー、ウレタン系モノマー、アミド系モノマー、エステル系モノマー、エーテル系モノマー、イミド系モノマー、アミド-イミド系モノマー、カーボネート系モノマー、アセタール系モノマー、スルホン系モノマー、フェニレンスルフィド系モノマー、ビニルエーテル系モノマー、エーテルエーテルケトン系モノマー、シリコーン系モノマー、スチレン系モノマー、ブタジエン系モノマーおよびAES樹脂、ジアリルフタレート樹脂、ABS樹脂、もしくはシリコーン樹脂などを重合により形成するモノマーが挙げられる。 In the present specification, the "monomer" means a compound obtained by polymerizing two or more of them to form a polymer. Examples of the monomers of the present disclosure include (meth) acrylic monomers, ethylene-based monomers, urethane-based monomers, amide-based monomers, ester-based monomers, ether-based monomers, imide-based monomers, amide-imide-based monomers, and carbonate-based monomers. Acetal monomer, sulfone monomer, phenylene sulfide monomer, vinyl ether monomer, ether ether ketone monomer, silicone monomer, styrene monomer, butadiene monomer and AES resin, diallyl phthalate resin, ABS resin, silicone resin, etc. Examples thereof include monomers formed by polymerization.
 本明細書において、「ビニルエーテルモノマー」および「ビニルエーテル系モノマー」とは、交換可能に使用され、ビニルオキシ基(即ち、-O-CH=CH)を含むモノマーである。その例としては、4-ヒドロキシブチルビニルエーテル(HBVE)の他、2-ヒドロキシエチルビニルエーテル(HEVE)、ジエチレングリコールモノビニルエーテル(DEGV)、n-プロピルビニルエーテル(NPVE)、イソプロピルビニルエーテル(IPVE)、n-ブチルビニルエーテル(NBVE)、イソブチルビニルエーテル(IBVE)、2-エチルヘキシルビニルエーテル(2-EHVE)、シクロヘキシルビニルエーテル(CHVE)、1,4-シクロヘキサンジメタノール モノビニルエーテル(CHMVE)、1,4-ブタンジオールジビニルエーテル(BDVE)、トリエチレングリコールジビニルエーテル(TEGDVE)、ジエチレングリコールジビニルエーテル(DEGDVE)、1,4-シクロヘキサンジメタノール ジビニルエーテル(CHDVE)等が挙げられるが、本開示は、かかる例示のみに限定されるものではない。 As used herein, the "vinyl ether monomer" and the "vinyl ether-based monomer" are monomers that are interchangeably used and contain a vinyl oxy group (that is, —O—CH = CH 2 ). Examples include 4-hydroxybutyl vinyl ether (HBVE), 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEVGV), n-propyl vinyl ether (NPVE), isopropyl vinyl ether (IPVE), and n-butyl vinyl ether. (NBVE), isobutyl vinyl ether (IBVE), 2-ethylhexyl vinyl ether (2-EHVE), cyclohexyl vinyl ether (CHVE), 1,4-cyclohexanedimethanol monovinyl ether (CHMVE), 1,4-butanediol divinyl ether (BDVE) , Triethylene glycol divinyl ether (TEGDVE), diethylene glycol divinyl ether (DEGDVE), 1,4-cyclohexanedimethanol divinyl ether (CHDVE) and the like, but the present disclosure is not limited to these examples.
 本明細書において「焼結」(sintering)とは原料粉末が高温で焼き固まる現象をいい、原料粉末の粒子間に隙間が見られるが、高温環境下(融点よりも低い温度)で焼結が起こると、粒子間の接触面積が増加して隙間が減少し、焼き固まる。残った隙間を「空隙」又は「空孔」という。 In the present specification, "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".
 本明細書において「キット」とは、通常2つ以上の区画に分けて、提供されるべき部分(例えば、コーティング成分、導電成分、溶剤、説明書など)が提供されるユニットをいう。安定性等のため、混合されて提供されるべきでなく、使用直前に混合して使用することが好ましいような組成物の提供を目的とするときに、このキットの形態は好ましい。そのようなキットは、好ましくは、提供される部分(例えば、導電成分、コーティング成分)をどのように使用するか、あるいは、試薬あるいは使用後の廃液をどのように処理すべきかを記載する指示書または説明書を備えていることが有利である。本明細書においてキットが使用される場合、キットには、通常、溶剤等の使い方などを記載した指示書などを含み得る。 In the present specification, 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. When the kit is used in the present specification, the kit may usually include instructions and the like that describe how to use the solvent and the like.
 (導電材の基本的な説明)
 本開示において提供される導電材は、当該分野で入手可能な任意の導電成分を含む。本開示の導電材は、本開示において提供される焼成温度を低下させるための組成物(焼成温度低下剤ともいう)を含むことにより、導電材を得るための焼成温度が低下することが特徴である。
(Basic explanation of conductive material)
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 firing temperature for obtaining the conductive material is lowered by containing the composition (also referred to as a firing temperature lowering agent) for lowering the firing temperature provided in the present disclosure. is there.
 本開示の導電材は、代表的に、導電成分の他基材を含み得る。 The conductive material of the present disclosure may typically contain other substrates of conductive components.
 (焼成温度低下剤の基本的な説明)
 本開示において提供される、導電材の焼成温度を低下させるための組成物(焼成温度低下剤)は、式(4)
Figure JPOXMLDOC01-appb-C000031
によって表される化合物を含む。式(4)において、Rは、水素原子またはメチル基であり、Rは、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であり、nは、0または1の整数である。
(Basic explanation of firing temperature lowering agent)
The composition (calcination temperature lowering agent) for lowering the firing temperature of the conductive material provided in the present disclosure is the formula (4).
Figure JPOXMLDOC01-appb-C000031
Includes compounds represented by. In formula (4), 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. , Substituted or unsubstituted aryl group, or substituted or unsubstituted heteroaryl group, where n is an integer of 0 or 1.
 代表的な実施形態において、本開示において提供される式(4)により表される化合物は、含まれる酸素含有基もしくは酸素含有環の種類、アルキル基の形態(炭素数、分岐・直鎖の状態など)、シクロアルキル基の形態(炭素数など)、メタクリルオキシ(n=1、R=メチル)、アクリルオキシ(n=1、R=H)、ビニルオキシ(n=0、R=H)、1-プロペン-2-イルオキシ(n=0、R=メチル)の別などにかかわらず、いずれも焼成温度を低下させるものである。 In a typical embodiment, the compound represented by the formula (4) provided in the present disclosure includes an oxygen-containing group or an oxygen-containing ring type, and an alkyl group form (carbon number, branched / linear state). Etc.), Cycloalkyl group morphology (carbon number, etc.), methacryloxy (n = 1, R 1 = methyl), acrylic oxy (n = 1, R 1 = H), vinyl oxy (n = 0, R 1 = H) ), 1-Propen-2-yloxy (n = 0, R 1 = methyl), etc., all of which lower the firing temperature.
 1つの実施形態では、Rが、酸素含有基で置換されていてもよいアルキル基またはシクロアルキル基である。 In one embodiment, R 2 is an alkyl or cycloalkyl group that may be substituted with an oxygen-containing group.
 1つの実施形態では、Rが、酸素含有基で置換されたアルキル基である。 In one embodiment, R 2 is an alkyl group substituted with an oxygen-containing group.
 1つの実施形態では、Rが、酸素含有環で置換されたアルキル基である。 In one embodiment, R 2 is an alkyl group substituted with an oxygen-containing ring.
 1つの実施形態では、式(4)により表される化合物が、酸素含有基で置換されたアルキル(メタ)アクリレートである。 In one embodiment, the compound represented by the formula (4) is an alkyl (meth) acrylate substituted with an oxygen-containing group.
 1つの実施形態では、式(4)により表される化合物が、酸素含有環で置換されたアルキル(メタ)アクリレートである。 In one embodiment, the compound represented by the formula (4) is an alkyl (meth) acrylate substituted with an oxygen-containing ring.
 1つの実施形態では、n=0である。1つの実施形態では、n=0であり、Rが、酸素含有基で置換されていてもよいアルキル基またはシクロアルキル基である In one embodiment, n = 0. In one embodiment, n = 0 and R 2 is an alkyl or cycloalkyl group optionally substituted with an oxygen-containing group.
 1つの実施形態では、n=0であり、式(4)により表される化合物が1個もしくは2個またはそれより多くのビニルオキシ基を有する。 In one embodiment, n = 0 and the compound represented by the formula (4) has one or two or more vinyloxy groups.
 1つの実施形態では、前記組成物(焼成温度低下剤)は、酸素含有基で置換されたアルキル(メタ)アクリレートを含む。1つの実施形態では、前記組成物(焼成温度低下剤)はまた、酸素含有環で置換されたアルキル(メタ)アクリレートを含む。1つの実施形態では、前記組成物(焼成温度低下剤)は、nが0であり、式(4)により表される化合物を含む。1つの実施形態では、前記組成物(焼成温度低下剤)は、nが0であり、Rが水素原子である式(4)により表される化合物を含む。 In one embodiment, the composition (calcination temperature lowering agent) comprises an alkyl (meth) acrylate substituted with an oxygen-containing group. In one embodiment, the composition (calcination temperature lowering agent) also comprises an alkyl (meth) acrylate substituted with an oxygen-containing ring. In one embodiment, the composition (calcination temperature lowering agent) comprises a compound having n of 0 and represented by the formula (4). In one embodiment, the composition (calcination temperature lowering agent) comprises a compound represented by the formula (4) in which n is 0 and R 1 is a hydrogen atom.
 1つの実施形態において、本開示において提供される酸素含有環で置換されたアルキル(メタ)アクリレートの一例は、式(1)
Figure JPOXMLDOC01-appb-C000032
によって表され、含まれる酸素含有環の種類、アルキル基の形態(炭素数、分岐・直鎖の状態など)、メタクリル、アクリルの別などにかかわらず、いずれも焼成温度を低下させるものである。
In one embodiment, an example of an alkyl (meth) acrylate substituted with an oxygen-containing ring provided in the present disclosure is of formula (1).
Figure JPOXMLDOC01-appb-C000032
Regardless of the type of oxygen-containing ring contained, the form of the alkyl group (carbon number, branched / linear state, etc.), methacrylic, acrylic, etc., all of them lower the firing temperature.
 1つの実施形態では、前記導電材が、式(4)により表される化合物のホモポリマーもしくはコポリマーおよび導電成分を含む。 In one embodiment, the conductive material comprises a homopolymer or copolymer of a compound represented by the formula (4) and a conductive component.
 1つの実施形態では、前記導電材が、前記酸素含有基で置換されたアルキル(メタ)アクリレートのホモポリマーもしくはコポリマーおよび導電成分を含む。 In one embodiment, the conductive material comprises a homopolymer or copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing group and a conductive component.
 1つの実施形態では、前記導電材が、前記酸素含有環で置換されたアルキル(メタ)アクリレートのホモポリマーもしくはコポリマーおよび導電成分を含む。 In one embodiment, the conductive material comprises a homopolymer or copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing ring and a conductive component.
 1つの実施形態では、前記コポリマーが、式(4)により表される化合物と、第2の(メタ)アクリルモノマーとのコポリマーである。 In one embodiment, the copolymer is a copolymer of a compound represented by the formula (4) and a second (meth) acrylic monomer.
 1つの実施形態では、前記コポリマーが、前記酸素含有基で置換されたアルキル(メタ)アクリレートと、第2の(メタ)アクリルモノマーとのコポリマーである。 In one embodiment, the copolymer is a copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing group and a second (meth) acrylic monomer.
