WO2021029361A1

WO2021029361A1 - Novel electric conductivity improving agent

Info

Publication number: WO2021029361A1
Application number: PCT/JP2020/030368
Authority: WO
Inventors: 慎一朗岡本
Original assignee: 大阪有機化学工業株式会社
Priority date: 2019-08-09
Filing date: 2020-08-07
Publication date: 2021-02-18
Also published as: KR20220046583A; TW202112953A; JPWO2021029361A1

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

New conductivity improver

This disclosure relates to new conductivity improvers and related technologies. More specifically, the present disclosure relates to a composition for improving the conductivity of a conductive material, which comprises an alkyl fluorinated (meth) acrylate.

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.

Japanese Unexamined Patent Publication No. 2019-102719 International Publication No. 2015/099049 International Publication No. 2019/039511 International Publication No. 2017/1663615 JP-A-2017-183207

The present disclosure provides a conductive material containing a desired combination of conductive components and a base material.

The disclosure provides, for example:

(Item 1) A composition for improving the conductivity of a conductive component or a conductive material, which contains an alkyl fluorinated (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).

Represented by
R ¹ is a hydrogen atom or a methyl group and
R ² is an alkyl group substituted with 1 to a substitutable number of fluorine atoms.
The composition according to any one of the preceding paragraphs.
(Item 5) The second (meth) acrylic monomer has the formula (2).

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 not a fluorinated alkyl group,
The composition according to any one of the preceding paragraphs.
(Item 5a) The composition according to any one of the preceding items, wherein R ⁴ is an unsubstituted alkyl group having 11 or more carbon atoms.
(Section 5b) R ⁴ is an unsubstituted alkyl group having 13 or more carbon atoms, the preceding composition according to any one of claims.
(Section 5c) R ⁴ is an unsubstituted alkyl group having 18 or more carbon atoms, the preceding composition according to any one of claims.
(Item 6) The composition according to any one of the preceding items, wherein the alkyl fluorinated (meth) acrylate is 2,2,2-trifluoroethyl acrylate.
(Item 7) The composition according to any one of the preceding items, wherein the second (meth) acrylic monomer is isostearyl acrylate, lauryl acrylate or stearyl acrylate.
(Item 7a) The composition according to any one of the preceding items, wherein the second (meth) acrylic monomer is isostearyl acrylate or lauryl acrylate.
(Item 8) A conductive material containing a copolymer of an alkyl fluorinated (meth) acrylate and a conductive component.
(Item 9) 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 10) A method for producing a copolymer of an alkyl fluorinated (meth) acrylate and a conductive material containing a conductive component.
A step of obtaining a copolymer by polymerizing the fluorinated alkyl (meth) acrylate 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 11) The method according to any one of the preceding items, which comprises one or more of the features described in the preceding item.
(Item 12) A homopolymer of an alkyl fluorinated (meth) acrylate.
The fluorinated alkyl (meth) acrylate is represented by the formula (1).

Represented by
R ¹ is a hydrogen atom or a methyl group and
R ² is an alkyl group substituted with 1 to a substitutable number of fluorine atoms.
Homopolymer.
(Item 13) The homopolymer according to any one of the preceding items, which comprises one or more of the features described in the preceding item.
(Item 14) A homopolymer of a (meth) acrylic monomer, which is a homopolymer.
The (meth) acrylic monomer has the formula (2).

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 not a fluorinated alkyl group,
Homopolymer.
(Section 14a) R ⁴ is an unsubstituted alkyl group having 11 or more carbon atoms, preceding homopolymer according to any one of claims.
(Section 14b) R ⁴ is an unsubstituted alkyl group having 13 or more carbon atoms, preceding homopolymer according to any one of claims.
(Section 14c) R ⁴ is an unsubstituted alkyl group having 18 or more carbon atoms, preceding homopolymer according to any one of claims.
(Item 15) The homopolymer according to any one of the preceding items, which comprises one or more of the features described in the preceding item.
(Item 16) A copolymer of an alkyl fluorinated (meth) acrylate and a second (meth) acrylic monomer.
The fluorinated alkyl (meth) acrylate is represented by the formula (1).

