Novel conductivity improver

Abstract

The present disclosure provides a composition for improving the electric conductivity of an electric conductive component or an electric conductive material, the composition containing a fluorinated alkyl (meth)acrylate. The present disclosure also provides: an electric conductive material comprising a copolymer of a fluorinated alkyl (meth)acrylate and an electric conductive component; and a method for producing the electric conductive material. The present disclosure also provides a use of a copolymer of a fluorinated alkyl (meth)acrylate as a matrix.

Description

Technical Field

[0001] The present disclosure relates to a novel conductivity improver and related technologies. More specifically, the present disclosure relates to a composition for improving the conductivity of a conductive material, including fluorinated alkyl (meth)acrylate, etc.

Background Art

[0002] Various improvements have been made to conductive materials and conductors. However, the current conductive materials provided are currently limited to those containing a specific combination of conductive components and a base material.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Means for Solving the Problems

[0004] The present disclosure provides a conductive material including a desired combination of conductive components and a base material.

[0005] The present disclosure provides, for example, the following.

[0006] (Item 1) A composition for improving the conductivity of a conductive component or a conductive material, including fluorinated alkyl (meth)acrylate. (Item 2) The composition according to item 1, wherein the conductive material contains a copolymer of the fluorinated alkyl (meth)acrylate and a conductive component. (Item 3) The composition according to any one of the preceding items, wherein the copolymer is a copolymer of the fluorinated alkyl (meth)acrylate and a second (meth)acrylic monomer. (Item 4) The fluorinated alkyl (meth)acrylate is represented by the formula (1)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0007] In the present disclosure, it is intended that the above one or more features can be provided in further combinations in addition to the explicitly stated combinations. Further embodiments and advantages of the present disclosure will be recognized by those skilled in the art upon reading the following detailed description as needed. [Advantages of the Invention]

[0008] According to the present disclosure, a conductivity improver is provided, and by using these, a technique capable of improving conductivity can be provided. [Modes for Carrying Out the Invention]

[0009] Hereinafter, the present disclosure will be described while showing the best mode. Throughout this specification, it should be understood that the singular expressions include the concepts of their plural forms unless otherwise specified. Therefore, singular articles (for example, "a", "an", "the", etc. in English) should be understood to include the concepts of their plural forms unless otherwise specified. Also, the terms used in this specification should be understood to be used in the meanings commonly used in the relevant field unless otherwise specified. Therefore, unless otherwise defined, all technical terms and scientific and technical terms used in this specification have the same meanings as those generally understood by those skilled in the field to which the present disclosure belongs. In case of contradiction, this specification (including definitions) shall prevail.

[0010] Hereinafter, the definitions of the terms particularly used in this specification and / or the basic technical contents will be appropriately described.

[0011] (Definition of terms) In this specification, "conductivity" is used in the ordinary meaning in the relevant field and means the property of conducting electricity. The physical quantity thereof is called "conductivity" and is defined as the reciprocal of the resistivity (specific resistance, also called volume resistivity in the resin field) of a certain object (also called a conductor). In this specification, the conductivity (or resistivity) is measured as follows. Specifically, unless otherwise specified, the measurement object (for example, a film, etc.) is cut out to a size of 0.5 cm in length × 2.00 cm in width × 0.2 cm in thickness, and the value measured by the four-terminal measurement method (for example, Loresta GP [manufactured by Mitsubishi Chemical Analytech Co., Ltd.] can be used, but not limited thereto) is adopted.

[0012] In this specification, "conductive material" refers to any material having conductivity. In this specification, the conductive material has a conductivity of 1.0×10 -1 Ω·cm or less, usually 1.0×10 -2 Ω·cm or less, preferably 1.0×10 -3Although it is targeted at those having a resistivity of 1 Ω·cm or less, it is not limited thereto. The conductive material contains a conductive component that imparts conductivity. Typically, the conductive material is composed of a base material and a conductive component.

[0013] In this specification, "improving the conductivity" means that when the component of the present disclosure is added to the conductive component or the conductive material, the conductivity is significantly increased as compared with the case where it is not added. For example, the conductivity is increased by at least about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 99%. It can also be expressed by a decrease in the volume resistivity. For example, compared with the comparison target, the volume resistivity is decreased by about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 99%.

[0014] In this specification, the "base material", also referred to as the matrix, refers to the basic part of the structure of the 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.

[0015] In this specification, the "conductive component" means any component that imparts conductivity. Examples of the conductive component include, but are not limited to, any metal component, metal oxide, metal carbide and other metal-based components, conductive carbon-based components, conductive organic compounds, conductive polymers, etc.

[0016] In this specification, the "metal-based component" is a component that contains metal atoms in some form as its constituent elements, and is a concept that includes metal components such as metals, and components derived from metals (for example, metal oxides, metal carbides, metal sulfides, etc.).

[0017] In this specification, "metal component" includes a metal or an alloy.

[0018] In this specification, "conductive carbon-based component" means a conductive material containing carbon. Specific examples thereof include natural graphite such as flake graphite, graphite such as artificial graphite, carbon blacks such as acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, carbon-based materials such as graphene, carbon nanotubes, and fullerenes; carbon fibers; carbon fluorides, etc., but are not limited thereto. Metal carbides are not included in the conductive carbon-based components. "Conductive carbon-based component" may also be referred to as "carbon-based component".

[0019] In this specification, "(meth)acrylic monomer" is a monomer containing an acrylic group and / or a methacrylic group, and examples thereof include acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, etc.

[0020] In this specification, "(meth)acrylic" means "acrylic" or "methacrylic", and "(meth)acrylate" means "acrylate" or "methacrylate".

[0021] For example, the (meth)acrylic monomer is represented by formula (2)

Chemical formula

[0022] A typical example of the "fluorinated alkyl (meth)acrylate" in this specification is the (meth)acrylate represented by the formula (1) [Chemical formula] wherein R 1 is a hydrogen atom or a methyl group, and R 2 is an alkyl group substituted with from 1 to the substitutable number of fluorine atoms.

[0023] In this specification, the "substitutable number" means the maximum number of hydrogens that can be substituted on a certain group, provided that the resulting group is chemically stable when substituting the hydrogen on the group with a substituent.

[0024] In this specification, the "alkyl group" refers to a monovalent group formed by losing one hydrogen atom from an aliphatic hydrocarbon (alkane) such as methane, ethane, or propane, and is generally represented by C n H 2n+1 -(where n is a positive integer). The alkyl group can be linear or branched. Examples of alkyl (C 1~4 alkyl) groups having 1 to 4 carbon atoms include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, etc., but the present disclosure is not limited to such examples only. Examples of alkyl (C 1~6 alkyl) groups having 1 to 6 carbon atoms include, for example, a C 1~4 alkyl group, an n-pentyl group, an isoamyl group, an n-hexyl group, an isohexyl group, etc., but the present disclosure is not limited to such examples only. Examples of alkyl (C 1~10 alkyl) groups having 1 to 10 carbon atoms include, for example, a C 1~6 alkyl group, an n-octyl group, an n-nonyl group, an isononyl group, a branched nonyl group, an n-decanyl group, an isodecyl group, etc., but the present disclosure is not limited to such examples only. Examples of alkyl (C 1~18 alkyl) groups having 1 to 18 carbon atoms include, for example, a C 1~10Examples of the alkyl group include undecyl, lauryl, tridecyl, myristyl, pentadecyl, palmitoyl, heptadecyl, stearyl, isostearyl, etc., but the present disclosure is not limited to such examples only.