 1つの実施形態では、前記コポリマーが、前記酸素含有環で置換されたアルキル(メタ)アクリレートと、第2の(メタ)アクリルモノマーとのコポリマーである。 In one embodiment, the copolymer is a copolymer of an alkyl (meth) acrylate substituted with the oxygen-containing ring and a second (meth) acrylic monomer.
 1つの実施形態では、Rが、酸素含有基で置換されていてもよいアルキル基またはシクロアルキル基であり、前記酸素含有基が、ヒドロキシ、ヒドロキシアルキル、ビニルオキシアルキル、アルコキシ、オキシラン環もしくはオキセタン環、または-(CHCHO)-Rであり、Rが水素またはビニルであり、yが1から5の整数である。 In one embodiment, R 2 is an alkyl or cycloalkyl group optionally substituted with an oxygen-containing group, wherein the oxygen-containing group is a hydroxy, hydroxyalkyl, vinyloxyalkyl, alkoxy, oxylan ring or oxetane. The ring, or-(CH 2 CH 2 O) y- R 7 , where R 7 is hydrogen or vinyl and y is an integer from 1 to 5.
 1つの実施形態では、前記酸素含有基が、アルコキシ、オキシラン環またはオキセタン環である。 In one embodiment, the oxygen-containing group is an alkoxy, oxylan ring or oxetane ring.
 1つの実施形態では、前記酸素含有環が、オキシラン環またはオキセタン環である。 In one embodiment, the oxygen-containing ring is an oxylan ring or an oxetane ring.
 1つの実施形態では、前記酸素含有基が、ヒドロキシまたはアルコキシである。 In one embodiment, the oxygen-containing group is hydroxy or alkoxy.
 1つの実施形態では、Rが、ビニルオキシもしくはヒドロキシで置換されていてもよいアルキル基、シクロアルキル基、もしくはアルキルシクロアルキルアルキル基、または-(CHCHO)-Rであり、Rが水素またはビニルであり、yが1以上の整数である。 In one embodiment, R 2 is an alkyl group, a cycloalkyl group, or an alkylcycloalkylalkyl group that may be substituted with vinyloxy or hydroxy, or-(CH 2 CH 2 O) y- R 7 . R 7 is hydrogen or vinyl, and y is an integer of 1 or more.
 1つの実施形態では、Rは、水素原子またはメチル基であり、Rは、ヒドロキシ、アルコキシ、オキシラン環およびオキセタン環からなる群より選択される1個から置換可能数までの置換基で置換されたアルキル基である。 In one embodiment, R 1 is a hydrogen atom or a methyl group and R 2 is substituted with one to a substitutable substituent selected from the group consisting of hydroxy, alkoxy, oxylan and oxetane rings. Alkoxy group.
 1つの実施形態では、前記酸素含有基で置換されたアルキル(メタ)アクリレートが、式(1)
Figure JPOXMLDOC01-appb-C000033
によって表され、Rは、水素原子またはメチル基であり、Rは、アルコキシ、オキシラン環およびオキセタン環からなる群より選択される1個から置換可能数までの置換基で置換されたアルキル基である。
In one embodiment, the alkyl (meth) acrylate substituted with the oxygen-containing group is the formula (1).
Figure JPOXMLDOC01-appb-C000033
Represented by, R 1 is a hydrogen atom or a methyl group, and R 2 is an alkyl group substituted with one to a substitutable number selected from the group consisting of an alkoxy, an oxylan ring and an oxetane ring. Is.
 1つの実施形態では、前記酸素含有環で置換されたアルキル(メタ)アクリレートが、式(1)
Figure JPOXMLDOC01-appb-C000034
によって表され、Rは、水素原子またはメチル基であり、Rは、1個またはそれより多くのオキシラン環またはオキセタン環で置換されたアルキル基である。
In one embodiment, the alkyl (meth) acrylate substituted with the oxygen-containing ring is the formula (1).
Figure JPOXMLDOC01-appb-C000034
Represented by, R 1 is a hydrogen atom or a methyl group and R 2 is an alkyl group substituted with one or more oxylan or oxetane rings.
 1つの実施形態では、Rは、水素原子またはメチル基であり、Rが、ビニルオキシもしくはヒドロキシで置換されていてもよいアルキル基、シクロアルキル基、もしくはアルキルシクロアルキルアルキル基、または-(CHCHO)-Rであり、Rが水素またはビニルであり、yが1から5の整数であり、n=0である。 In one embodiment, R 1 is a hydrogen atom or a methyl group and R 2 is an alkyl group, a cycloalkyl group, or an alkylcycloalkylalkyl group, which may be substituted with vinyloxy or hydroxy, or-(CH). 2 CH 2 O) y- R 7 , where R 7 is hydrogen or vinyl, y is an integer from 1 to 5, and n = 0.
 1つの実施形態では、n=0のとき、Rは水素原子である。 In one embodiment, when n = 0, R 1 is a hydrogen atom.
 1つの実施形態では、前記第2の(メタ)アクリルモノマーは、式(2)
Figure JPOXMLDOC01-appb-C000035
によって表され、
は、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは、酸素含有環で置換されたアルキル基でも、アルコキシ置換されたアルキルでもない。
In one embodiment, the second (meth) acrylic monomer is of formula (2).
Figure JPOXMLDOC01-appb-C000035
Represented by
R 3 is a hydrogen atom or a methyl group and
R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkoxy-substituted alkyl.
 1つの実施形態では、式(4)により表される化合物が、4-ヒドロキシブチルビニルエーテル、2-メトキシエチルアクリレート、(3-エチルオキセタン-3-イル)メチルアクリレートまたは2,3-エポキシプロピルメタクリレートである。 In one embodiment, the compound represented by formula (4) is 4-hydroxybutyl vinyl ether, 2-methoxyethyl acrylate, (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate. is there.
 1つの実施形態では、前記酸素含有基で置換されたアルキル(メタ)アクリレートが、2-メトキシエチルアクリレート、(3-エチルオキセタン-3-イル)メチルアクリレートまたは2,3-エポキシプロピルメタクリレートである。 In one embodiment, the alkyl (meth) acrylate substituted with the oxygen-containing group is 2-methoxyethyl acrylate, (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate.
 1つの実施形態では、前記酸素含有環で置換されたアルキル(メタ)アクリレートが、(3-エチルオキセタン-3-イル)メチルアクリレートまたは2,3-エポキシプロピルメタクリレートである。 In one embodiment, the alkyl (meth) acrylate substituted with the oxygen-containing ring is (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate.
 1つの実施形態では、式(4)により表される化合物が、4-ヒドロキシブチルビニルエーテルである。 In one embodiment, the compound represented by the formula (4) is 4-hydroxybutyl vinyl ether.
 1つの実施形態では、前記第2の(メタ)アクリルモノマーが、エチルアクリレート、ステアリルアクリレート、イソステアリルアクリレートまたはラウリルアクリレートである。 In one embodiment, the second (meth) acrylic monomer is ethyl acrylate, stearyl acrylate, isostearyl acrylate or lauryl acrylate.
 1つの好ましい実施形態では、式(4)により表される化合物が、(3-エチルオキセタン-3-イル)メチルアクリレートまたは2,3-エポキシプロピルメタクリレートであり、前記第2の(メタ)アクリルモノマーが、イソステアリルアクリレートである。1つの好ましい実施形態では、式(4)により表される化合物が、(3-エチルオキセタン-3-イル)メチルアクリレートであり、前記第2の(メタ)アクリルモノマーが、イソステアリルアクリレートである。1つの好ましい実施形態では、式(4)により表される化合物が、2,3-エポキシプロピルメタクリレートであり、前記第2の(メタ)アクリルモノマーが、イソステアリルアクリレートである。 In one preferred embodiment, the compound represented by formula (4) is (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate, said second (meth) acrylic monomer. Is isostearyl acrylate. In one preferred embodiment, the compound represented by formula (4) is (3-ethyloxetane-3-yl) methyl acrylate and the second (meth) acrylic monomer is isostearyl acrylate. In one preferred embodiment, the compound represented by the formula (4) is 2,3-epoxypropyl methacrylate, and the second (meth) acrylic monomer is an isostearyl acrylate.
 1つの好ましい実施形態では、式(4)により表される化合物が、4-ヒドロキシブチルビニルエーテルまたは2-メトキシエチルアクリレートであり、前記第2の(メタ)アクリルモノマーが、エチルアクリレートである。1つの好ましい実施形態では、式(4)により表される化合物が、2-メトキシエチルアクリレートであり、前記第2の(メタ)アクリルモノマーが、エチルアクリレートである。1つの好ましい実施形態では、式(4)により表される化合物が、4-ヒドロキシブチルビニルエーテルであり、前記第2の(メタ)アクリルモノマーが、エチルアクリレートである。 In one preferred embodiment, the compound represented by the formula (4) is 4-hydroxybutyl vinyl ether or 2-methoxyethyl acrylate, and the second (meth) acrylic monomer is ethyl acrylate. In one preferred embodiment, the compound represented by the formula (4) is 2-methoxyethyl acrylate, and the second (meth) acrylic monomer is ethyl acrylate. In one preferred embodiment, the compound represented by formula (4) is 4-hydroxybutyl vinyl ether and the second (meth) acrylic monomer is ethyl acrylate.
 焼成温度低下剤の基本的な使用方法は、以下のとおりである。 The basic usage of the firing temperature lowering agent is as follows.
 (焼成温度低下剤が対象とする導電材)
 本開示の焼成温度低下剤が対象とし得る導電材は、任意の導電成分およびポリマーマトリクスを含有する材料であり、好ましくは任意の導電成分が金属系成分を含み、さらに好ましくは任意の導電成分が金属成分を含むものである。
(Conductive material targeted by firing temperature lowering agent)
The conductive material that can be targeted by the firing temperature lowering agent of the present disclosure is a material containing an arbitrary conductive component and a polymer matrix, preferably any conductive component contains a metal-based component, and more preferably any conductive component. It contains a metal component.
 (導電材の一般製法)
 (1)ポリマーマトリクスの製造方法
 代表的な実施形態において、本開示のポリマーマトリクスは、モノマーを加熱することで、および/または、モノマーに特定の照度の紫外線を照射して重合させることにより調製できる。このような紫外線照射は当業者が任意に設定して実施することができる。ポリマーマトリクスを調製する際に、紫外線を使用して重合させて調製した場合、煩雑な操作である溶媒を除去するための乾燥操作が不要であり、作業性に優れる。
(General manufacturing method of conductive material)
(1) Method for Producing Polymer Matrix In a typical embodiment, 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. When the polymer matrix is prepared by polymerizing using ultraviolet rays, a drying operation for removing the solvent, which is a complicated operation, is not required, and the workability is excellent.
 ここで、紫外線とは、可視光線より波長が短く、X線より波長の長い電磁波をいう。上限の可視光の短波長端は400nmであり、紫外線はこれ以下の波長をもつ電磁波と定義され得る。紫外線の波長の下限は10nm程度であり、これより長い波長を有する電磁波であれば紫外線の範疇に入ると理解される。本開示において用いられる紫外線の波長は、どのような波長でもよく、目的に応じて適切なものを選択することができる。例えば、本開示において、モノマーに対して初期の効果を奏することができる限りどの波長のものでもよい。代表的には、実施例において使用される光源によって照射され得る波長のものである。具体的には150nm~400nm程度の光源が使用され、好ましくは300nm~400nmである。 Here, 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. For example, in the present disclosure, any wavelength may be used as long as it can exert an initial effect on the monomer. Typically, it is of a wavelength that can be emitted by the light source used in the examples. Specifically, a light source of about 150 nm to 400 nm is used, preferably 300 nm to 400 nm.
 本開示で用いられる紫外線の好ましい照度は、出発物質により異なる。紫外線照射装置は特に限定されるものではなく、例えば、低圧水銀ランプ、中圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、メタルハライドランプ、ブラックライトランプ、UV無電極ランプ、ショートアークランプ、LED等が挙げられる。 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.