Represented by
R ¹ is a hydrogen atom or a methyl group and
R ² is an alkyl group substituted with 1 to a substitutable number of fluorine atoms.
The second (meth) acrylic monomer has the formula (2).

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 not a fluorinated alkyl group,
Copolymer.
(Section 16a) R ⁴ is an unsubstituted alkyl group having 11 or more carbon atoms, the copolymer according to any one of the preceding claim.
(Section 16b) R ⁴ is an unsubstituted alkyl group having 13 or more carbon atoms, the copolymer according to any one of the preceding claim.
(Section 16c) R ⁴ is an unsubstituted alkyl group having 18 or more carbon atoms, the copolymer according to any one of the preceding claim.
(Item 17) The copolymer according to any one of the preceding items, which comprises one or more of the features described in the preceding item.
(Item 18) The homopolymer of the fluorinated alkyl (meth) acrylate according to any one of the preceding items.
A homopolymer of the (meth) acrylic monomer according to any one of the preceding paragraphs, or a copolymer of an alkyl fluorinated (meth) acrylate according to any one of the preceding paragraphs.
A composition for use as a matrix in a conductive material containing a conductive component.
(Item 19) The composition according to any one of the preceding items, which comprises one or more of the features described in the preceding item.
(Item 20) A mixture of a homopolymer of an alkyl fluorinated (meth) acrylate and a metal component or a conductive carbon-based component.
(Item 21) A mixture of a homopolymer of a (meth) acrylic monomer and a metal component or a conductive carbon-based component.
(Item 22) A copolymer of an alkyl fluorinated (meth) acrylate and a second (meth) acrylic monomer and a mixture of a metal component or a conductive carbon-based component.
(Item 23) The mixture according to any one of the preceding items, which comprises one or more of the features described in the preceding item.
(Item 24) The mixture according to any one of the preceding items, wherein the metal component comprises silver, copper, gold, aluminum, zinc, nickel, tin, and / or iron.
(Item 24a) The mixture according to any one of the preceding items, wherein the metal is silver.
(Item 25) The conductive carbon-based component is scaly graphite, graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, graphene, carbon nanotube, fullerene, carbon fiber, carbon fluoride. The mixture according to any one of the preceding terms, selected from the group consisting of.
(Item 25a) The mixture according to any one of the preceding items, wherein the conductive carbon-based component is a carbon nanotube.
(Item 26) The fluorinated alkyl (meth) acrylate is of the formula (1).

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 not a fluorinated alkyl group,
The mixture according to any one of the preceding paragraphs.
(Section 26a) R ⁴ is an unsubstituted alkyl group having 11 or more carbon atoms, the preceding mixture according to any one of claims.
(Section 26b) R ⁴ is an unsubstituted alkyl group having 13 or more carbon atoms, the preceding mixture according to any one of claims.
(Section 26c) R ⁴ is an unsubstituted alkyl group having 18 or more carbon atoms, the preceding mixture according to any one of claims.

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.

According to the present disclosure, conductivity improvers are provided, and by using these, it is possible to provide a technique capable of improving the conductivity.

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.

The definitions of terms and / or basic technical contents particularly used in this specification will be described below as appropriate.

(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).

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.

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.

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.

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. ..

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.).

In the present specification, the "metal component" includes a metal or an alloy.

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".

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.

In the present specification, "(meth) acrylic" means "acrylic" or "methacryl", and "(meth) acrylate" means "acrylate" or "methacrylate".

For example, the (meth) acrylic monomer has the formula (2).

In the formula, 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, is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, with the proviso, R ⁴ is not a fluorinated alkyl group.

A typical example of the "alkyl fluorinated (meth) acrylate" in the present specification is the formula (1).

In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is an alkyl group substituted with 1 to a substitutable number of fluorine atoms.

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.

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.

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.

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.

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, for example, a C _1-6 fluorinated alkyl group, but the present disclosure is not limited to these examples. Examples of the haloalkyl group having 1 to 8 carbon atoms (C _1-8 haloalkyl group) include a C _1-8 fluorinated alkyl group, but the present disclosure is not limited to these examples.