[0025] As used herein, the "alkenyl group" refers to a monovalent group formed by removing one hydrogen atom from an aliphatic hydrocarbon (alkene) containing at least one double bond such as ethene, propene, or butene, and is generally represented by C m H 2m-1 (where m is an integer of 2 or more). The alkenyl group can be linear or branched. Examples of the alkenyl group having 2 to 6 carbon atoms include ethenyl, 1-propenyl, 2-propenyl, butenyl, pentenyl, hexenyl, etc., but the present disclosure is not limited to such examples only. Examples of the alkenyl group having 2 to 10 carbon atoms include the alkenyl group having 2 to 6 carbon atoms, heptenyl, octenyl, nonenyl, decenyl, etc., but the present disclosure is not limited to such examples only.

[0026] As used herein, the "alkoxy group" refers to a monovalent group formed by removing the hydrogen atom of the hydroxy group of alcohols, and is generally represented by C n H 2n+1 O- (where n is an integer of 1 or more). Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tert-butyloxy, sec-butyloxy, n-pentyloxy, isoamyloxy, n-hexyloxy, isohexyloxy, etc., but the present disclosure is not limited to such examples only.

[0027] As used herein, the term "haloalkyl group" refers to an alkyl group in which one or more hydrogen atoms on the above alkyl group are substituted with halogen atoms. Further, "perhaloalkyl" refers to an alkyl group in which all hydrogen atoms on the above alkyl group are substituted with halogen atoms. Examples of the haloalkyl group having 1 to 6 carbon atoms (C 1-6 haloalkyl group) include, for example, C 1-6 fluorinated alkyl groups, etc., but the present disclosure is not limited only to such examples. Examples of the haloalkyl group having 1 to 8 carbon atoms (C 1-8 haloalkyl group) include C 1-8 fluorinated alkyl groups, etc., but the present disclosure is not limited only to such examples.

[0028] As used herein, the term "fluorinated alkyl group" refers to an alkyl group in which one or more hydrogen atoms on the above alkyl group are substituted with fluorine atoms. Examples of the fluorinated alkyl group having 1 to 6 carbon atoms (C 1-6 fluorinated alkyl group) include, for example, trifluoromethyl group, trifluoroethyl group (such as 2,2,2-trifluoroethyl group), perfluoroethyl group, trifluoro n-propyl group, tetrafluoropropyl group (such as 2,2,3,3-tetrafluoropropyl group), perfluoro n-propyl group, trifluoroisopropyl group, perfluoroisopropyl group, trifluoro n-butyl group, perfluoro n-butyl group, trifluoroisobutyl group, perfluoroisobutyl group, trifluoro tert-butyl group, perfluoro tert-butyl group, trifluoro n-pentyl group, octafluoropentyl group (such as 2,2,3,3,4,4,5,5-octafluoropentyl group), perfluoro n-pentyl group, trifluoro n-hexyl group, perfluoro n-hexyl group, etc., but the present disclosure is not limited only to such examples. Examples of the fluorinated alkyl group having 1 to 8 carbon atoms (C 1-8 fluorinated alkyl group) include C 1-6Examples of the fluorinated alkyl group include an undecafluoro n-heptyl group, a perfluoro n-heptyl group, a tridecafluoro octyl group (such as 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro octyl group), a perfluoro n-octyl group, etc., but the present disclosure is not limited to such examples only. The "fluorinated alkyl group" can be used interchangeably with the "fluorinated alkyl" and the "alkyl group substituted with one to the maximum number of substitutable fluorine atoms".

[0029] As used herein, the "cycloalkyl group" means a monocyclic or polycyclic saturated hydrocarbon group, including those having a cross-linked structure. For example, "C 3-12 cycloalkyl group" means a cyclic alkyl group having 3 to 12 carbon atoms. C 6-12 Specific examples of the 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, etc., but the present disclosure is not limited to such examples only. C 5-12 Specific examples of the cycloalkyl group include a cyclopentyl group, C 6-12 cycloalkyl group, etc., but the present disclosure is not limited to such examples only. C 3-12 Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, C 5-12 cycloalkyl group, etc. Preferably, "C 6-12 cycloalkyl group" is mentioned, but the present disclosure is not limited to such examples only.

[0030] As used herein, the "cycloalkenyl group" means a monocyclic or polycyclic unsaturated hydrocarbon group containing a double bond, including those having a cross-linked structure. Examples include those in which one or more of the carbon-carbon bonds of the above "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 include "C 6-12In the case of a "cycloalkenyl group", examples include 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclononenyl group, etc. "C 3-12 In the case of a "cycloalkyl group", examples include cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, C 6-12 Cycloalkenyl groups and the like. Preferably, a "C 6-12 Cycloalkenyl group" is exemplified, but the present disclosure is not limited to such examples.

[0031] As used herein, "non-aryl heterocycloalkyl" and "non-aryl heterocycle" mean a cyclic group having 1 to 3 atoms, the same or different, selected from nitrogen, oxygen, and sulfur atoms in the ring, and the group may contain one or more unsaturated bonds but does not contain an aromatic group. For example, "3- to 8-membered non-aryl heterocycloalkyl" means a non-aryl heterocycloalkyl having 3 to 8 ring-constituting atoms. Specific examples of "non-aryl heterocycloalkyl" include oxiranyl group, oxetanyl group, pyranyl group, pyrrolidinyl group, imidazolidinyl group, piperidinyl group, morpholinyl group, thiomorpholinyl group, hexamethyleneiminyl group, thiazolidinyl group, tetrahydrofuranyl group, tetrahydropyridinyl group, tetrahydropyranyl group, 1,3-dioxolanyl group, 1,3-dioxanyl group, 1,4-dioxanyl group, etc., but the present disclosure is not limited to such examples. Note that the group also includes those having a crosslinked structure.

[0032] As used herein, an "aryl group" refers to a group formed by the removal of one hydrogen atom bonded to the ring of an aromatic hydrocarbon. For example, from benzene, a phenyl group (C6H5-), from toluene, a tolyl group (CH3C6H4-), from xylene, a xylyl group ((CH3)2C6H3-), and from naphthalene, a naphthyl group (C 10 H8-) is derived. "C 6~14 An aryl group" means an aromatic hydrocarbon group having 6 to 14 carbon atoms. "C 6~14Specific examples of the "aryl group" include, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, azulenyl group, acenaphthylenyl group, acenaphthyl group, anthryl group, fluorenyl group, phenalenyl group, phenanthryl group, etc. "C 6~18 Specific examples of the "aryl group" include, for example, C 6~14 aryl group, benzo[a]anthryl group, benzo[a]fluorenyl group, benzo[c]phenanthryl group, chrysenyl group, fluoranthenyl group, pyrenyl group, tetracenyl group, triphenylenyl group, etc. The arylthio group means an aryl-S-group. For example, phenyl-S-group (phenylthio group) etc. can be mentioned, but the present disclosure is not limited only to such examples.