 モノマーを重合させる際には、重合開始剤を用いることが好ましい。重合開始剤としては、例えば、熱重合開始剤、光重合開始剤、レドックス重合開始剤、ATRP(原子移動ラジカル重合)開始剤、ICAR ATRP開始剤、ARGET ATRP開始剤、RAFT(可逆的付加-開裂連鎖移動重合)剤、NMP(ニトロキシドを介した重合)剤、高分子重合開始剤などが挙げられる。これらの重合開始剤は、それぞれ単独で用いてもよく、2種類以上を併用してもよい。これらの重合開始剤のなかでは、ポリマーマトリクスに熱履歴を残さないようにする観点から、光重合開始剤が好ましい。 When polymerizing the monomer, it is preferable to use a polymerization initiator. Examples of 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). 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. Among these polymerization initiators, a photopolymerization initiator is preferable from the viewpoint of not leaving a thermal history in the polymer matrix.
 光重合開始剤としては、例えば、2,4,6-トリメチルベンゾイルジフェニルホスフィンオキシド、2,2’-ビス(o-クロロフェニル)-4,4’,5,5’-テトラフェニル-1,1’-ビイミダゾール、2,4,6-トリス(トリクロロメチル)-1,3,5-トリアジン、2,4-ビス(トリクロロメチル)-6-(p-メトキシフェニルビニル)-1,3,5-トリアジン、ジフェニルヨードニウムテトラフルオロボレート、ジフェニルヨードニウムヘキサフルオロホスフェート、4,4’-ジtert-ブチルジフェニルヨードニウムテトラフルオロボレート、4-ジエチルアミノフェニルベンゼンジアゾニウムヘキサフルオロホスフェート、ベンゾイン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-2-オン、ベンゾフェノン、チオキサントン、2,4,6-トリメチルベンゾイルジフェニルアシルホスフィンオキシド、トリフェニルブチルボレートテトラエチルアンモニウム、ジフェニル-4-フェニルチオフェニルスルホニウムヘキサフルオロホスフェート、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、フェニルグリオキシリックアシッドメチルエステル、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノプロパン-1-オン、ビス(2,4,6-トリメチルベンゾイル)-フェニルホスフィンオキシド、1,2-オクタンジオン,1-[4-(フェニルチオ)-2-(o-ベンゾイルオキシム)]、ビス(η5-2,4-シクロペンタジエン-1-イル)ビス〔2,6-ジフルオロ-3-(1H-ピロール-1-イル)フェニルチタニウム〕などの光ラジカル重合開始剤、2,4,6-トリス(トリクロロメチル)-1,3,5-トリアジン、2,4-ビス(トリクロロメチル)-6-(p-メトキシフェニルビニル)-1,3,5-トリアジン、ジフェニルヨードニウムテトラフルオロボレート、4,4’-ジtert-ブチルジフェニルヨードニウムテトラフルオロボレート、4-ジエチルアミノフェニルベンゼンジアゾニウムヘキサフルオロホスフェート、ジフェニル-4-フェニルチオフェニルスルホニウムヘキサフルオロホスフェートなどの光カチオン開環重合開始剤などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。これらの光重合開始剤は、それぞれ単独で用いてもよく、2種以上を併用してもよい。 Examples of the photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,1'. -Biimidazole, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (p-methoxyphenylvinyl) -1,3,5- Triazine, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, 4,4'-ditert-butyldiphenyliodonium tetrafluoroborate, 4-diethylaminophenylbenzenediazonium hexafluorophosphate, benzoin, 2-hydroxy-2-methyl-1 -Phenylpropan-2-one, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylacylphosphine oxide, triphenylbutylborate tetraethylammonium, diphenyl-4-phenylthiophenylsulfonium hexafluorophosphate, 2,2-dimethoxy- 1,2-Diphenylethane-1-one, phenylglycylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, bis (2,4,6) -Trimethylbenzoyl) -phenylphosphine oxide, 1,2-octanedione, 1- [4- (phenylthio) -2- (o-benzoyloxime)], bis (η5-2,4-cyclopentadiene-1-yl) Photoradical polymerization initiators such as bis [2,6-difluoro-3- (1H-pyrrole-1-yl) phenyltitanium], 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (p-methoxyphenyl vinyl) -1,3,5-triazine, diphenyliodonium tetrafluoroborate, 4,4'-ditert-butyldiphenyliodonium tetrafluoroborate, 4 Examples thereof include photocationic ring-opening polymerization initiators such as diethylaminophenylbenzenediazonium hexafluorophosphate and diphenyl-4-phenylthiophenylsulfonium hexafluorophosphate, but the present disclosure is not limited to these examples. These photopolymerization initiators may be used alone or in combination of two or more.
 重合開始剤として光重合開始剤を用いる場合、当該光重合開始剤の量は、全モノマーの100重量部あたり、通常、約0.01重量部~約20重量部であることが好ましい。 When a photopolymerization initiator is used as the polymerization initiator, 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.
 熱重合開始剤としては、例えば、アゾビスイソブチロニトリル(AIBN)、2,2’-アゾビス(イソ酪酸メチル)、2,2’-アゾビス(2,4-ジメチルバレロニトリル)、2,2’-アゾビス(2-メチルブチロニトリル)、1,1’-アゾビス(シクロヘキサン-1-カルボニトリル)などのアゾ系重合開始剤、過酸化ベンゾイル、過硫酸カリウム、過硫酸アンモニウムなどの過酸化物系重合開始剤などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。これらの重合開始剤は、それぞれ単独で用いてもよく、2種類以上を併用してもよい。 Examples of the thermal polymerization initiator 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.
 重合開始剤として熱重合開始剤を用いる場合、当該熱重合開始剤の量は、全モノマーの100重量部あたり、通常、約0.01重量部~約20重量部であることが好ましい。 When a thermal polymerization initiator is used as the polymerization initiator, 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.
 AIBNなどの、重合反応時に窒素(N)が発生する重合開始剤を使用した場合、結果として生じる複合材は気泡を含む場合がある。このような気泡は破断の起点となりうるため、複合材の伸長性などの性質が低下するおそれがある一方で、衝撃吸収能は向上し得ることが予測される。なお、複合材に含まれる気泡は、重合開始剤に由来するものに限定されず、発泡剤を添加することで得られるものや、溶媒の除去により得られるものなど、樹脂等に気泡を含ませることができる公知の方法により得られる気泡であってよい。 When a polymerization initiator that generates nitrogen (N 2 ) during the polymerization reaction, such as AIBN, is used, 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.
 本開示において使用可能な他の重合開始剤としては、例えば、過酸化水素と鉄(II)塩、過硫酸塩と亜硫酸水素ナトリウムなどのレドックス重合開始剤、金属触媒下でハロゲン化アルキルを用いるATRP(原子移動ラジカル重合)開始剤、金属と窒素含有配位子を用いるICAR ATRP開始剤やARGET ATRP開始剤、RAFT(可逆的付加-開裂連鎖移動重合)剤、NMP(ニトロキシドを介した重合)剤、ポリジメチルシロキサンユニット含有高分子アゾ重合開始剤、ポリエチレングリコールユニット含有高分子アゾ重合開始剤などの高分子重合開始剤などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。これらの重合開始剤は、それぞれ単独で用いてもよく、2種類以上を併用してもよい。 Other polymerization initiators that can be used in the present disclosure include, for example, 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. (Atom transfer radical polymerization) initiator, ICAR ATRP initiator or ARGET ATRP initiator using metal and nitrogen-containing ligand, RAFT (reversible addition-cleavage chain transfer polymerization) agent, NMP (nitroxide-mediated polymerization) agent , 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.
 モノマーを重合させる際には、分子量を調整するために連鎖移動剤を用いてもよい。連鎖移動剤は、通常、モノマーと混合することによって用いることができる。連鎖移動剤としては、例えば、2-(ドデシルチオカルボノチオイルチオ)-2-メチルプロピオン酸、2-(ドデシルチオカルボノチオイルチオ)プロピオン酸、メチル2-(ドデシルチオカルボノチオイルチオ)-2-メチルプロピオネート、2-(ドデシルチオカルボノチオイルチオ)-2-メチルプロピオン酸3-アジド-1-プロパノールエステル、2-(ドデシルチオカルボノチオイルチオ)-2-メチルプロピオン酸ペンタフルオロフェニルエステル、ラウリルメルカプタン、ドデシルメルカプタン、チオグリセロールなどのメルカプタン基含有化合物、次亜リン酸ナトリウム、亜硫酸水素ナトリウムなどの無機塩などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。これらの連鎖移動剤は、それぞれ単独で用いてもよく、2種類以上を併用してもよい。連鎖移動剤の量は、特に限定されないが、通常、全モノマーの100重量部あたり約0.01重量部~約10重量部であればよい。 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)-. 2-Methylpropionate, 2- (dodecylthiocarbonothiolthio) -2-methylpropionate 3-azido-1-propanol ester, 2- (dodecylthiocarbonothiolthio) -2-methylpropionate pentafluoro Examples thereof include mercaptan group-containing compounds such as phenyl ester, lauryl mercaptan, dodecyl mercaptan and thioglycerol, and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite, but the present disclosure is not limited to such examples. Absent. Each of these chain transfer agents may be used alone, or two or more of them may be used in combination. The amount of the chain transfer agent is not particularly limited, but is usually about 0.01 parts by weight to about 10 parts by weight per 100 parts by weight of all the monomers.
 モノマーを重合させる際の雰囲気は、特に限定がなく、大気であってもよく、あるいは窒素ガス、アルゴンガスなどの不活性ガスであってもよい。 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.
 モノマーを重合させる際の温度は、特に限定がなく、通常、5~100℃程度の温度であることが好ましい。モノマーを重合させるのに要する時間は、重合条件によって異なるので一概には決定することができないことから任意であるが、通常、1~20時間程度である。 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.
 重合反応は、残存しているモノマーの量が20質量%以下になった時点で、任意に終了することができる。なお、残存しているモノマーの量は、例えば、ゲルパーミエイションクロマトグラフィー(GPC)を用いて測定することができる。 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).
 以上のようにしてモノマーを塊状重合させることにより、ポリマーマトリクスを得ることができる。 A polymer matrix can be obtained by bulk polymerization of the monomers as described above.
 一実施形態において、前記モノマーが架橋剤の非存在下で重合される。別の実施形態において、前記モノマーが架橋剤の存在下で重合される。 In one embodiment, 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.
 一実施形態において、前記ポリマーマトリクスは熱重合または光重合されたものである。別の実施形態において、前記ポリマーマトリクスは熱重合されたものである。別の実施形態において、前記ポリマーマトリクスは光重合されたものである。 In one embodiment, 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.
 モノマーを重合させる方法としては、例えば、塊状重合法、溶液重合法、乳化重合法、懸濁重合法などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。これらの重合法のなかでは、塊状重合法および溶液重合法が好ましい。 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. Among these polymerization methods, a massive polymerization method and a solution polymerization method are preferable.
 また、モノマーの重合は、例えば、ラジカル重合法、リビングラジカル重合法、アニオン重合法、カチオン重合法、付加重合法、重縮合法、触媒重合などの方法によって行うことができる。 Further, 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.
 モノマーを溶液重合法によって重合させる場合には、例えば、モノマーを溶媒に溶解させ、得られた溶液を攪拌しながら重合開始剤を当該溶液に添加することによってモノマーを重合させることができるほか、重合開始剤を溶媒に溶解させ、得られた溶液を撹拌しながらモノマーを当該溶液に添加することによってモノマーを重合させることができる。溶媒は、モノマーと相溶する有機溶媒であることが好ましい。 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.