As used herein, the term "fluorinated alkyl group" refers to an alkyl group in which one or more hydrogen atoms on the 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 a trifluoromethyl group, a trifluoroethyl group (2,2,2-trifluoroethyl group, etc.), and perfluoroethyl. Group, trifluoron-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) , 4, 5, 5-Octafluoropentyl group, etc.), perfluoro n-pentyl group, trifluoro n-hexyl group, perfluoro n-hexyl group, etc., but the present disclosure is limited to such examples. is not it. _{Examples of the} fluorinated alkyl group having 1 to 8 carbon atoms (C _1-8 fluorinated alkyl group) include C _1-6 fluorinated alkyl group, undecafluoro n-heptyl group, perfluoro n-heptyl group, and tridecafluorooctyl. Groups (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group, etc.), perfluoron-octyl group, etc. may be mentioned. Is not limited to such examples. The "fluorinated alkyl group" can be used interchangeably with "fluorinated alkyl" and "alkyl groups substituted with one to a substitutable number of fluorine atoms".

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.

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.

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.

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.

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.

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.

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).

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.

In the present specification, the "copolymer containing a monomer component" means a copolymer produced by polymerizing the monomer component.

In the present specification, the copolymer of monomer A means a copolymer in which one of the contained monomers is monomer A.

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.

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.

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-based monomer, sulfone-based monomer, phenylene sulfide-based monomer, ether ether ketone-based monomer, silicone-based monomer, styrene-based monomer, butadiene-based monomer and AES resin, diallyl phthalate resin, ABS resin, silicone resin, etc. are formed by polymerization. Monomers can be mentioned.

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".

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.

(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 conductivity is improved by containing a composition (also referred to as a conductivity improver) for improving the conductivity provided in the present disclosure.

The conductive material of the present disclosure may typically contain other substrates of conductive components.

(Basic explanation of conductivity improver)
The composition (conductivity improver) for improving the conductivity provided in the present disclosure contains an alkyl fluorinated (meth) acrylate.

In a representative embodiment, an example of the alkyl fluorinated (meth) acrylate provided in the present disclosure is of formula (1).

Represented by, R ¹ is a hydrogen atom or a methyl group, and R ² is an alkyl group substituted with 1 to a substitutable number of fluorine atoms. In the alkyl fluorinated (meth) acrylate represented by the formula (1), regardless of the number of fluorine contained, the form of the alkyl group (carbon number, branched / linear state, etc.), methacrylic or acrylic, etc. , All of which improve the conductivity of the conductive component or the conductive material.

The basic usage of the conductivity improver is as follows.

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 alkyl fluorinated (meth) acrylate as a constituent unit.

(Conductive component targeted by the conductivity improver)
The conductive component that can be targeted by the conductivity improver of the present disclosure is a component having arbitrary conductivity. Preferred examples include a metal-based component and a conductive carbon-based component. More preferably, metal components, carbon black, graphene and carbon nanotubes are mentioned. More preferably, silver and carbon nanotubes can be mentioned.

(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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

When the monomer is polymerized by a solution polymerization method, for example, the monomer can be polymerized by dissolving the monomer in a solvent and adding a polymerization initiator to the solution while stirring the obtained solution. The monomer can be polymerized by dissolving the initiator in a solvent and adding the monomer to the solution while stirring the obtained solution. The solvent is preferably an organic solvent that is compatible with the monomer.

The homopolymers or copolymers contained in the conductive materials of the present disclosure use peroxide-based initiators (for example, benzoyl peroxide and azobisisobutyronitrile, and their analogs) as polymerization initiators. May be polymerized by.

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.

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.

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) Method for Producing Polymer Matrix Contained in Conductive Material The polymer (or polymer matrix) contained in the conductive material of the present disclosure is prepared by mixing one or more specific monomers and under appropriate polymerization conditions. It can be produced by polymerizing with an appropriate additive such as a polymerization initiator, if necessary. 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.

In one aspect, the present disclosure relates to equation (1).

The present invention relates to a method for producing a homopolymer obtained by polymerizing an alkyl fluorinated (meth) acrylate represented by the above in the presence or absence of a cross-linking agent.

In one aspect, the present disclosure relates to equation (2).

The present invention relates to a method for producing a homopolymer obtained by polymerizing a (meth) acrylic monomer represented by the above in the presence or absence of a cross-linking agent.