[0033] In this specification, the "heteroaryl group" means a monocyclic or polycyclic heteroatom-containing aromatic group, and the group contains one or more (for example, 1 to 4) same or different heteroatoms selected from nitrogen atoms, sulfur atoms and oxygen atoms. For example, the "5- to 18-membered heteroaryl group" means a heteroaryl group having 5 to 18 ring-constituting atoms. The "haloheteroaryl group" refers to a group in which one or more hydrogens on the ring-constituting atoms are substituted with halogen. Specific examples of the "heteroaryl group" include, for example, pyrrolyl group, thienyl group, benzothienyl group, benzofuranyl group, benzoxazolyl group, benzothiazolyl group, furyl group, oxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, benzoisoxazolyl group, benzoisothiazolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazyl group, pyrimidinyl group, pyridazinyl group, quinolyl group, isoquinolyl group, triazolyl group, triazinyl group, tetrazolyl group, indolyl group, imidazo[1,2-a]pyridyl group, pyrazolo[1,5-a]pyridyl group, [1,2,4]triazolo[1,5-a]pyridyl group, benzimidazolyl group, quinoxalyl group, cinnolyl group, quinazolinyl group, indazolyl group, naphthyridyl group, quinolinolyl group, isoquinolinolyl group, etc., but the present disclosure is not limited only to such examples.

[0034] Generally, the term "substituted" refers to the replacement of one or more hydrogen radicals in a given structure by the radical of a specific substituent. It is recognized that the phrase "may be substituted" is used interchangeably with the phrase "unsubstituted or substituted". For example, "C 1~10 which may be substituted with an alkyl group C 6~18 aryl group" is synonymous with "unsubstituted C 6~18 aryl group, or C 1~10 aryl group substituted with an alkyl group C 6~18 ". In this specification, the number of substituents in a group defined using "substituted" or "may be substituted" is not particularly limited as long as substitution is possible, and is one or more. Also, unless otherwise indicated, the description of each group applies also when the group is part of another group or a substituent. When indicating the number of carbon atoms in the definition of a "substituent", it may be expressed as, for example, "C 1-6 ", etc. Specifically, the notation "C 1-6 alkyl" is synonymous with an alkyl group having 1 to 6 carbon atoms. Also, in this specification, a substituent for which the term "substituted" or "may be substituted" is not specifically indicated means an "unsubstituted" substituent.

[0035] In this specification, the term "polymer" refers to a compound formed by the polymerization of a plurality of monomers. In this case, the monomer is the "starting material", and the polymer is the product (final product).

[0036] In this specification, a "homopolymer" is a compound formed by the polymerization of only one type of monomer, and a "copolymer" is a compound formed by the polymerization of two or more types of monomers.

[0037] In this specification, a "copolymer containing a monomer component" refers to a copolymer produced by polymerizing the monomer component.

[0038] In this specification, the copolymer of monomer A means a copolymer in which one of the monomers contained is monomer A.

[0039] In this specification, “(meth)acrylate” means acrylate or methacrylate, and acrylate and methacrylate may each be used alone or in combination. “(meth)acryloyloxy” means acryloyloxy or methacryloyloxy, and acryloyloxy and methacryloyloxy may each be used alone or in combination. “(meth)acrylic acid” means acrylic acid or methacrylic acid, and acrylic acid and methacrylic acid may each be used alone or in combination.

[0040] In this specification, “(meth)acrylic polymer” and “(meth)acrylic-based polymer” refer to homopolymers or copolymers such as (meth)acrylic acid, (meth)acrylate, or salts or derivatives thereof.

[0041] In this specification, “monomer” refers to a compound that polymerizes with two or more other monomers to form a polymer. Examples of the monomers of the present disclosure include (meth)acrylic monomers, ethylene monomers, urethane monomers, amide monomers, ester monomers, ether monomers, imide monomers, amide-imide monomers, carbonate monomers, acetal monomers, sulfone monomers, phenylene sulfide monomers, ether-ether-ketone monomers, silicone monomers, styrene monomers, butadiene monomers, and monomers that form AES resin, diallyl phthalate resin, ABS resin, or silicone resin by polymerization.

[0042] In this specification, “sintering” refers to the phenomenon in which raw material powder solidifies at high temperature. Although gaps are observed between the particles of the raw material powder, when sintering occurs in a high-temperature environment (a temperature lower than the melting point), the contact area between the particles increases and the gaps decrease, resulting in solidification. The remaining gaps are referred to as “voids” or “pores”.

[0043] As used herein, the term "kit" refers to a unit that is usually divided into two or more compartments and in which the parts to be provided (e.g., coating components, conductive components, solvents, instructions, etc.) are provided. When aiming to provide a composition that should not be provided in a mixed state for reasons such as stability and is preferably mixed and used immediately before use, this kit form is preferred. Such a kit preferably includes an instruction manual or description that describes how to use the provided parts (e.g., conductive components, coating components), or how to handle reagents or waste liquids after use. When a kit is used herein, the kit may usually include an instruction manual that describes how to use solvents and the like.

[0044] (Basic description of the 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 its conductivity is improved by including a composition (also referred to as a conductivity improver) for improving the conductivity provided in the present disclosure.

[0045] The conductive material of the present disclosure may typically include other substrates in addition to the conductive component.

[0046] (Basic description of the conductivity improver) The composition (conductivity improver) for improving the conductivity provided in the present disclosure includes fluorinated alkyl (meth)acrylate.

[0047] In a representative embodiment, an example of the fluorinated alkyl (meth)acrylate provided in the present disclosure is represented by formula (1) [Chemical formula] represented by, where R 1 is a hydrogen atom or a methyl group, and R 2is an alkyl group substituted with fluorine atoms from 1 to the replaceable number. In the fluorinated alkyl (meth)acrylate represented by formula (1), regardless of the number of fluorine atoms contained, the form of the alkyl group (number of carbon atoms, branched / linear state, etc.), whether it is methacryl or acrylic, etc., all improve the conductivity of the conductive component or the conductive material.

[0048] The basic usage method of the conductivity improver is as follows.

[0049] In the present disclosure, when the base material is a polymer, the polymer contains a conductivity improver. That is, the polymer provided in the present disclosure is a homopolymer or a copolymer containing the above-mentioned fluorinated alkyl (meth)acrylate as a structural unit.

[0050] (Conductive component targeted by the conductivity improver) The conductive component that the conductivity improver of the present disclosure can target is a component having any conductivity. Preferably, metal-based components and conductive carbon-based components are included. More preferably, metal components, carbon black, graphene, and carbon nanotubes are included. Even more preferably, silver and carbon nanotubes can be mentioned.

[0051] (General manufacturing method of the conductive material) (1) Method for manufacturing the polymer matrix In a representative embodiment, the polymer matrix of the present disclosure can be prepared by heating the monomer and / or irradiating the monomer with ultraviolet light of a specific illuminance for polymerization. Such ultraviolet irradiation can be arbitrarily set and implemented by those skilled in the art. When preparing the polymer matrix, when it is prepared by polymerization using ultraviolet light, a drying operation for removing a solvent, which is a complicated operation, is not required, and the workability is excellent.