 本開示の導電材に含まれるコポリマーは、重合開始剤として過酸化物系の開始剤(例えば、過酸化ベンゾイル、およびアゾビスイソブチロニトリル、ならびにそれらの類似体)を使用することによって重合されてもよい。 The copolymers contained in the conductive materials of the present disclosure are polymerized by using peroxide-based initiators (eg, benzoyl peroxide and azobisisobutyronitrile, and their analogs) as polymerization initiators. You may.
 重合開始剤として上記使用可能な重合開始剤を用いる場合、当該重合開始剤の量は、全モノマーの100重量部あたり、通常、約0.01重量部~約20重量部であることが好ましい。 When the above-mentioned usable polymerization initiator is used as the polymerization initiator, 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.
 一実施形態では、モノマーに電子線を照射することにより、電子線重合が行われる。一実施形態では、電子線のみの照射によってモノマーを重合させることができる。電子線重合において、電子線は、一実施形態では、光重合開始剤の存在下で照射され、別の実施形態では光重合開始剤の非存在下で照射される。いずれの実施形態も、本開示の範囲内である。 In one embodiment, electron beam polymerization is performed by irradiating the monomer with an electron beam. In one embodiment, the monomer can be polymerized by irradiation with only an electron beam. In electron beam polymerization, 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.
 モノマーを重合させる際の重合反応温度および雰囲気については、特に限定がない。通常、重合反応温度は、約50℃~約120℃である。重合反応時の雰囲気は、例えば、窒素ガスなどの不活性ガス雰囲気であることが好ましい。また、モノマーの重合反応時間は、重合反応温度などによって異なるので一概には決定することができないが、通常、約3~20時間である。 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. Further, 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.
 (2)導電材に含まれるポリマーマトリクスの製造方法
 本開示の導電材に含まれるポリマー(またはポリマーマトリクス)は、特定のモノマーを2種以上混合して、適宜の重合条件のもと、必要に応じて適宜の重合開始剤等の添加剤を用いて、重合させることにより、製造することができる。そして、このポリマーマトリクスに導電成分および任意の他の成分を混合し、加熱することによって、本開示の導電材を製造することができる。ポリマーについては、以下に、個々の成分や具体的な製造条件などについて詳述する。
(2) Method for Producing Polymer Matrix Contained in Conductive Material 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.
 1つの局面において、本開示は、式(4)
Figure JPOXMLDOC01-appb-C000036
により表される化合物と第2の(メタ)アクリルモノマーとのコポリマーを製造する方法に関しており、
式中、Rは、水素原子またはメチル基であり、Rは、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であり、nは、0または1の整数であり、
該第2の(メタ)アクリルモノマーは、式(2)
Figure JPOXMLDOC01-appb-C000037
によって表され、Rは、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは、酸素含有環で置換されたアルキル基でも、アルコキシ置換されたアルキルでもない。
In one aspect, the present disclosure relates to equation (4).
Figure JPOXMLDOC01-appb-C000036
It relates to a method for producing a copolymer of a compound represented by the above and a second (meth) acrylic monomer.
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 An unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, where n is an integer of 0 or 1.
The second (meth) acrylic monomer has the formula (2).
Figure JPOXMLDOC01-appb-C000037
Represented by, R 3 is a hydrogen atom or a methyl group,
R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkoxy-substituted alkyl.
 1つの実施形態において、本開示は、酸素含有環で置換されたアルキル(メタ)アクリレートと第2の(メタ)アクリルモノマーとのコポリマーを製造する方法に関しており、
該酸素含有環で置換されたアルキル(メタ)アクリレートは、式(1)
Figure JPOXMLDOC01-appb-C000038
によって表され、Rは、水素原子またはメチル基であり、
は、1個またはそれより多くのオキシラン環またはオキセタン環で置換されたアルキル基であり、
該第2の(メタ)アクリルモノマーは、式(2)
Figure JPOXMLDOC01-appb-C000039
によって表され、Rは、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは酸素含有環で置換されたアルキル基ではない。
In one embodiment, the disclosure relates to a method of making a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring and a second (meth) acrylic monomer.
The alkyl (meth) acrylate substituted with the oxygen-containing ring has the formula (1).
Figure JPOXMLDOC01-appb-C000038
Represented by, R 1 is a hydrogen atom or a methyl group,
R 2 is an alkyl group substituted with one or more oxylan or oxetane rings.
The second (meth) acrylic monomer has the formula (2).
Figure JPOXMLDOC01-appb-C000039
Represented by, R 3 is a hydrogen atom or a methyl group,
R 4 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, However, R 4 is not an alkyl group substituted with an oxygen-containing ring.
 本開示の一実施形態において、前記モノマーの重合は、塊状重合法、溶液重合法、乳化重合法、および懸濁重合法からなる群より選択される重合法にしたがって行われる。理論により拘泥されることを望むものではないが、本開示のモノマーは、連鎖重合、逐次重合、またはリビング重合により重合され得る。 In one embodiment of the present disclosure, 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. Although not desired to be bound by theory, the monomers of the present disclosure can be polymerized by chain polymerization, step-growth polymerization, or living polymerization.
 (3-1)モノマーの調製方法
 本開示において使用されるフッ素化アルキル(メタ)アクリレートおよび(メタ)アクリルモノマーは、実施例に例示される製造業者などから市販されるものであってもよく、当業者に周知の方法に従って調製してもよい。
(3-1) Method for Preparing Monomer The alkyl fluorinated (meth) acrylate and (meth) acrylic monomer used in the present disclosure may be commercially available from a manufacturer exemplified in Examples. It may be prepared according to a method well known to those skilled in the art.
 (3-2)光重合による製造方法
 一実施形態では、本開示のポリマーマトリクスは、モノマー(複数種のモノマーを含む)を、重合開始剤の存在下、露光重合することによって1工程で得られる。
 一実施形態では、本開示のポリマーマトリクスは、1種の(メタ)アクリルモノマー、および酸素含有環で置換されたアルキル(メタ)アクリレートを重合開始剤の存在下、紫外線を照射することにより製造することができる。
 重合開始剤の好ましい例としては、2,4,6-トリメチルベンゾイルジフェニルホスフィンオキシドが挙げられる。
 本工程は、通常室温にて約2時間で行われるが、これに限定されず、0.5~3時間、もしくは0.5時間~24時間またはそれ以上の時間をかけてもよい。
(3-2) Production Method by Photopolymerization In one embodiment, the polymer matrix of the present disclosure is obtained in one step by exposure-polymerizing a monomer (including a plurality of types of monomers) in the presence of a polymerization initiator. ..
In one embodiment, the polymer matrix of the present disclosure is prepared by irradiating one (meth) acrylic monomer and an alkyl (meth) acrylate substituted with an oxygen-containing ring with ultraviolet light in the presence of a polymerization initiator. be able to.
Preferred examples of the 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, or 0.5 to 24 hours or more.
 (3-3)樹脂溶液の調製方法
 一実施形態では、モノマーを重合することにより得られる本開示のポリマーマトリクスを、溶媒に溶解させて、樹脂溶液を生成する。好ましい溶媒の例としては、ヘプタン、オクタン、およびリモネンなどが挙げられる。
(3-3) Method for Preparing Resin Solution In one embodiment, the polymer matrix of the present disclosure obtained by polymerizing a monomer is dissolved in a solvent to produce a resin solution. Examples of preferred solvents include heptane, octane, limonene and the like.
 (3-4)導電材の調製方法
 一実施形態では、導電材は、(3-3)で得た樹脂溶液を導電成分、および必要に応じて分散剤と混合し、得られた混合物を、加熱して得られる。当業者は、本明細書の記載および当該分野で公知の任意の手法を用いて、この手法以外を用いても導電材を製造することができる。
(3-4) Method for preparing conductive material In one embodiment, 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.
 (導電成分の説明)
 導電成分としては、例えば、鱗片状黒鉛などの天然黒鉛、人造黒鉛などのグラファイト、アセチレンブラック、ケッチェンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、サーマルブラックなどのカーボンブラック、グラフェン、カーボンナノチューブ、フラーレンなどの炭素系材料;炭素繊維、金属繊維などの導電性繊維;フッ化カーボン;銅、金、ニッケル、錫、アルミニウム、亜鉛、鉄、銀などの金属粒子の粉末;酸化亜鉛、チタン酸カリウムなどの導電性ウィスカー;酸化チタンなどの導電性金属酸化物;ポリフェニレン誘導体などの有機導電性材料などが挙げられるが、本開示は、かかる例示のみに限定されるものではない。これらの導電成分は、それぞれ単独で用いてもよく、2種類以上を併用してもよい。これらの導電成分のなかでは、作業性および成形性に優れるとともに、柔軟性および伸長性に優れた導電性フィルムを得る観点から、カーボンナノチューブ、カーボンブラック、グラフェンおよび金属粒子が好ましく、カーボンナノチューブ、カーボンブラック、グラフェンおよび銀粒子がより好ましい。
(Explanation of conductive components)
Examples of conductive components include natural graphite such as scaly graphite, graphite such as artificial graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black and other carbon black, graphene, carbon nanotubes, and fullerene. Carbon-based materials such as; conductive fibers such as carbon fiber and metal fiber; carbon fluoride; powder of metal particles such as copper, gold, nickel, tin, aluminum, zinc, iron and silver; zinc oxide, potassium titanate, etc. Examples thereof include conductive whiskers; conductive metal oxides such as titanium oxide; organic conductive materials such as polyphenylene derivatives, but the present disclosure is not limited to these examples. Each of these conductive components may be used alone, or two or more types may be used in combination. Among these conductive components, carbon nanotubes, carbon black, graphene and metal particles are preferable, and carbon nanotubes and carbon are preferable from the viewpoint of obtaining a conductive film having excellent workability and moldability as well as excellent flexibility and extensibility. Black, graphene and silver particles are more preferred.
 ポリマーマトリクスおよび導電成分の合計固形分における導電成分の固形分の含有率は、当該導電成分の種類などによって異なるので一概には決定することができないが、通常、作業性および成形性に優れるとともに、柔軟性および伸長性に優れた導電性フィルムを得る観点から、好ましくは1質量%以上であり、作業性および成形性に優れるとともに、柔軟性および伸長性に優れた導電性フィルムを得る観点から、好ましくは100質量%以下である。 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.
 カーボンナノチューブとしては、例えば、1枚のシート状グラファイト(グラフェンシート)を筒状に丸めた中空円筒構造のシングルウォールカーボンナノチューブ、直径の異なるシングルウォールカーボンナノチューブを同心円状に複数積層した構造のマルチウォールカーボンナノチューブ、スーパーグロース法により製造されるシングルウォールカーボンナノチューブ、シングルウォールカーボンナノチューブの端部が円錐状で閉じた形状のカーボンナノコーン、内部にフラーレンを内包するカーボンナノチューブなどが挙げられるが、本開示は、かかる例示のみに限定されるものではない。これらのカーボンナノチューブは、それぞれ単独で用いてもよく、2種類以上を併用してもよい。これらのカーボンナノチューブのなかでは、マルチウォールカーボンナノチューブが好ましい。 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. Among these carbon nanotubes, multi-wall carbon nanotubes are preferable.
 カーボンナノチューブの長さは、作業性および成形性に優れるとともに、柔軟性および伸長性に優れた導電性フィルムを得る観点から、好ましくは0.1~1000μm、より好ましくは1~500μmであり、さらに好ましくは1~90μmである。 The length of the carbon nanotubes is preferably 0.1 to 1000 μm, more preferably 1 to 500 μm, 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 μm.
 カーボンナノチューブの直径は、作業性および成形性に優れるとともに、柔軟性および伸長性に優れた導電性フィルムを得る観点から、好ましくは10~50nm、より好ましくは10~20nmである。 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.