In one aspect, the present disclosure relates to a method of making a copolymer of an alkyl fluorinated (meth) acrylate and a second (meth) acrylic monomer.
The fluorinated alkyl (meth) acrylate is represented by the formula (1).

Represented by, R ¹ is a hydrogen atom or a methyl group, R ² is an alkyl group substituted with 1 to a substitutable number of fluorine atoms.
The second (meth) acrylic monomer has the formula (2).

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, provided that, R ⁴ is not a fluorinated alkyl group.

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) 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) Production Method by Photopolymerization In one embodiment, the polymer matrix of the present disclosure is one step by exposure-polymerizing a monomer (including one or more kinds of monomers) in the presence of a polymerization initiator. Obtained at.

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

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

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

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, 0.5 hours to 24 hours or more.

(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) 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.

(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.

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. Among these carbon nanotubes, multi-wall carbon nanotubes are preferable.

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.

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%.

(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.

(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.

(Use for improving conductivity)
In one aspect, the present disclosure relates to conductivity improving applications.
More specifically, in a specific aspect, the present disclosure provides compositions for improving the conductivity of conductive materials, including alkyl fluorinated (meth) acrylates.

Conventionally, in a system in which a large amount of silver filler is present as in the present disclosure, it has been considered that the polymer composition does not affect the conductivity, so that sufficient studies have not been made. However, as a result of polymer studies, it was confirmed that the resistivity of the copolymerized fluorinated alkyl acrylate was lower than that of the conventional product. As a result of further scrutiny, 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.

In one specific embodiment, the conductive material of the present disclosure comprises a copolymer of an alkyl fluorinated (meth) acrylate and a conductive component. In this way, the alkyl fluorinated (meth) acrylate can be included as a copolymer to improve the conductivity of the conductive component.

In one embodiment, homopolymers of alkyl fluorinated (meth) acrylates can be used. Here, as the conductive component, a metal-based component and a conductive carbon-based component can be typically used, and specifically, silver, copper, gold, aluminum, zinc, nickel, tin, iron, and carbon. Black, graphene and carbon nanotubes can be used, preferably silver and carbon nanotubes.

By providing this technique of the present disclosure, the conductivity of any conductive component can be improved.

In one preferred embodiment, it is advantageous that the copolymer used in the present disclosure is a copolymer of an alkyl fluorinated (meth) acrylate and a second (meth) acrylic monomer. The reason for this is the effect of repelling compounds (surfactant effect), although we do not want to be bound by theory. Fluorine-based resins are used as antifouling coating agents and mold release agents, and have an effect of repelling compounds (surfactant effect). It is considered that the reason why the resistivity is lowered in the present disclosure is that the silver particles are more densely packed due to the repulsion between the alkyl fluorinated (meth) acrylate and the silver particles due to the surface active effect of the fluorine compound. .. Furthermore, it is an unexpected result that the effect is considered to be exhibited with a small amount of addition as in the examples.

In one embodiment, the alkyl fluorinated (meth) acrylate is of formula (1).

Represented by
R ¹ is a hydrogen atom or a methyl group and
R ² is an alkyl group substituted with 1 to a substitutable number of fluorine atoms.

In one embodiment, the second (meth) acrylic monomer is of formula (2).

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 fluorinated group.

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.

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.

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.

In yet another embodiment, the alkyl fluorinated (meth) acrylate is 2,2,2-trifluoroethyl acrylate. As described above, it is considered that the reason why the resistivity is lowered in the present disclosure is that the silver particles are more densely packed with each other due to the repulsion with the silver particles due to the surface active effect of the fluorine compound.

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

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

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

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.

(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 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.

(Manufacturing method)
In one aspect, the present disclosure provides a method of making the conductive material and the conductivity improver of the present disclosure.

In a specific aspect, the present disclosure provides a method for producing a copolymer of an alkyl fluorinated (meth) acrylate and a conductive material containing a conductive component. This method includes a step of obtaining a copolymer by polymerizing the alkyl fluorinated (meth) acrylate and a polymerizable monomer, a step of mixing the copolymer and a conductive component to obtain a mixture, and a step of heating the mixture to obtain a conductive material. Includes the process of producing. 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 (Use for improving conductivity) in the present specification. Can be applied as one or a combination of two or more.

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

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.

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.

In another aspect, the present disclosure provides homopolymers of alkyl fluorinated (meth) acrylates.