[0052] Here, ultraviolet rays refer to electromagnetic waves with wavelengths shorter than visible light and longer than X-rays. The short-wavelength end of the upper limit of visible light is 400 nm, and ultraviolet rays can be defined as electromagnetic waves with wavelengths below this. The lower limit of the wavelength of ultraviolet rays is about 10 nm, and it is understood that electromagnetic waves with wavelengths longer than this fall within the category of ultraviolet rays. The wavelength of ultraviolet rays used in the present disclosure can be any wavelength, and an appropriate one can be selected according to the purpose. For example, in the present disclosure, any wavelength can be used as long as it can have an initial effect on the monomer. Typically, it is a wavelength that can be irradiated by the light source used in the examples. Specifically, a light source with a wavelength of about 150 nm to 400 nm is used, preferably 300 nm to 400 nm.

[0053] The preferred illuminance of the ultraviolet rays used in the present disclosure varies depending on the starting material. The ultraviolet irradiation device is not particularly limited, and examples include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, black light lamps, UV electrodeless lamps, short arc lamps, LEDs, and the like.

[0054] When polymerizing the monomer, it is preferable to use a polymerization initiator. Examples of the polymerization initiator include thermal polymerization initiators, photopolymerization initiators, redox polymerization initiators, ATRP (atom transfer radical polymerization) initiators, ICAR ATRP initiators, ARGET ATRP initiators, RAFT (reversible addition-fragmentation chain transfer polymerization) agents, NMP (polymerization via nitroxide) agents, polymer polymerization initiators, and the like. These polymerization initiators may be used alone or in combination of two or more. Among these polymerization initiators, photopolymerization initiators are preferable from the viewpoint of not leaving a thermal history in the polymer matrix.

[0055] Examples of the photoinitiator include 2,4,6-trimethylbenzoyldiphenylphosphine 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'-di-tert-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, phenylglyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-2-(o-benzoyloxime)], photo radical polymerization initiators such as bis(η5-2,4-cyclopentadien-1-yl)bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyltitanium], 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(p-methoxyphenylvinyl)-1,3,5-triazine, diphenyliodonium tetrafluoroborate, 4,4'-di-tert-butyldiphenyliodonium tetrafluoroborate, 4-diethylaminophenylbenzenediazonium hexafluorophosphate, diphenyl-4-phenylthiophenylsulfonium hexafluorophosphate and other photo cationic ring-opening polymerization initiators, but the present disclosure is not limited to such examples. These photoinitiators may be used alone or in combination of two or more thereof.

[0056] When a photoinitiator is used as the polymerization initiator, the amount of the photoinitiator is preferably usually about 0.01 part by weight to about 20 parts by weight per 100 parts by weight of the total monomers.

[0057] Examples of the thermal polymerization initiator include azo-based polymerization initiators such as azobisisobutyronitrile (AIBN), 2,2'-azobis(isobutyric acid methyl), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), peroxide-based polymerization initiators such as benzoyl peroxide, potassium persulfate, ammonium persulfate, etc. However, the present disclosure is not limited to such examples only. These polymerization initiators may be used alone or in combination of two or more.

[0058] When a thermal polymerization initiator is used as the polymerization initiator, the amount of the thermal polymerization initiator is preferably usually about 0.01 part by weight to about 20 parts by weight per 100 parts by weight of the total monomers.

[0059] When a polymerization initiator that generates nitrogen (N2) during the polymerization reaction, such as AIBN, is used, the resulting composite material may contain bubbles. Since such bubbles can be the starting point of fracture, while the properties such as the extensibility of the composite material may decrease, it is predicted that the impact absorption ability can be improved. It should be noted that the bubbles contained in the composite material are not limited to those derived from the polymerization initiator, and may be bubbles obtained by known methods such as adding a foaming agent or removing a solvent, which can include bubbles in resins and the like.

[0060] Other polymerization initiators that can be used in the present disclosure include, for example, redox polymerization initiators such as hydrogen peroxide and iron(II) salts, persulfates and sodium bisulfite, ATRP (atom transfer radical polymerization) initiators using alkyl halides under metal catalysts, ICAR ATRP initiators and ARGET ATRP initiators using metals and nitrogen-containing ligands, RAFT (reversible addition-fragmentation chain transfer polymerization) agents, NMP (nitroxide-mediated polymerization) agents, polymer azo polymerization initiators containing polydimethylsiloxane units, polymer azo polymerization initiators containing polyethylene glycol units, etc. However, the present disclosure is not limited only to such examples. These polymerization initiators may be used alone or in combination of two or more.

[0061] When polymerizing the monomer, a chain transfer agent may be used to adjust the molecular weight. The chain transfer agent can usually be used by mixing with the monomer. Examples of the chain transfer agent include mercaptan group-containing compounds such as 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid, 2-(dodecylthiocarbonothioylthio)propionic acid, methyl 2-(dodecylthiocarbonothioylthio)-2-methylpropionate, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid 3-azido-1-propanol ester, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid pentafluorophenyl ester, lauryl mercaptan, dodecyl mercaptan, thioglycerol, etc., and inorganic salts such as sodium hypophosphite and sodium bisulfite. However, the present disclosure is not limited only to such examples. These chain transfer agents may be used alone or in combination of two or more. The amount of the chain transfer agent is not particularly limited, but usually may be about 0.01 parts by weight to about 10 parts by weight per 100 parts by weight of the total monomer.

[0062] The atmosphere during the polymerization of the monomer is not particularly limited and may be air, or an inert gas such as nitrogen gas or argon gas.

[0063] When polymerizing the monomer, the temperature is not particularly limited, and it is usually preferably about 5 to 100 °C. The time required to polymerize the monomer is arbitrary because it varies depending on the polymerization conditions and cannot be determined unconditionally, but it is usually about 1 to 20 hours.

[0064] The polymerization reaction can be arbitrarily terminated when the amount of the remaining monomer reaches 20% by mass or less. The amount of the remaining monomer can be measured, for example, using gel permeation chromatography (GPC).

[0065] By bulk polymerizing the monomer as described above, a polymer matrix can be obtained.

[0066] 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.

[0067] 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.

[0068] Examples of the method for polymerizing the monomer include bulk polymerization method, solution polymerization method, emulsion polymerization method, suspension polymerization method, etc., but the present disclosure is not limited only to such examples. Among these polymerization methods, bulk polymerization method and solution polymerization method are preferred.

[0069] Also, the polymerization of the monomer can be carried out by methods such as radical polymerization method, living radical polymerization method, anionic polymerization method, cationic polymerization method, addition polymerization method, polycondensation polymerization method, catalytic polymerization, etc.

[0070] When polymerizing a monomer by solution polymerization, for example, the monomer can be polymerized by dissolving the monomer in a solvent and adding a polymerization initiator to the resulting solution while stirring the solution. Alternatively, the monomer can be polymerized by dissolving the polymerization initiator in a solvent and adding the monomer to the resulting solution while stirring the solution. The solvent is preferably an organic solvent compatible with the monomer.