 ポリマーマトリクスおよびカーボンナノチューブの合計固形分におけるカーボンナノチューブの固形分の含有率は、作業性および成形性に優れるとともに、柔軟性および伸長性に優れた導電性フィルムを得る観点から、好ましくは1質量%以上、より好ましくは1.5質量%以上、さらに好ましくは2質量%以上であり、作業性および成形性に優れるとともに、柔軟性および伸長性に優れた導電性フィルムを得る観点から、好ましくは25質量%以下、より好ましくは20質量%以下、さらに好ましくは15質量%以下であり、さらに一層好ましくは3.5~10質量%である。 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%.
 (導電材の用途)
 本開示の導電材は、例えば、アクチュエータ、産業用ロボットなどに使用されるセンサ、配線、電極、基板、発電素子、スピーカー、マイクロフォン、ノイズキャンセラ、トランスデューサ、人工筋肉、小型ポンプ、医療用器具などに好適に使用することができる導電性フィルムおよび当該導電性フィルムの原料として好適に使用することができる。
(Use of conductive material)
The conductive material of the present disclosure is suitable for, for example, sensors, wirings, electrodes, substrates, power generation 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 used in the above and as a raw material of the conductive film.
 (好ましい実施形態)
 以下に本開示の好ましい実施形態を説明する。以下に提供される実施形態は、本開示のよりよい理解のために提供されるものであり、本開示の範囲は以下の記載に限定されるべきでないことが理解される。従って、当業者は、本明細書中の記載を参酌して、本開示の範囲内で適宜改変を行うことができることは明らかである。また、本開示の以下の実施形態は単独でも使用されあるいはそれらを組み合わせて使用することができることが理解される。
(Preferable embodiment)
The preferred embodiments of the present disclosure will be described below. It is understood that the embodiments provided below are provided for a better understanding of the present disclosure and the scope of the present disclosure should not be limited to the following description. Therefore, it is clear that a person skilled in the art can make appropriate modifications within the scope of the present disclosure in consideration of the description in the present specification. It is also understood that the following embodiments of the present disclosure may be used alone or in combination.
 (焼成温度低下用途)
 1局面において、本開示は、焼成温度低下用途に関する。
(Use for lowering firing temperature)
In one aspect, the present disclosure relates to a firing temperature lowering application.
 より特定すると、具体的な局面では、本開示は酸素含有環で置換されたアルキル(メタ)アクリレートを含む、導電材を生成するための焼成温度を低下させるための組成物(焼成温度低下剤)を提供する。 More specifically, in a specific aspect, the present disclosure is a composition for lowering the calcination temperature for producing a conductive material (calcination temperature lowering agent) containing an alkyl (meth) acrylate substituted with an oxygen-containing ring. I will provide a.
 1つの具体的な実施形態では、本開示の焼成温度低下剤は、ポリマーマトリクスの一部として取り込まれて使用される。この実施形態では、本開示の導電材は、酸素含有環で置換されたアルキル(メタ)アクリレートのコポリマーおよび導電成分を含む。好ましい実施形態では、酸素含有環で置換されたアルキル(メタ)アクリレートは、コポリマーとして含まれることにより、導電材を生成するための焼成温度を低下させることができる。理論に束縛されることを望まないが、焼成温度低下剤である酸素含有環で置換されたアルキル(メタ)アクリレートをモノマーとして添加して、重合により生じるコポリマー(ポリマーマトリクス)の組成を調整することで焼成温度の低下を達成することができることが本開示により見出された。 In one specific embodiment, the calcination temperature lowering agent of the present disclosure is incorporated and used as part of a polymer matrix. In this embodiment, the conductive material of the present disclosure comprises a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring and a conductive component. In a preferred embodiment, the alkyl (meth) acrylate substituted with the oxygen-containing ring can be included as a copolymer to lower the calcination temperature for producing the conductive material. Although not bound by theory, adding an alkyl (meth) acrylate substituted with an oxygen-containing ring, which is a calcination temperature lowering agent, as a monomer to adjust the composition of the copolymer (polymer matrix) produced by the polymerization. It has been found by the present disclosure that a reduction in firing temperature can be achieved.
 1つの好ましい実施形態において、本開示において使用されるコポリマーは、酸素含有基で置換されたアルキル(メタ)アクリレートと、第2の(メタ)アクリルモノマーとのコポリマーであることが有利である。 In one preferred embodiment, it is advantageous that the copolymer used in the present disclosure is a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing group and a second (meth) acrylic monomer.
 1つの好ましい実施形態において、本開示において使用されるコポリマーは、酸素含有環で置換されたアルキル(メタ)アクリレートと、第2の(メタ)アクリルモノマーとのコポリマーであることが有利である。 In one preferred embodiment, it is advantageous that the copolymer used in the present disclosure is a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring and a second (meth) acrylic monomer.
 1つの好ましい実施形態において、本開示において使用されるコポリマーは、nが0であり、Rが水素原子であり、Rが酸素含有基で置換されたアルキルである式(4)により表される化合物と、第2の(メタ)アクリルモノマーとのコポリマーであることが有利である。 In one preferred embodiment, the copolymers used in the present disclosure are represented by formula (4), where n is 0, R 1 is a hydrogen atom, and R 2 is an alkyl substituted with an oxygen-containing group. It is advantageous that the compound is a copolymer of a second (meth) acrylic monomer.
 1つの実施形態では、酸素含有環で置換されたアルキル(メタ)アクリレートが、式(1)
Figure JPOXMLDOC01-appb-C000040
によって表され、Rは、水素原子またはメチル基であり、Rは、1個またはそれより多くのオキシラン環またはオキセタン環で置換されたアルキル基である。
In one embodiment, the alkyl (meth) acrylate substituted with the oxygen-containing ring is of formula (1).
Figure JPOXMLDOC01-appb-C000040
Represented by, R 1 is a hydrogen atom or a methyl group and R 2 is an alkyl group substituted with one or more oxylan or oxetane rings.
 1つの実施形態では、第2の(メタ)アクリルモノマーは、式(2)
Figure JPOXMLDOC01-appb-C000041
によって表され、
は、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは酸素含有環で置換されたアルキル基ではない。
In one embodiment, the second (meth) acrylic monomer is of formula (2).
Figure JPOXMLDOC01-appb-C000041
Represented by
R 3 is a hydrogen atom or a methyl group and
R 4 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, However, R 4 is not an alkyl group substituted with an oxygen-containing ring.
 1つの実施形態では、Rが11個またはそれより多くの炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは11個~30個の炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは11個~24個の炭素原子を有する非置換アルキル基である。 In one embodiment, R 4 is an unsubstituted alkyl group having 11 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 24 carbon atoms.
 別の実施形態では、Rは13個またはそれより多くの炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは13個~30個の炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは13個~24個の炭素原子を有する非置換アルキル基である。 In another embodiment, R 4 is an unsubstituted alkyl group having 13 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 24 carbon atoms.
 さらに別の実施形態では、Rは、18個またはそれより多くの炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは18個~30個の炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは18個~24個の炭素原子を有する非置換アルキル基である。 In yet another embodiment, R 4 is an unsubstituted alkyl group having 18 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 24 carbon atoms.
 別の実施形態では、Rは、2~10個の炭素原子を有する非置換アルキル基である。 In another embodiment, R 4 is an unsubstituted alkyl group having 2 to 10 carbon atoms.
 さらに別の実施形態では、酸素含有環で置換されたアルキル(メタ)アクリレートは、(3-エチルオキセタン-3-イル)メチルアクリレートまたは2,3-エポキシプロピルメタクリレートである。 In yet another embodiment, the alkyl (meth) acrylate substituted with the oxygen-containing ring is (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate.
 別の実施形態では、第2の(メタ)アクリルモノマーは、イソステアリルアクリレートまたはラウリルアクリレートである。 In another embodiment, the second (meth) acrylic monomer is isostearyl acrylate or lauryl acrylate.
 (導電材)
 別の局面では、本開示は、導電性が向上された導電材を提供する。
(Conductive material)
In another aspect, the present disclosure provides a conductive material with improved conductivity.
 1つの具体的な局面では、本開示は、フッ素化アルキル(メタ)アクリレートのコポリマーおよび導電成分を含む、導電材を提供する。導電材の好ましい実施形態は、本明細書に記載されている任意の実施形態またはその組み合わせを利用することができ、本明細書における(導電率向上用途)の項で記載される任意の実施形態を1つまたは複数組み合わせて適用することができる。 In one specific aspect, the present disclosure provides a conductive material comprising a copolymer of an alkyl fluorinated (meth) acrylate and a conductive component. As a preferred embodiment of the conductive material, 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.
 (製造法)
 1つの局面では、本開示は、本開示の導電材および焼成温度低下剤の製造方法をも提供する。
(Manufacturing method)
In one aspect, the present disclosure also provides a method for producing the conductive material and the firing temperature lowering agent of the present disclosure.
 具体的な局面では、本開示は、酸素含有環で置換されたアルキル(メタ)アクリレートのコポリマーおよび導電成分を含む導電材を製造する方法を提供する。この方法は、前記酸素含有環で置換されたアルキル(メタ)アクリレートおよび重合性モノマーを重合することによりコポリマーを得る工程、該コポリマーおよび導電成分を混合して、混合物を得る工程、および該混合物を加熱して導電材を生成する工程を包含する。製造法の好ましい実施形態は、本明細書に記載されている任意の実施形態またはその組み合わせを利用することができ、本明細書における(焼成温度低下用途)の項で記載される任意の実施形態を1つまたは複数組み合わせて適用することができる。 In a specific aspect, the present disclosure provides a method for producing a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring and a conductive material containing a conductive component. In this method, a step of obtaining a copolymer by polymerizing an alkyl (meth) acrylate substituted with the oxygen-containing ring and a polymerizable monomer, a step of mixing the copolymer and a conductive component to obtain a mixture, and a step of obtaining the mixture. It includes a step of heating to produce a conductive material. As a preferred embodiment of the production method, any embodiment described in the present specification or a combination thereof can be utilized, and any embodiment described in the section (Baking temperature lowering use) in the present specification. Can be applied as one or a combination of two or more.
 本開示の製造法における酸素含有環で置換されたアルキル(メタ)アクリレートおよび重合性モノマーを重合することによりコポリマーを得る工程では、代表的には、以下のような条件が好ましい:大気圧下、5℃~100℃。 In the step of obtaining a copolymer by polymerizing an alkyl (meth) acrylate substituted with an oxygen-containing ring and a polymerizable monomer in the production method of the present disclosure, the following conditions are typically preferable: under atmospheric pressure. 5 ° C to 100 ° C.
本開示の製造法におけるコポリマーおよび導電成分を混合して、混合物を得る工程では、代表的には、以下のような条件が好ましい:大気圧下、室温にて遊星式混合撹拌装置による撹拌。 In the step of mixing the copolymer and the conductive component in the production method of the present disclosure to obtain a mixture, the following conditions are typically preferable: stirring by a planetary mixing stirrer at room temperature under atmospheric pressure.
 本開示の製造法における混合物を加熱して導電材を生成する工程では、代表的には、以下のような条件が好ましい:大気圧下、120℃~150℃。 In the step of heating the mixture to produce the conductive material in the production method of the present disclosure, the following conditions are typically preferable: 120 ° C. to 150 ° C. under atmospheric pressure.
 (コポリマー)
 本開示は、本開示の技術を用いるコポリマーを提供する。
(Copolymer)
The present disclosure provides copolymers using the techniques of the present disclosure.