In a specific aspect, the present disclosure is a homopolymer of an alkyl fluorinated (meth) acrylate.
The fluorinated alkyl (meth) acrylate is represented by the formula (1).

Represented by
R ¹ is a hydrogen atom or a methyl group and
R ² is an alkyl group substituted with 1 to a substitutable number of fluorine atoms.
Provided is a homopolymer. Preferred embodiments of the fluorinated alkyl (meth) acrylate homopolymers used in the present disclosure can utilize any of the embodiments described herein or combinations thereof, as used herein (conductive). Any embodiment described in the section (Rate improvement application) can be applied to one or a plurality of combinations. This homopolymer of fluorinated alkyl (meth) acrylate is used, for example, as a matrix of conductive materials.

In another aspect, the present disclosure provides homopolymers of (meth) acrylic monomers.
In a specific aspect, the present disclosure is a homopolymer of a (meth) acrylic monomer,
The (meth) acrylic monomer has the formula (2).

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 not a fluorinated alkyl group,
Provided is a homopolymer. This homopolymer is used, for example, as a matrix of conductive materials.

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

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

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

(Copolymer)
The present disclosure provides copolymers using the techniques of the present disclosure.

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

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 not a fluorinated alkyl group,
Provide copolymers. This copolymer is used, for example, as a matrix of conductive materials.

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.

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.

The present disclosure provides matrix use.

In one aspect,
A homopolymer of an alkyl fluorinated (meth) acrylate represented by the formula (1),
A homopolymer of a (meth) acrylic monomer represented by the formula (2) or a copolymer of an alkyl fluorinated (meth) acrylate represented by the formula (1).
Provided is a composition for use as a matrix in a conductive material containing a conductive component.

(blend)
In one aspect, the present disclosure provides a mixture.

In one aspect, the disclosure provides homopolymers + metals of alkyl fluorinated (meth) acrylates. Here it can be a mixture of homopolymers and metals of alkyl fluorinated (meth) acrylates.

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

Specifically, the present disclosure provides a mixture of homopolymers of (meth) acrylic monomers and metals.

The present disclosure provides a mixture as a substance (ie, a composition comprising a copolymer and a metallic component).
In one aspect, the disclosure provides a copolymer of an alkyl fluorinated (meth) acrylate (monomer) 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 (first) alkyl fluorinated (meth) acrylate monomer of the copolymer.

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.

In one embodiment, the alkyl fluorinated (meth) acrylate is of formula (1).

The second (meth) acrylic monomer has the formula (2).

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.

(Note) In this specification, "or" is used when "at least one" of the items 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.

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.

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.

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.

(Example 1: Preparation of polymer matrix)
In this example, a polymer matrix was prepared.

(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 Viscoat V # 3F) as monomer B, and polymerization initiation. By mixing 2,4,6-trimethylbenzoyldiphenylphosphine oxide (0.10 g, manufactured by BASF, trade name Irgacure (registered trademark) TPO) as an agent, a monomer component containing a polymerization initiator was obtained. 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.

3.00 g of the obtained polymer 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.

(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 and monomer B was changed as shown in the table below.

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

(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 the monomer A and the ratio of the monomer A to the monomer B was changed as shown in the table below.

(Example 2: Preparation of conductive film)
In this example, a conductive film was prepared.

(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.

(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.

(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.

(result)
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.

* Add 1 part by weight each of 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a polymerization initiator.
* ISTA: isostearyl acrylate, LA: lauryl acrylate, STA: stearyl acrylate, AA: acrylic acid, EA: ethyl acrylate, V # 3F: 2,2,2-trifluoroethyl acrylate

(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).

(result)
The results are shown in Table 1.

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

(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.

(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

(result)
The results are shown in Table 1.

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

Short multi-wall carbon nanotubes (6.67 g, manufactured by KNC Laboratories Co., Ltd., CNT dispersion) were added to an acrylic resin solution (10.0 g) prepared with the monomer ratios shown in the table below by the same method as in Example 1. And a dispersant (0.13 g, manufactured by Elementis, product number: NUOSPERSE (registered trademark) AP657) were mixed with a Mazelstar manufactured by Kurabou to obtain a conductive material precursor.

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.