[0071] The homopolymer or copolymer contained in the conductive material of the present disclosure may be polymerized by using a peroxide-based initiator (e.g., benzoyl peroxide, azobisisobutyronitrile, and their analogs) as a polymerization initiator.

[0072] When using the polymerization initiator that can be used as described above as a polymerization initiator, the amount of the polymerization initiator is preferably usually about 0.01 parts by weight to about 20 parts by weight per 100 parts by weight of all monomers.

[0073] 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 photoinitiator in one embodiment and in the absence of a photoinitiator in another embodiment. Any of these embodiments is within the scope of the present disclosure.

[0074] There are no particular limitations on the polymerization reaction temperature and atmosphere when polymerizing the monomer. Usually, 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, for example. Also, the polymerization reaction time of the monomer varies depending on the polymerization reaction temperature and the like, and thus cannot be determined unconditionally, but is usually about 3 to 20 hours.

[0075] (2) Method for producing the polymer matrix contained in the conductive material The polymer (or polymer matrix) contained in the conductive material of the present disclosure can be produced by mixing one or more specific monomers and polymerizing them under appropriate polymerization conditions using additives such as an appropriate polymerization initiator as needed. Then, the conductive material of the present disclosure can be produced by mixing a conductive component and any other components into this polymer matrix and heating. Regarding the polymer, the individual components, specific production conditions, etc. will be described in detail below.

[0076] In one aspect, the present disclosure relates to a method for producing a homopolymer obtained by polymerizing a fluorinated alkyl (meth)acrylate represented by formula (1)

Chemical formula

[0077] In one aspect, the present disclosure relates to a method for producing a homopolymer obtained by polymerizing a (meth)acrylic monomer represented by formula (2)

Chemical formula

[0078] In one aspect, the present disclosure relates to a method for producing a copolymer of a fluorinated alkyl (meth)acrylate and a second (meth)acrylic monomer, wherein the fluorinated alkyl (meth)acrylate is represented by formula (1)

Chemical formula

Chemical formula

[0079] 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 bulk polymerization method, solution polymerization method, emulsion polymerization method, and suspension polymerization method. Without wishing to be bound by theory, the monomers of the present disclosure can be polymerized by chain polymerization, sequential polymerization, or living polymerization.

[0080] (3-1) Method for preparing monomer The fluorinated alkyl (meth)acrylate and (meth)acrylic monomer used in the present disclosure may be commercially available from manufacturers exemplified in the examples, etc., or may be prepared according to methods well known to those skilled in the art.

[0081] (3-2) Manufacturing method by photopolymerization In one embodiment, the polymer matrix of the present disclosure is obtained in one step by exposing and polymerizing a monomer (including one or more monomers) in the presence of a polymerization initiator.

[0082] In one embodiment, the polymer matrix of the present disclosure can be produced by irradiating one kind of fluorinated alkyl (meth)acrylate with ultraviolet rays in the presence of a polymerization initiator.

[0083] In one embodiment, the polymer matrix of the present disclosure can be produced by irradiating one kind of (meth)acrylic monomer with ultraviolet rays in the presence of a polymerization initiator.

[0084] In one embodiment, the polymer matrix of the present disclosure can be produced by irradiating ultraviolet light to a (meth)acrylic monomer and a fluorinated alkyl (meth)acrylate in the presence of a polymerization initiator.

[0085] Preferred examples of the polymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0086] This step is usually carried out at room temperature for about 2 hours, but is not limited thereto, and may be carried out over 0.5 to 3 hours, or 0.5 hour to 24 hours or more.

[0087] (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, and limonene.

[0088] (3-4) Method for preparing conductive material In one embodiment, the conductive material is obtained by mixing the resin solution obtained in (3-3) with a conductive component and, if necessary, a dispersant, and heating the resulting mixture. Those skilled in the art can produce the conductive material using any method described herein and known in the art other than this method.

[0089] (Description of conductive component) Examples of the conductive component include natural graphite such as flaky graphite, graphite such as artificial graphite, carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, carbon-based materials such as graphene, carbon nanotubes, and fullerenes; conductive fibers such as carbon fibers and metal fibers; carbon fluoride; powders of metal particles such as copper, gold, nickel, tin, aluminum, zinc, iron, and silver; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and organic conductive materials such as polyphenylene derivatives. However, the present disclosure is not limited to such examples only. These conductive components may be used alone or in combination of two or more. Among these conductive components, from the viewpoint of obtaining a conductive film excellent in workability and moldability, as well as flexibility and extensibility, carbon nanotubes, carbon black, graphene, and metal particles are preferable, and carbon nanotubes, carbon black, graphene, and silver particles are more preferable.

[0090] Since the content of the solid component of the conductive component in the total solid component of the polymer matrix and the conductive component varies depending on the type of the conductive component and the like, it cannot be determined unconditionally. However, usually, from the viewpoint of obtaining a conductive film excellent in workability and moldability, as well as flexibility and extensibility, it is preferably 1% by mass or more, and from the viewpoint of obtaining a conductive film excellent in workability and moldability, as well as flexibility and extensibility, it is preferably 100% by mass or less.

[0091] Examples of the carbon nanotube include a single-walled carbon nanotube having a hollow cylindrical structure formed by rolling up a single sheet of graphite (graphene sheet) into a cylinder, a multi-walled carbon nanotube having a structure in which a plurality of single-walled carbon nanotubes with different diameters are concentrically stacked, a single-walled carbon nanotube manufactured by a super growth method, a carbon nanocone having a shape in which the ends of the single-walled carbon nanotube are conically closed, a carbon nanotube encapsulating fullerene inside, etc., but the present disclosure is not limited only to such examples. These carbon nanotubes may be used alone or in combination of two or more kinds. Among these carbon nanotubes, multi-walled carbon nanotubes are preferred.

[0092] From the viewpoint of obtaining a conductive film excellent in workability, moldability, flexibility, and stretchability, the length of the carbon nanotube is preferably 0.1 to 1000 μm, more preferably 1 to 500 μm, and still more preferably 1 to 90 μm.

[0093] From the viewpoint of obtaining a conductive film excellent in workability, moldability, flexibility, and stretchability, the diameter of the carbon nanotube is preferably 10 to 50 nm, more preferably 10 to 20 nm.

[0094] From the viewpoint of obtaining a conductive film excellent in workability, moldability, flexibility, and stretchability, the content ratio of the solid content of the carbon nanotube in the total solid content of the polymer matrix and the carbon nanotube is preferably 1% by mass or more, more preferably 1.5% by mass or more, still more preferably 2% by mass or more, and from the viewpoint of obtaining a conductive film excellent in workability, moldability, flexibility, and stretchability, it is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and even more preferably 3.5 to 10% by mass.

[0095] (Use of the conductive material) The conductive material of the present disclosure can be suitably used, for example, in sensors, wirings, electrodes, substrates, power generation elements, speakers, microphones, noise cancelers, transducers, artificial muscles, small pumps, medical instruments, etc. used in actuators, industrial robots, etc., and as a raw material for the conductive film.