 代表的な局面では、本開示は、式(4)
Figure JPOXMLDOC01-appb-C000042
により表される化合物と第2の(メタ)アクリルモノマーとのコポリマーであって、式(4)において、Rは、水素原子またはメチル基であり、Rは、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であり、nは、0または1の整数であり、
該第2の(メタ)アクリルモノマーは、式(2)
Figure JPOXMLDOC01-appb-C000043
によって表され、Rは、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは、酸素含有環で置換されたアルキル基でも、アルコキシ置換されたアルキルでもない、
コポリマーを提供する。このコポリマーは、例えば、導電材のマトリクスとして使用される。
In a representative aspect, the present disclosure is expressed in equation (4).
Figure JPOXMLDOC01-appb-C000042
A copolymer of the compound represented by the above and a second (meth) acrylic monomer, in formula (4), R 1 is a hydrogen atom or a methyl group, and R 2 is a hydrogen atom, substituted or unsubstituted. Alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted non-aryl heterocycloalkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted heteroaryl group, n being an integer of 0 or 1. ,
The second (meth) acrylic monomer has the formula (2).
Figure JPOXMLDOC01-appb-C000043
Represented by, R 3 is a hydrogen atom or a methyl group,
R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkyl are alkoxy-substituted,
Provide copolymers. This copolymer is used, for example, as a matrix of conductive materials.
 1つの具体的な実施形態では、前記酸素含有基で置換されたアルキル(メタ)アクリレートは、式(1)
Figure JPOXMLDOC01-appb-C000044
によって表され、Rは、水素原子またはメチル基であり、
は、1個またはそれより多くの酸素含有基で置換されたアルキル基である。
In one specific embodiment, the alkyl (meth) acrylate substituted with the oxygen-containing group is of formula (1).
Figure JPOXMLDOC01-appb-C000044
Represented by, R 1 is a hydrogen atom or a methyl group,
R 2 is an alkyl group substituted with one or more oxygen-containing groups.
 別の具体的な実施形態では、式(4)
Figure JPOXMLDOC01-appb-C000045
により表される化合物において、Rは、水素原子であり、Rは、ビニルオキシもしくはヒドロキシで置換されていてもよいアルキル基、シクロアルキル基、もしくはアルキルシクロアルキルアルキル基、または-(CHCHO)-Rであり、Rが水素またはビニルであり、yが1以上の整数であり、nは0である。
In another specific embodiment, equation (4)
Figure JPOXMLDOC01-appb-C000045
In the compound represented by, R 1 is a hydrogen atom and R 2 is an alkyl group, a cycloalkyl group, or an alkylcycloalkylalkyl group, which may be substituted with vinyloxy or hydroxy, or-(CH 2 CH). 2 O) y- R 7 , where R 7 is hydrogen or vinyl, y is an integer greater than or equal to 1, and n is 0.
 本開示はまた、酸素含有環で置換されたアルキル(メタ)アクリレートと第2の(メタ)アクリルモノマーとのコポリマーを提供し、該酸素含有基で置換されたアルキル(メタ)アクリレートは、式(1)
Figure JPOXMLDOC01-appb-C000046
によって表され、Rは、水素原子またはメチル基であり、
は、1個またはそれより多くのオキシラン環またはオキセタン環で置換されたアルキル基であり、
該第2の(メタ)アクリルモノマーは、式(2)
Figure JPOXMLDOC01-appb-C000047
によって表され、Rは、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは酸素含有環で置換されたアルキル基ではない。このコポリマーは、例えば、導電材のマトリクスとして使用される。
The present disclosure also provides a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring and a second (meth) acrylic monomer, wherein the alkyl (meth) acrylate substituted with the oxygen-containing group is of the formula ( 1)
Figure JPOXMLDOC01-appb-C000046
Represented by, R 1 is a hydrogen atom or a methyl group,
R 2 is an alkyl group substituted with one or more oxylan or oxetane rings.
The second (meth) acrylic monomer has the formula (2).
Figure JPOXMLDOC01-appb-C000047
Represented by, R 3 is a hydrogen atom or a methyl group,
R 4 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, However, R 4 is not an alkyl group substituted with an oxygen-containing ring. This copolymer is used, for example, as a matrix of conductive materials.
 1つの実施形態では、Rは、11個またはそれより多くの炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは11個~30個の炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは11個~24個の炭素原子を有する非置換アルキル基である。 In one embodiment, R 4 is an unsubstituted alkyl group having 11 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 24 carbon atoms.
 1つの実施形態では、Rは、13個またはそれより多くの炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは13個~30個の炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは13個~24個の炭素原子を有する非置換アルキル基である。 In one embodiment, R 4 is an unsubstituted alkyl group having 13 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 24 carbon atoms.
 1つの実施形態では、Rは、18個またはそれより多くの炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは18個~30個の炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは18個~24個の炭素原子を有する非置換アルキル基である。 In one embodiment, R 4 is an unsubstituted alkyl group having 18 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 24 carbon atoms.
 別の実施形態では、Rは、2~10個の炭素原子を有する非置換アルキル基である。 In another embodiment, R 4 is an unsubstituted alkyl group having 2 to 10 carbon atoms.
 本開示は、マトリクス用途を提供する。
 1つの局面では、本開示は、式(1)により表される酸素含有環で置換されたアルキル(メタ)アクリレートのコポリマーを含む、導電成分を含む導電材中のマトリクスとして使用するための組成物を提供する。
The present disclosure provides matrix applications.
In one aspect, the present disclosure is a composition for use as a matrix in a conductive material containing a conductive component, comprising a copolymer of an alkyl (meth) acrylate substituted with an oxygen-containing ring represented by formula (1). I will provide a.
 (混合物)
 本開示はまた、混合物を提供する。
(blend)
The present disclosure also provides a mixture.
 1つの局面では、本開示は、物質としての混合物(すなわち、コポリマーと金属系成分とを含む組成物)を提供する。 In one aspect, the present disclosure provides a mixture as a substance (ie, a composition comprising a copolymer and a metallic component).
 1つの局面では、本開示は、式(4)により表される化合物と(第2の)(メタ)アクリルモノマーとのコポリマーおよび金属の混合物を提供する。ここで、「第2の」(メタ)アクリルモノマーとは、コポリマーの(第1の)式(4)により表される化合物の相方としてのモノマーを意味する。 In one aspect, the disclosure provides a copolymer of a compound represented by formula (4) with a (second) (meth) acrylic monomer and a mixture of metals. Here, the "second" (meth) acrylic monomer means a monomer as a companion to the compound represented by the (first) formula (4) of the copolymer.
 1つの実施形態において、前記混合物は、酸素含有基で置換されたアルキル(メタ)アクリレート(モノマー)と(第2の)(メタ)アクリルモノマーとのコポリマーおよび金属の混合物である。 In one embodiment, the mixture is a copolymer and metal mixture of an alkyl (meth) acrylate (monomer) substituted with an oxygen-containing group and a (second) (meth) acrylic monomer.
 別の実施形態において、前記混合物は、Rは、水素原子であり、Rは、ビニルオキシもしくはヒドロキシで置換されていてもよいアルキル基、シクロアルキル基、もしくはアルキルシクロアルキルアルキル基、または-(CHCHO)-Rであり、Rが水素またはビニルであり、yが1以上の整数であり、nは0である、式(4)により表される化合物と(第2の)(メタ)アクリルモノマーとのコポリマーおよび金属の混合物である。 In another embodiment, in the mixture, R 1 is a hydrogen atom and R 2 is an alkyl group, a cycloalkyl group, or an alkylcycloalkylalkyl group, which may be substituted with vinyloxy or hydroxy, or-(. CH 2 CH 2 O) y- R 7 , where R 7 is hydrogen or vinyl, y is an integer greater than or equal to 1, and n is 0, and the compound represented by the formula (4) (second). A mixture of a copolymer with a (meth) acrylic monomer and a metal.
 本開示はまた、酸素含有環で置換されたアルキル(メタ)アクリレート(モノマー)と(第2の)(メタ)アクリルモノマーとのコポリマーおよび金属の混合物を提供する。ここで、「第2の」(メタ)アクリルモノマーとは、コポリマーの(第1の)酸素含有環で置換されたアルキル(メタ)アクリレートモノマーの相方としてのモノマーを意味する。 The present disclosure also provides a copolymer of an alkyl (meth) acrylate (monomer) substituted with an oxygen-containing ring and a (second) (meth) acrylic monomer and a mixture of metals. Here, the "second" (meth) acrylic monomer means a monomer as a companion to the alkyl (meth) acrylate monomer substituted with the (first) oxygen-containing ring of the copolymer.
 1つの実施形態では、金属は、銀、銅、金、アルミニウム、亜鉛、錫、ニッケル、および/または鉄を含む。好ましい実施形態では、金属は銀である。理論に束縛されることを望まないが、銀は、導電性に優れ、耐性もよいからである。 In one embodiment, the metal comprises silver, copper, gold, aluminum, zinc, tin, nickel, and / or iron. In a preferred embodiment, the metal is silver. I don't want to be bound by theory, because silver has excellent conductivity and resistance.
 1つの実施形態では、酸素含有基で置換されたアルキル(メタ)アクリレートは、式(1)
Figure JPOXMLDOC01-appb-C000048
によって表され、Rは、水素原子またはメチル基であり、
は、アルコキシ、オキシラン環およびオキセタン環からなる群より選択される1個から置換可能数までの置換基で置換されたアルキル基である。また、第2の(メタ)アクリルモノマーは、式(2)
Figure JPOXMLDOC01-appb-C000049
によって表され、Rは、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは、酸素含有環で置換されたアルキル基でも、アルコキシ置換されたアルキルでもない。
In one embodiment, the alkyl (meth) acrylate substituted with an oxygen-containing group is of formula (1).
Figure JPOXMLDOC01-appb-C000048
Represented by, R 1 is a hydrogen atom or a methyl group,
R 2 is alkoxy, oxirane ring and an alkyl group substituted by a substituent from one selected from the group consisting of oxetane ring to substitutable number. The second (meth) acrylic monomer has the formula (2).
Figure JPOXMLDOC01-appb-C000049
Represented by, R 3 is a hydrogen atom or a methyl group,
R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkoxy-substituted alkyl.
 1つの実施形態では、酸素含有環で置換されたアルキル(メタ)アクリレートは、式(1)
Figure JPOXMLDOC01-appb-C000050
によって表され、Rは、水素原子またはメチル基であり、
は、1個またはそれより多くのオキシラン環またはオキセタン環で置換されたアルキル基である。また、第2の(メタ)アクリルモノマーは、式(2)
Figure JPOXMLDOC01-appb-C000051
によって表され、Rは、水素原子またはメチル基であり、
は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは酸素含有環で置換されたアルキル基ではない。
In one embodiment, the alkyl (meth) acrylate substituted with the oxygen-containing ring is of formula (1).
Figure JPOXMLDOC01-appb-C000050
Represented by, R 1 is a hydrogen atom or a methyl group,
R 2 is an alkyl group substituted with one or more oxylan or oxetane rings. The second (meth) acrylic monomer has the formula (2).
Figure JPOXMLDOC01-appb-C000051
Represented by, R 3 is a hydrogen atom or a methyl group,
R 4 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, However, R 4 is not an alkyl group substituted with an oxygen-containing ring.
 1つの実施形態では、Rは11個またはそれより多くの炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは11個~30個の炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは11個~24個の炭素原子を有する非置換アルキル基である。 In one embodiment, R 4 is an unsubstituted alkyl group having 11 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 11 to 24 carbon atoms.
 別の実施形態では、Rは13個またはそれより多くの炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは13個~30個の炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは13個~24個の炭素原子を有する非置換アルキル基である。 In another embodiment, R 4 is an unsubstituted alkyl group having 13 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 13 to 24 carbon atoms.
 別の実施形態では、Rは、18個またはそれより多くの炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは18個~30個の炭素原子を有する非置換アルキル基である。1つの実施形態では、Rは18個~24個の炭素原子を有する非置換アルキル基である。 In another embodiment, R 4 is an unsubstituted alkyl group having 18 or more carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 30 carbon atoms. In one embodiment, R 4 is an unsubstituted alkyl group having 18 to 24 carbon atoms.
 別の実施形態では、Rは、2~10個の炭素原子を有する非置換アルキル基である。 In another embodiment, R 4 is an unsubstituted alkyl group having 2 to 10 carbon atoms.
 (注記)
 本明細書において「または」は、文章中に列挙されている事項の「少なくとも1つ以上」を採用できるときに使用される。「もしくは」も同様である。本明細書において「2つの値の範囲内」と明記した場合、その範囲には2つの値自体も含む。
(Note)
As used herein, "or" is used when "at least one" of the matters listed in the text can be adopted. The same applies to "or". When specified as "within the range of two values" in the present specification, the range also includes the two values themselves.
 本明細書において引用された、科学文献、特許、特許出願などの参考文献は、その全体が、各々具体的に記載されたのと同じ程度に本明細書において参考として援用される。 References such as scientific literature, patents, and patent applications cited in this specification are incorporated herein by reference in their entirety to the same extent as they are specifically described.
 以上、本開示を、理解の容易のために好ましい実施形態を示して説明してきた。以下に、実施例に基づいて本開示を説明するが、上述の説明および以下の実施例は、例示の目的のみに提供され、本開示を限定する目的で提供したのではない。従って、本開示の範囲は、本明細書に具体的に記載された実施形態にも実施例にも限定されず、特許請求の範囲によってのみ限定される。 The present disclosure has been described above by showing preferred embodiments for ease of understanding. Hereinafter, the present disclosure will be described based on examples, but the above description and the following examples are provided for purposes of illustration only and not for the purpose of limiting the present disclosure. Therefore, the scope of the present disclosure is not limited to the embodiments or examples specifically described in the present specification, but is limited only by the scope of claims.
 以下に実施例を記載する。以下の実施例で用いる生物の取り扱いは、必要な場合、監督官庁で規定される基準を遵守した。試薬類は具体的には実施例中に記載した製品を使用したが、他メーカー(Sigma-Aldrich、など)の同等品でも代用可能である。 Examples are described below. The handling of organisms used in the following examples complied with the standards set by the regulatory agency, if necessary. Specifically, the products described in the examples were used as the reagents, but equivalent products of other manufacturers (Sigma-Aldrich, etc.) can be substituted.
 (実施例1:ポリマーマトリクスの調製)
 本実施例では、ポリマーマトリクスを調製した。
(Example 1: Preparation of polymer matrix)
In this example, a polymer matrix was prepared.
 (実施例a)
 モノマーAとしてイソステアリルアクリレート(ISTA、9.50g)、モノマーCとして(3-エチルオキセタン-3-イル)メチルアクリレート(4.00g、大阪有機化学工業株式会社製、商品名OXE-10)、及び重合開始剤として2,4,6-トリメチルベンゾイルジフェニルホスフィンオキシド(0.14g、BASF社製、商品名Irgacure(登録商標) TPO)を混合することにより、重合開始剤を含有するモノマー成分を得た。得られたモノマー成分を透明ガラス製の成形型(縦:100mm、横:100mm、深さ:2mm)内に注入した後、当該モノマー成分に照射線量が0.36mW/cmとなるように紫外線を照射し、モノマー成分を2時間塊状重合することによって重合体を得た。
(Example a)
Isostearyl acrylate (ISTA, 9.50 g) as monomer A, (3-ethyloxetane-3-yl) methyl acrylate (4.00 g, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name OXE-10) as monomer C, and A monomer component containing a polymerization initiator was obtained by mixing 2,4,6-trimethylbenzoyldiphenylphosphine oxide (0.14 g, manufactured by BASF, trade name Irgacure (registered trademark) TPO) as a polymerization initiator. .. After injecting the obtained monomer component into a molding mold made of transparent glass (length: 100 mm, width: 100 mm, depth: 2 mm), ultraviolet rays are applied to the monomer component so that the irradiation dose is 0.36 mW / cm 2. The monomer component was bulk-polymerized for 2 hours to obtain a polymer.
 (実施例b~d、比較例1)
 モノマーAとモノマーCの比率を表1に記載の通りに変更した以外は、実施例aと同様にして重合体を得た。
(Examples b to d, Comparative Example 1)
A polymer was obtained in the same manner as in Example a except that the ratio of the monomer A and the monomer C was changed as shown in Table 1.
 (実施例e~g)
 同様に、モノマーCとしてGMA(4.00g、東京化成工業株式会社製、商品名 メタクリル酸グリシジル)をOXE-10の代わりに用いて対応する重合体を得た。使用したモノマーAとモノマーCの組成の重量部は、表1に記載のとおりである。
(Examples e to g)
Similarly, GMA (4.00 g, manufactured by Tokyo Chemical Industry Co., Ltd., trade name glycidyl methacrylate) was used as the monomer C instead of OXE-10 to obtain a corresponding polymer. The parts by weight of the compositions of Monomer A and Monomer C used are as shown in Table 1.
 (実施例h)
  モノマーAとしてエチルアクリレート(EA、4.30g)、モノマーCとして2-メトキシエチルアクリレート(5.60g、大阪有機化学工業株式会社製、商品名 2-MTA)、及び重合開始剤として2,4,6-トリメチルベンゾイルジフェニルホスフィンオキシド(0.14g、BASF社製、商品名Irgacure(登録商標) TPO)を混合することにより、重合開始剤を含有するモノマー成分を得た。得られたモノマー成分を透明ガラス製の成形型(縦:100mm、横:100mm、深さ:2mm)内に注入した後、当該モノマー成分に照射線量が0.36mW/cmとなるように紫外線を照射し、モノマー成分を2時間塊状重合することによって重合体を得た。
(Example h)
Ethyl acrylate (EA, 4.30 g) as monomer A, 2-methoxyethyl acrylate (5.60 g, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name 2-MTA) as monomer C, and 2,4 as a polymerization initiator. A monomer component containing a polymerization initiator was obtained by mixing 6-trimethylbenzoyldiphenylphosphine oxide (0.14 g, manufactured by BASF, trade name Irgacure (registered trademark) TPO). After injecting the obtained monomer component into a molding mold made of transparent glass (length: 100 mm, width: 100 mm, depth: 2 mm), ultraviolet rays are applied to the monomer component so that the irradiation dose is 0.36 mW / cm 2. The monomer component was bulk-polymerized for 2 hours to obtain a polymer.
 (実施例i~k、比較例2)
 同様に、モノマーAとしてエチルアクリレート(EA、X.XXXg)、モノマーCとして4-ヒドロキシブチルビニルエーテル(X.XXg、大阪有機化学工業株式会社製、商品名 4HBVE)を用いて対応する重合体を得た。使用したモノマーAとモノマーCの組成の重量部は、表1に記載のとおりである。
(Examples i to k, Comparative Example 2)
Similarly, ethyl acrylate (EA, X.XXXg) was used as the monomer A, and 4-hydroxybutyl vinyl ether (X.XXg, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name 4HBVE) was used as the monomer C to obtain the corresponding polymer. It was. The parts by weight of the compositions of Monomer A and Monomer C used are as shown in Table 1.
 得られた各重合体3.00gを適宜の溶媒(ヘプタン、オクタン、またはリモネン)(7.00g)と混合し、溶解するかどうかを確認した。溶解した場合は、生じた溶液(アクリル樹脂溶液と称する場合もある)を、導電性フィルムの調製に使用した。 3.00 g of each of the obtained polymers was mixed with an appropriate solvent (heptane, octane, or limonene) (7.00 g), and it was confirmed whether or not it was dissolved. When dissolved, the resulting solution (sometimes referred to as an acrylic resin solution) was used to prepare the conductive film.
 (実施例2:導電性フィルムの調製)
 本実施例では、導電性フィルムを調製した。
(Example 2: Preparation of conductive film)
In this example, a conductive film was prepared.
 (導電材前駆体)
 実施例1で得られた各アクリル樹脂溶液(6.00g)に銀フィラー(7.20g、福田金属箔粉工業社製、商品名 AgC-A)、および分散剤として2-(2-ブトキシエトキシ)エタノール(0.10g)をクラボウ社製マゼルスターにて混合して、導電材前駆体を得た。
(Conductive material precursor)
Silver filler (7.20 g, manufactured by Fukuda Metal Leaf Powder Industry Co., Ltd., trade name AgC-A) and 2- (2-butoxyethoxy) as a dispersant are added to each acrylic resin solution (6.00 g) obtained in Example 1. ) Ethanol (0.10 g) was mixed with a Mazelstar manufactured by Kurabou Co., Ltd. to obtain a conductive material precursor.
 (塗膜形成)
得られた導電材前駆体を剥離フィルムとして離形ポリエチレンテレフタレートフィルム(三井化学東セロ株式会社製、商品名セパレーターSP-PET PET-01-Bu)に塗工して、塗膜を形成した。
(Coating film formation)
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.
 (導電性フィルム)
 得られた塗膜について、オーブンにて150℃で60分間加熱し、およそ30μm厚の導電性フィルムを得た。
(Conductive film)
The obtained coating film was heated in an oven at 150 ° C. for 60 minutes to obtain a conductive film having a thickness of about 30 μm.
 (結果)
 結果を下記表1に示す。
Figure JPOXMLDOC01-appb-T000052
Figure JPOXMLDOC01-appb-T000053
*重合開始剤として2,4,6-トリメチルベンゾイルジフェニルホスフィンオキシドを各1重量部ずつ添加。
*ISTA:イソステアリルアクリレート、GMA:2,3-エポキシプロピルメタクリレート、OXE-10:(3-エチルオキセタン-3-イル)メチルアクリレート、EA:エチルアクリレート、2-MTA:2-メトキシエチルアクリレート、4HBVE:4-ヒドロキシブチルビニルエーテル。
(result)
The results are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000052
Figure JPOXMLDOC01-appb-T000053
* Add 1 part by weight each of 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a polymerization initiator.
* ISTA: Isostearyl acrylate, GMA: 2,3-epoxypropyl methacrylate, OXE-10: (3-ethyloxetane-3-yl) methyl acrylate, EA: ethyl acrylate, 2-MTA: 2-methoxyethyl acrylate, 4HBVE : 4-Hydroxybutyl vinyl ether.
 以上から、2-MTAまたは4HBVEの割合を増やすことで、体積抵抗率および抵抗値変化が低下していることが示された。 From the above, it was shown that the volume resistivity and the change in resistance value were reduced by increasing the ratio of 2-MTA or 4HBVE.
 (実施例3:体積抵抗率の測定)
 実施例2で得られた導電性フィルムを縦0.5cm、横2.00cmに切り出し、ロレスタGP(三菱化学アナリテック社製)を用いて4端子法で測定した。
(Example 3: Measurement of volume resistivity)
The conductive film obtained in Example 2 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).
 (結果)
 結果を表1に示す。
(result)
The results are shown in Table 1.
 (実施例4:抵抗値変化の確認)
 本実施例では、抵抗値変化を確認した。
(Example 4: Confirmation of resistance value change)
In this example, the change in resistance value was confirmed.
 (抵抗値の測定)
 上記で得られた導電性フィルムを縦0.5cm、横2.00cmに切り出し、電極間距離を1.00cmに固定したデジタルマルチメータ〔三和電機計器株式会社製 商品名PC773〕にて伸張前抵抗値(ΩA)を測定した。
(Measurement of resistance value)
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 (ΩA) was measured.