[0096] (Preferred Embodiment) The preferred embodiments of the present disclosure will be described below. It is understood that the embodiments provided below are for better understanding of the present disclosure, and the scope of the present disclosure should not be limited to the following description. Therefore, it is obvious that those skilled in the art can make appropriate modifications within the scope of the present disclosure in consideration of the descriptions in this specification. Also, it is understood that the following embodiments of the present disclosure can be used alone or in combination.

[0097] (For Improving Conductivity) In one aspect, the present disclosure relates to applications for improving conductivity. More specifically, in a specific aspect, the present disclosure provides a composition for improving the conductivity of a conductive material, which contains fluorinated alkyl (meth)acrylate.

[0098] Conventionally, in a system where a large amount of silver filler is present as in the present disclosure, it was thought that the polymer composition did not affect conductivity, so sufficient examination has not been done. However, as a result of polymer examination, it was confirmed that the resistivity decreased in a system copolymerized with fluorinated alkyl acrylate compared to conventional products. Furthermore, as a result of further investigation, it was also confirmed that the higher the fluorine atom content contained in the copolymer, the lower the resistivity. From the viewpoint of resin solubility, 2,2,2-trifluoroethyl acrylate (V#3F) was used in this system.

[0099] In one specific embodiment, the conductive material of the present disclosure includes a copolymer of fluorinated alkyl (meth)acrylate and a conductive component. In this way, by being included as a copolymer, the fluorinated alkyl (meth)acrylate can improve the conductivity of the conductive component.

[0100] In one embodiment, a homopolymer of fluorinated alkyl (meth)acrylate can be used. Here, as the conductive component, typically, a metal-based component and a conductive carbon-based component can be used. Specifically, silver, copper, gold, aluminum, zinc, nickel, tin, iron, as well as carbon black, graphene, and carbon nanotubes can be used. Preferably, silver and carbon nanotubes can be used.

[0101] By providing this technology of the present disclosure, the conductivity of any conductive component can be improved.

[0102] In one preferred embodiment, it is advantageous that the copolymer used in the present disclosure is a copolymer of fluorinated alkyl (meth)acrylate and a second (meth)acrylic monomer. The reason is, although not wishing to be bound by theory, the effect of repelling compounds (surface-active effect). Fluorine-based resins have been used as antifouling coatings and release agents and have the effect of repelling compounds (surface-active effect). Regarding the reason for the decrease in resistivity in the present disclosure, it is considered that due to the surface-active effect of the fluorine compound, the fluorinated alkyl (meth)acrylate and the silver particles repelled each other, resulting in the silver particles being more densely packed. Furthermore, it is an unexpected result that the effect was manifested with a small addition amount as in the examples.

[0103] In one embodiment, the fluorinated alkyl (meth)acrylate is represented by formula (1)

Chemical formula

[0104] In one embodiment, the second (meth)acrylic monomer has the formula (2)

Chemical formula

[0105] 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.

[0106] 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.

[0107] 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 4is an unsubstituted alkyl group having 18 to 24 carbon atoms.

[0108] In yet another embodiment, the fluorinated alkyl (meth)acrylate is 2,2,2-trifluoroethyl acrylate. As described above, the reason for the reduced resistivity in the present disclosure is considered to be that the silver particles repelled each other due to the surface-active effect of the fluorine compound, resulting in denser packing of the silver particles.

[0109] In another embodiment, the second (meth)acrylic monomer is isostearyl acrylate or lauryl acrylate.

[0110] In another embodiment, the second (meth)acrylic monomer is isostearyl acrylate, lauryl acrylate or stearyl acrylate.

[0111] In one embodiment, the combination of monomers for producing the polymer matrix of the present disclosure is a combination of 2,2,2-trifluoroethyl acrylate and isostearyl acrylate, lauryl acrylate or stearyl acrylate.

[0112] In one embodiment, the combination of monomers for producing the polymer matrix of the present disclosure is 2,2,2-trifluoroethyl acrylate and isostearyl acrylate. In one embodiment, the combination of monomers for producing the polymer matrix of the present disclosure is 2,2,2-trifluoroethyl acrylate and lauryl acrylate. In one embodiment, the combination of monomers for producing the polymer matrix of the present disclosure is 2,2,2-trifluoroethyl acrylate and stearyl acrylate.

[0113] (Conductive material) In another aspect, the present disclosure provides a conductive material with improved conductivity. In one specific aspect, the present disclosure provides a conductive material comprising a copolymer of a fluorinated alkyl (meth)acrylate and a conductive component. Preferred embodiments of the conductive material can utilize any of the embodiments described herein or combinations thereof, and one or more of any of the embodiments described in the section (for applications of improving conductivity) herein can be applied in combination.

[0114] (Manufacturing method) In one aspect, the present disclosure provides a method for manufacturing the conductive material and the conductivity improver of the present disclosure.

[0115] In a specific aspect, the present disclosure provides a method for manufacturing a conductive material comprising a copolymer of a fluorinated alkyl (meth)acrylate and a conductive component. This method includes a step of obtaining a copolymer by polymerizing the fluorinated alkyl (meth)acrylate and a polymerizable monomer, a step of mixing the copolymer and the conductive component to obtain a mixture, and a step of heating the mixture to produce the conductive material. Preferred embodiments of the manufacturing method can utilize any of the embodiments described herein or combinations thereof, and one or more of any of the embodiments described in the section (for applications of improving conductivity) herein can be applied in combination.

[0116] In the step of obtaining a copolymer by polymerizing the fluorinated alkyl (meth)acrylate and the polymerizable monomer in the manufacturing method of the present disclosure, typically, the following conditions are preferred: under atmospheric pressure, 5°C to 100°C.

[0117] In the step of mixing the copolymer and the conductive component in the manufacturing method of the present disclosure to obtain a mixture, typically, the following conditions are preferred: under atmospheric pressure, stirring with a planetary mixing and stirring device at room temperature.

[0118] In the step of heating the mixture in the manufacturing method of the present disclosure to produce the conductive material, typically, the following conditions are preferred: under atmospheric pressure, 120°C to 150°C.

[0119] In another aspect, the present disclosure provides a homopolymer of a fluorinated alkyl (meth)acrylate.

[0120] In a specific aspect, the present disclosure provides a homopolymer of a fluorinated alkyl (meth)acrylate, wherein the fluorinated alkyl (meth)acrylate is represented by formula (1)

Chemical formula

[0121] In another aspect, the present disclosure provides a homopolymer of a (meth)acrylic monomer. In a specific aspect, the present disclosure provides a homopolymer of a (meth)acrylic monomer, wherein the (meth)acrylic monomer is represented by formula (2)

Chemical formula

[0122] In a preferred embodiment, in the homopolymer of the (meth)acrylic monomer of the present disclosure, R 4 is an unsubstituted alkyl group having 11 or more carbon atoms. In another preferred embodiment, in the homopolymer of the (meth)acrylic monomer of the present disclosure, R 4 is an unsubstituted alkyl group having 11 to 30 carbon atoms. In another preferred embodiment, in the homopolymer of the (meth)acrylic monomer of the present disclosure, R 4 is an unsubstituted alkyl group having 11 to 24 carbon atoms.