 (抵抗値変化)
 次いで、導電性フィルムをマルチメータ電極上に固定したまま、電極間距離を2.00cmとし、その状態での抵抗値(ΩB)を測定した。抵抗値変化を、以下のように算出した。
   抵抗値変化=ΩB/ΩA
(Change in resistance value)
Next, with the conductive film fixed on the multimeter electrode, the distance between the electrodes was set to 2.00 cm, and the resistance value (ΩB) in that state was measured. The change in resistance value was calculated as follows.
Resistance value change = ΩB / ΩA
 (結果)
 結果は表1に示す。
(result)
The results are shown in Table 1.
 (注記)
 以上のように、本開示の好ましい実施形態を用いて本開示を例示してきたが、本開示は、特許請求の範囲によってのみその範囲が解釈されるべきであることが理解される。本願は、日本国特許出願第2019-148115号(2019年8月9日出願)に対して優先権を主張するものであり、その内容は、その全体が本明細書において参考として援用される。本明細書において引用した特許、特許出願及び他の文献は、その内容自体が具体的に本明細書に記載されているのと同様にその内容が本明細書に対する参考として援用されるべきであることが理解される。
(Note)
As described above, the present disclosure has been illustrated using the preferred embodiments of the present disclosure, but it is understood that the scope of the present disclosure should be interpreted only by the scope of claims. The present application claims priority to Japanese Patent Application No. 2019-148115 (filed on August 9, 2019), the entire contents of which are incorporated herein by reference in its entirety. The patents, patent applications and other documents cited herein should be incorporated herein by reference in their content as they are specifically described herein. Is understood.
 本開示の導電材向上剤を用いて、効率の良い導電材を提供することができ、導電材を必要とする産業において利用可能である。 The conductive material improver of the present disclosure can be used to provide an efficient conductive material, which can be used in industries that require a conductive material.

Claims (19)

  1. 式(4)
    Figure JPOXMLDOC01-appb-C000001
    により表される化合物を含む、導電材の焼成温度を低下させるための組成物であって、
    は、水素原子またはメチル基であり、
    は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であり、
    nは、0または1の整数である、
    組成物。
    Equation (4)
    Figure JPOXMLDOC01-appb-C000001
    A composition for lowering the firing temperature of a conductive material, which comprises the compound represented by.
    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. ,
    n is an integer of 0 or 1,
    Composition.
  2. 前記導電材が、式(4)により表される化合物のホモポリマーもしくはコポリマーおよび導電成分を含む、請求項1に記載の組成物。 The composition according to claim 1, wherein the conductive material contains a homopolymer or copolymer of a compound represented by the formula (4) and a conductive component.
  3. 前記コポリマーが、式(4)により表される化合物と、第2の(メタ)アクリルモノマーとのコポリマーである、請求項2に記載の組成物。 The composition according to claim 2, wherein the copolymer is a copolymer of a compound represented by the formula (4) and a second (meth) acrylic monomer.
  4. が、酸素含有基で置換されていてもよいアルキル基またはシクロアルキル基であり、前記酸素含有基が、ヒドロキシ、ヒドロキシアルキル、ビニルオキシアルキル、アルコキシ、オキシラン環もしくはオキセタン環、または-(CHCHO)-Rであり、Rが水素またはビニルであり、yが1から5の整数である、請求項1~3のいずれか一項に記載の組成物。 R 2 is an alkyl or cycloalkyl group that may be substituted with an oxygen-containing group, wherein the oxygen-containing group is a hydroxy, hydroxyalkyl, vinyloxyalkyl, alkoxy, oxylan ring or oxetane ring, or-(CH). 2 CH 2 O) a y -R 7, an R 7 is hydrogen or vinyl, y is an integer from 1 to 5, the composition according to any one of claims 1-3.
  5. は、水素原子またはメチル基であり、
    は、ヒドロキシ、アルコキシ、オキシラン環およびオキセタン環からなる群より選択される1個から置換可能数までの置換基で置換されたアルキル基である、
    請求項1~4のいずれか一項に記載の組成物。
    R 1 is a hydrogen atom or a methyl group and
    R 2 is hydroxy, alkoxy, oxirane ring and an alkyl group substituted by a substituent from one selected from the group consisting of oxetane ring to substitutable number,
    The composition according to any one of claims 1 to 4.
  6. 前記第2の(メタ)アクリルモノマーは、式(2)
    Figure JPOXMLDOC01-appb-C000002
    によって表され、
    は、水素原子またはメチル基であり、
    は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは、酸素含有環で置換されたアルキル基でも、アルコキシ置換されたアルキルでもない、
    請求項3~5のいずれか一項に記載の組成物。
    The second (meth) acrylic monomer has the formula (2).
    Figure JPOXMLDOC01-appb-C000002
    Represented by
    R 3 is a hydrogen atom or a methyl group and
    R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkyl are alkoxy-substituted,
    The composition according to any one of claims 3 to 5.
  7. 式(4)により表される化合物が、4-ヒドロキシブチルビニルエーテル、2-メトキシエチルアクリレート、(3-エチルオキセタン-3-イル)メチルアクリレートまたは2,3-エポキシプロピルメタクリレートである、請求項1~6のいずれか一項に記載の組成物。 The compound represented by the formula (4) is 4-hydroxybutyl vinyl ether, 2-methoxyethyl acrylate, (3-ethyloxetane-3-yl) methyl acrylate or 2,3-epoxypropyl methacrylate. The composition according to any one of 6.
  8. 前記第2の(メタ)アクリルモノマーが、エチルアクリレート、ステアリルアクリレート、イソステアリルアクリレートまたはラウリルアクリレートである、請求項3~6のいずれか一項に記載の組成物。 The composition according to any one of claims 3 to 6, wherein the second (meth) acrylic monomer is ethyl acrylate, stearyl acrylate, isostearyl acrylate or lauryl acrylate.
  9. 式(4)
    Figure JPOXMLDOC01-appb-C000003
    により表される化合物のコポリマーおよび導電成分を含む、導電材であって、
    は、水素原子またはメチル基であり、
    は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であり、
    nは、0または1の整数である、
    導電材。
    Equation (4)
    Figure JPOXMLDOC01-appb-C000003
    A conductive material containing a copolymer of the compound represented by and a conductive component.
    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. ,
    n is an integer of 0 or 1,
    Conductive material.
  10. 請求項1~8に記載の1つまたは複数の特徴を含む、請求項9に記載の導電材。 The conductive material according to claim 9, which comprises one or more of the features according to claims 1-8.
  11. 式(4)
    Figure JPOXMLDOC01-appb-C000004
    により表される化合物のコポリマーおよび導電成分を含む導電材を製造する方法であって、前記方法は、
    前記式(4)により表される化合物および重合性モノマーを重合することによりコポリマーを得る工程、
    該コポリマーおよび導電成分を混合して、混合物を得る工程、および
    該混合物を加熱して導電材を生成する工程
    を包含し、
    は、水素原子またはメチル基であり、
    は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であり、
    nは、0または1の整数である、
    方法。
    Equation (4)
    Figure JPOXMLDOC01-appb-C000004
    A method for producing a copolymer of a compound represented by the above and a conductive material containing a conductive component.
    A step of obtaining a copolymer by polymerizing a compound represented by the formula (4) and a polymerizable monomer.
    Including the steps of mixing the copolymer and the conductive components to obtain a mixture, and heating the mixture to produce a conductive material.
    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. ,
    n is an integer of 0 or 1,
    Method.
  12. 請求項1~10に記載の1つまたは複数の特徴を含む、請求項11に記載の方法。 11. The method of claim 11, comprising one or more of the features of claims 1-10.
  13. 式(4)
    Figure JPOXMLDOC01-appb-C000005
    により表される化合物と第2の(メタ)アクリルモノマーとのコポリマーであって、
    は、水素原子またはメチル基であり、
    は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であり、
    nは、0または1の整数であり、
    該第2の(メタ)アクリルモノマーは、式(2)
    Figure JPOXMLDOC01-appb-C000006
    によって表され、
    は、水素原子またはメチル基であり、
    は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であるが、ただし、Rは、酸素含有環で置換されたアルキル基でも、アルコキシ置換されたアルキルでもない、
    コポリマー。
    Equation (4)
    Figure JPOXMLDOC01-appb-C000005
    It is a copolymer of a compound represented by and a second (meth) acrylic monomer.
    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. ,
    n is an integer of 0 or 1 and
    The second (meth) acrylic monomer has the formula (2).
    Figure JPOXMLDOC01-appb-C000006
    Represented by
    R 3 is a hydrogen atom or a methyl group and
    R 4 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, but however, R 4 is also an alkyl group substituted with an oxygen-containing rings, nor alkyl are alkoxy-substituted,
    Copolymer.
  14. 請求項1~12に記載の1つまたは複数の特徴を含む、請求項13に記載のコポリマー。 The copolymer according to claim 13, which comprises one or more of the features of claims 1-12.
  15. 請求項13または14に記載の式(4)により表される化合物のコポリマーを含む、導電成分を含む導電材中のマトリクスとして使用するための組成物。 A composition for use as a matrix in a conductive material containing a conductive component, which comprises a copolymer of a compound represented by the formula (4) according to claim 13 or 14.
  16. 請求項1~14に記載の1つまたは複数の特徴を含む、請求項15に記載の組成物。 15. The composition of claim 15, comprising one or more of the features of claims 1-14.
  17. 式(4)
    Figure JPOXMLDOC01-appb-C000007
    により表される化合物と第2の(メタ)アクリルモノマーとのコポリマーおよび
    金属
    の混合物であって、
    は、水素原子またはメチル基であり、
    は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基であり、
    nは、0または1の整数である、
    混合物。
    Equation (4)
    Figure JPOXMLDOC01-appb-C000007
    A copolymer of a compound represented by and a second (meth) acrylic monomer and a mixture of metals.
    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. ,
    n is an integer of 0 or 1,
    blend.
  18. 前記金属が、銀、銅、金、アルミニウム、亜鉛、ニッケル、錫、および/または鉄を含む、請求項17に記載の混合物。 The mixture according to claim 17, wherein the metal comprises silver, copper, gold, aluminum, zinc, nickel, tin, and / or iron.
  19. 請求項1~16に記載の1つまたは複数の特徴を含む、請求項17または18に記載の混合物。 The mixture according to claim 17 or 18, which comprises one or more of the characteristics of claims 1-16.
PCT/JP2020/030369 2019-08-09 2020-08-07 Novel firing temperature reducing agent for conductive material WO2021029362A1 (en)

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JP2004315719A (en) * 2003-04-18 2004-11-11 Nippon Shokubai Co Ltd Resin composition for baking
JP2010250109A (en) * 2009-04-16 2010-11-04 Fujifilm Corp Positive photosensitive composition, transparent conductive film, display element and integrated solar battery
JP2011246711A (en) * 2010-05-28 2011-12-08 Dongwoo Fine-Chem Co Ltd Adhesive composition and polarizing plate containing the same
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JPH04170482A (en) * 1990-11-02 1992-06-18 Kansai Paint Co Ltd Curable resin composition
JP2004315719A (en) * 2003-04-18 2004-11-11 Nippon Shokubai Co Ltd Resin composition for baking
JP2010250109A (en) * 2009-04-16 2010-11-04 Fujifilm Corp Positive photosensitive composition, transparent conductive film, display element and integrated solar battery
JP2011246711A (en) * 2010-05-28 2011-12-08 Dongwoo Fine-Chem Co Ltd Adhesive composition and polarizing plate containing the same
WO2018235907A1 (en) * 2017-06-23 2018-12-27 積水化学工業株式会社 Resin composition, inorganic fine particle-dispersed slurry composition, inorganic fine particle-dispersed sheet, method for manufacturing all-solid-state battery, and method for manufacturing laminated ceramic capacitor

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023074722A1 (en) * 2021-10-27 2023-05-04 大阪有機化学工業株式会社 Composition for forming electroconductive elastomer, electroconductive elastomer, and polymer

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