[0123] In a preferred embodiment, in the homopolymer of the (meth)acrylic monomer of the present disclosure, R 4 is an unsubstituted alkyl group having 13 or more carbon atoms. In another preferred embodiment, in the homopolymer of the (meth)acrylic monomer of the present disclosure, R 4 is an unsubstituted alkyl group having 13 to 30 carbon atoms. In another preferred embodiment, in the homopolymer of the (meth)acrylic monomer of the present disclosure, R 4 is an unsubstituted alkyl group having 13 to 24 carbon atoms.

[0124] In a preferred embodiment, in the homopolymer of the (meth)acrylic monomer of the present disclosure, R 4 is an unsubstituted alkyl group having 18 or more carbon atoms. In another preferred embodiment, in the homopolymer of the (meth)acrylic monomer of the present disclosure, R 4 is an unsubstituted alkyl group having 18 to 30 carbon atoms. In another preferred embodiment, in the homopolymer of the (meth)acrylic monomer of the present disclosure, R 4 is an unsubstituted alkyl group having 18 to 24 carbon atoms.

[0125] (Copolymer) The present disclosure provides a copolymer using the technology of the present disclosure.

[0126] In a specific aspect, the present disclosure is a copolymer of a fluorinated alkyl (meth)acrylate and a second (meth)acrylic monomer, wherein the fluorinated alkyl (meth)acrylate has the formula (1)

Chemical formula

Chemical formula

[0127] 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.

[0128] In one embodiment, R 4is 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.

[0129] 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.

[0130] The present disclosure provides matrix applications.

[0131] In one aspect, a homopolymer of a fluorinated alkyl (meth)acrylate represented by formula (1), a homopolymer of a (meth)acrylic monomer represented by formula (2), or a copolymer of a fluorinated alkyl (meth)acrylate represented by formula (1), and provides a composition for use as a matrix in a conductive material containing a conductive component.

[0132] (Mixture) In one aspect, the present disclosure provides a mixture.

[0133] In one aspect, the present disclosure provides a homopolymer of a fluorinated alkyl (meth)acrylate + metal. Here, it can be a mixture of a homopolymer of a fluorinated alkyl (meth)acrylate and a metal.

[0134] In one aspect, the present disclosure provides a mixture as a substance (here, a homopolymer of a (meth)acrylic monomer + metal).

[0135] Specifically, the present disclosure provides a mixture of a homopolymer of a (meth)acrylic monomer and a metal.

[0136] The present disclosure provides a mixture as a substance (i.e., a composition containing a copolymer and a metal-based component). In one aspect, the present disclosure provides a mixture of a copolymer of a fluorinated alkyl (meth)acrylate (monomer) and a (second) (meth)acrylic monomer and a metal. Here, the “second” (meth)acrylic monomer means a monomer as a partner of the (first) fluorinated alkyl (meth)acrylate monomer of the copolymer.

[0137] In one embodiment, the metal includes silver, copper, gold, aluminum, zinc, tin, nickel, and / or iron. In a preferred embodiment, the metal is silver. Without wishing to be bound by theory, silver is excellent in conductivity and has good resistance.

[0138] In one embodiment, the fluorinated alkyl (meth)acrylate is represented by formula (1)

Chemical formula

[0139] Also, the second (meth)acrylic monomer is represented by formula (2)

Chemical formula

[0140] 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.

[0141] 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.

[0142] 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.

[0143] (Note) In this specification, "or" is used when "at least one or more" of the items listed in the text can be adopted. The same applies to "or". When it is specified in this specification that it is "within the range of two values", the range includes the two values themselves.

[0144] References such as scientific literature, patents, and patent applications cited in this specification are hereby incorporated by reference in their entirety to the same extent as if each was specifically set forth herein.

[0145] As described above, the present disclosure has been described by showing preferred embodiments for ease of understanding. Hereinafter, the present disclosure will be described based on examples. However, the above description and the following examples are provided for illustrative purposes 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 herein, but is limited only by the claims.

Examples

[0146] Examples are described below. The handling of organisms used in the following examples complied with the standards stipulated by the regulatory authorities when necessary. Specifically, the products described in the examples were used for the reagents, but equivalents from other manufacturers (such as Sigma-Aldrich, etc.) can also be substituted.

[0147] (Example 1: Preparation of Polymer Matrix) In this example, a polymer matrix was prepared.

[0148] (Example a) Isostearyl acrylate (ISTA, 6.70 g) as monomer A, 2,2,2-trifluoroethyl acrylate (3.20 g, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name Biscoat V#3F) as monomer B, and 2,4,6-trimethylbenzoyl diphenylphosphine oxide (0.10 g, manufactured by BASF, trade name Irgacure® TPO) as a polymerization initiator were mixed to obtain a monomer component containing a polymerization initiator. After injecting the obtained monomer component into a transparent glass mold (length: 100 mm, width: 100 mm, depth: 2 mm), the monomer component was irradiated with ultraviolet light so that the irradiation dose was 0.36 mW / cm 2 and polymerized in bulk for 2 hours to obtain a polymer.

[0149] 3.00 g of the obtained polymer was mixed with an appropriate solvent (heptane, octane, or limonene) (7.00 g) to check whether it dissolved. When it dissolved, the resulting solution (sometimes referred to as an acrylic resin solution) was used for the preparation of the conductive film.

[0150] (Examples b and c) An acrylic resin solution was obtained in the same manner as in Example a, except that the ratio of monomer A to monomer B was changed as shown in the following table.

[0151] (Example f) An acrylic resin solution was obtained in the same manner as in Example a, except that lauryl acrylate (LA) was used as monomer A and the ratio of monomer A to monomer B was changed as shown in the following table.

[0152] (Examples g and h) An acrylic resin solution was obtained in the same manner as in Example a, except that stearyl acrylate (STA) was used as monomer A and the ratio of monomer A to monomer B was changed as shown in the following table.

[0153] (Example 2: Preparation of Conductive Film) In this example, a conductive film was prepared.

[0154] (Conductive Material Precursor) To each acrylic resin solution (6.00 g) obtained in Example 1, silver filler (7.20 g, manufactured by Fukuda Metal Foil & Powder Co., Ltd., trade name AgC-A), and 2-(2-butoxyethoxy)ethanol (0.10 g) as a dispersant were mixed in a Maglester manufactured by Kurabo Industries Ltd. to obtain a conductive material precursor.

[0155] (Coating Film Formation) The obtained conductive material precursor was coated on a release polyethylene terephthalate film (manufactured by Mitsui Chemicals Toagosei Co., Ltd., trade name Separator SP-PET PET-01-Bu) as a release film to form a coating film.

[0156] (Conductive Film) The obtained coating film was heated in an oven at 150 °C for 60 minutes to obtain a conductive film with a thickness of approximately 30 μm.

[0157] (Results) In Comparative Examples 1 to 3, conductive films were prepared according to the methods described in Examples 1 and 2, except that acrylic acid or ethyl acrylate was used instead of 2,2,2-trifluoroethyl acrylate. The results are shown in Table 1.

Table 1

[0158] (Example 3: Measurement of volume resistivity) The conductive film obtained in Example 2 was cut into pieces with a length of 0.5 cm and a width of 2.00 cm, and measured by the four-terminal method using Loresta GP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.).

[0159] (Results) The results are shown in Table 1.

[0160] (Example 4: Confirmation of resistance value change) In this example, the change in resistance value was confirmed.

[0161] (Measurement of resistance value) The conductive film obtained above was cut into pieces with a length of 0.5 cm and a width of 2.00 cm, and the resistance value before stretching (ΩA) was measured with a digital multimeter [trade name PC773, manufactured by Sanwa Electric Instrument Co., Ltd.] with the electrode distance fixed at 1.00 cm.

[0162] (Change in resistance value) Next, while fixing the conductive film on the multimeter electrodes, the distance between the electrodes was set to 2.00 cm, and the resistance value (ΩB) in that state was measured. The change in the resistance value was calculated as follows. Change in resistance value = ΩB / ΩA

[0163] (Results) The results are shown in Table 1.

[0164] (Example 5: Preparation of a conductive material containing a carbon-based component) In this example, a conductive material having a carbon-based component as a conductive component is prepared.

[0165] Using the same method as in Example 1, short multi-wall carbon nanotubes (6.67 g, manufactured by Kobe Natural Chemical Co., Ltd., CNT dispersion), and a dispersant (0.13 g, manufactured by Elementis, product number: NUOSPERSE® AP657) were mixed in a 10.0 g acrylic resin solution prepared at the monomer ratio shown in the following table using a Mizer Star manufactured by Kurabo Industries Ltd. to obtain a conductive material precursor.

[0166] The obtained conductive material precursor was applied to a release polyethylene terephthalate film (manufactured by Mitsui Chemicals Toagosei Co., Ltd., trade name Separator SP-PET PET-01-Bu) as a release film to form a coating film.

[0167] The obtained coating film was heated on a hot plate at 60 °C for 30 minutes to obtain a conductive film having a thickness of approximately 30 μm.

[0168] The volume resistivity of the obtained conductive film was measured by the method described in Example 3. The results are shown in Table 2.

Table 2

[0169] In Example e (Film No. 16), compared with Example d (Film No. 15), the use of fluorinated alkyl acrylate V#3F significantly reduced the volume resistivity.

[0170] (Note) As described above, the present disclosure has been illustrated using preferred embodiments of the present disclosure. However, it is understood that the scope of the present disclosure should be construed only by the claims. This application claims priority to Japanese Patent Application No. 2019-148114 (filed on August 9, 2019), the contents of which are incorporated herein by reference in their entirety. It is understood that patents, patent applications, and other documents cited herein should be incorporated by reference in their entirety as if the contents themselves were specifically set forth herein.

Industrial Applicability

[0171] Using the electrical conductive material improver of the present disclosure, an efficient electrical conductive material can be provided and used in industries that require electrical conductive materials.

Claims

**Claim 1**: A composition for improving the conductivity of a conductive component or a conductive material, comprising a copolymer of a fluorinated alkyl (meth)acrylate and a second (meth)acrylic monomer, wherein the fluorinated alkyl (meth)acrylate is represented by formula (1) 【Chemical 24】 and is represented by R １ is a hydrogen atom or a methyl group, R ２ is an alkyl group substituted with from 1 to a replaceable number of fluorine atoms, the second (meth)acrylic monomer is represented by formula (2) 【Chemical 25】 and is represented by R ３ is a hydrogen atom or a methyl group, R ４ A composition wherein R is an unsubstituted alkyl group having 11 or more carbon atoms. **Claim 2** The composition according to claim 1, wherein the fluorinated alkyl (meth)acrylate is 2,2,2-trifluoroethyl acrylate. **Claim 3** The composition according to claim 1, wherein the second (meth)acrylic monomer is isostearyl acrylate, stearyl acrylate, or lauryl acrylate. **Claim 4** A conductive material comprising a copolymer of a fluorinated alkyl (meth)acrylate and a conductive component, wherein the copolymer is a copolymer of the fluorinated alkyl (meth)acrylate and a second (meth)acrylic monomer, the fluorinated alkyl (meth)acrylate is represented by formula (1) 【Chemical 24】 and is represented by R １ is a hydrogen atom or a methyl group, R ２ is an alkyl group substituted with from 1 to the replaceable number of fluorine atoms, the second (meth)acrylic monomer is represented by formula (2) 【Chemical Formula 25】 and is represented by R ３ is a hydrogen atom or a methyl group, R ４ is a conductive material that is an unsubstituted alkyl group having 11 or more carbon atoms. **Claim 5** The conductive material according to claim 4, wherein the fluorinated alkyl (meth)acrylate is 2,2,2-trifluoroethyl acrylate. **Claim 6** The conductive material according to claim 4, wherein the second (meth)acrylic monomer is isostearyl acrylate, stearyl acrylate, or lauryl acrylate. **Claim 7** A method for manufacturing a conductive material comprising a copolymer of a fluorinated alkyl (meth)acrylate and a second (meth)acrylic monomer and a conductive component, comprising: obtaining a copolymer by polymerizing the fluorinated alkyl (meth)acrylate and the second (meth)acrylic monomer; mixing the copolymer and the conductive component to obtain a mixture; and heating the mixture to produce a conductive material, wherein the fluorinated alkyl (meth)acrylate is represented by formula (1) and is represented by 【Chemical 24】 the second (meth)acrylic monomer is represented by formula (2) R １ is a hydrogen atom or a methyl group, R ２ is an alkyl group substituted with from 1 to a replaceable number of fluorine atoms, and is represented by 【Chemical Formula 25】 **Claim 8** R ３ is a hydrogen atom or a methyl group, R ４ is an unsubstituted alkyl group having 11 or more carbon atoms, a method. A copolymer of a fluorinated alkyl (meth)acrylate and a second (meth)acrylic monomer, wherein the fluorinated alkyl (meth)acrylate is represented by formula (1) and is represented by 【Chemical formula 28】 the second (meth)acrylic monomer is represented by formula (2) R １ is a hydrogen atom or a methyl group, R ２ is an alkyl group substituted with from 1 to a replaceable number of fluorine atoms, and is represented by 【Chemical Formula 29】 copolymer. R ３ is a hydrogen atom or a methyl group, R ４ is an unsubstituted alkyl group having 11 or more carbon atoms, provided that R ４ is not a fluorinated alkyl group, ​ **Claim 9**: A composition for use as a matrix in a conductive material containing a conductive component, the composition containing the copolymer according to claim 8. **Claim 10**: A mixture of a copolymer of a fluorinated alkyl (meth)acrylate and a second (meth)acrylic monomer and a metal component or a conductive carbon-based component, wherein the fluorinated alkyl (meth)acrylate is represented by formula (1) 【Chemical Formula 30】 and R １ is a hydrogen atom or a methyl group, R ２ is an alkyl group substituted with from 1 to a replaceable number of fluorine atoms, the second (meth)acrylic monomer is represented by formula (2). 【Chemical 31】 ​ R ３ is a hydrogen atom or a methyl group, R ４ is an unsubstituted alkyl group having 11 or more carbon atoms, provided that R ４ is not a fluorinated alkyl group, mixture.

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