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 about 30 μm.

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

In Example e (Film No. 16), the volume resistivity was significantly reduced by using the fluorinated alkyl acrylate V # 3F as compared with Example d (Film No. 15).

(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. 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. 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.

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

A composition for improving the conductivity of a conductive component or a conductive material, which comprises an alkyl fluorinated (meth) acrylate.
The composition according to claim 1, wherein the conductive material contains a copolymer of the alkyl fluorinated (meth) acrylate and a conductive component.
The composition according to claim 2, 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 the formula (1).

Represented by
R 1 is a hydrogen atom or a methyl group and
R 2 is an alkyl group substituted with 1 to a substitutable number of fluorine atoms.
The composition according to any one of claims 1 to 3.
The second (meth) acrylic monomer has the formula (2).

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 not a fluorinated alkyl group,
The composition according to any one of claims 1 to 4.
The composition according to any one of claims 1 to 5, wherein the fluorinated alkyl (meth) acrylate is 2,2,2-trifluoroethyl acrylate.
The composition according to any one of claims 3 to 6, wherein the second (meth) acrylic monomer is isostearyl acrylate, stearyl acrylate, or lauryl acrylate.
A conductive material containing a copolymer of an alkyl fluorinated (meth) acrylate and a conductive component.
The conductive material according to claim 8, which comprises one or more of the features according to claims 1-7.
A method for producing a copolymer of an alkyl fluorinated (meth) acrylate and a conductive material containing a conductive component.
A step of obtaining a copolymer by polymerizing the fluorinated alkyl (meth) acrylate 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.
10. The method of claim 10, comprising one or more of the features of claims 1-9.
A homopolymer of an alkyl fluorinated (meth) acrylate,
The fluorinated alkyl (meth) acrylate is represented by the formula (1).

Represented by
R 1 is a hydrogen atom or a methyl group and
R 2 is an alkyl group substituted with 1 to a substitutable number of fluorine atoms.
Homopolymer.
The homopolymer of claim 12, which comprises one or more of the features of claims 1-11.
(Meta) Acrylic monomer homopolymer
The (meth) acrylic monomer has the formula (2).

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 not a fluorinated alkyl group,
Homopolymer.
The homopolymer of claim 14, comprising one or more of the features of claims 1-13.
A copolymer of an alkyl fluorinated (meth) acrylate and a second (meth) acrylic monomer.
The fluorinated alkyl (meth) acrylate is represented by the formula (1).

Represented by
R 1 is a hydrogen atom or a methyl group and
R 2 is an alkyl group substituted with 1 to a substitutable number of fluorine atoms.
The second (meth) acrylic monomer has the formula (2).

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 not a fluorinated alkyl group,
Copolymer.
The copolymer according to claim 16, which comprises one or more of the features of claims 1-15.
The homopolymer of the alkyl fluorinated (meth) acrylate according to claim 12 or 13, the homopolymer of the (meth) acrylic monomer according to claim 14 or 15, or the alkyl fluorinated (meth) according to claim 16 or 17. ) Includes acrylate copolymers,
A composition for use as a matrix in a conductive material containing a conductive component.
The composition of claim 18, which comprises one or more of the features of claims 1-17.
A mixture of homopolymers of alkyl fluorinated (meth) acrylates and metallic or conductive carbon-based components.
A mixture of homopolymers of (meth) acrylic monomers and metallic or conductive carbon-based components.
A copolymer of an alkyl fluorinated (meth) acrylate and a second (meth) acrylic monomer and a mixture of a metal component or a conductive carbon-based component.
The mixture according to any one of claims 20 to 22, which comprises one or more of the characteristics of claims 1-19.
The mixture according to any one of claims 20 to 23, wherein the metal component comprises silver, copper, gold, aluminum, zinc, nickel, tin, and / or iron.
From the group in which the conductive carbon-based component consists of scaly graphite, graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, graphene, carbon nanotubes, fullerenes, carbon fibers, and carbon fluoride. The mixture according to any one of claims 20 to 24, which is selected.
The fluorinated alkyl (meth) acrylate is of the formula (1).

Represented by
R 1 is a hydrogen atom or a methyl group and
R 2 is an alkyl group substituted with 1 to a substitutable number of fluorine atoms.
The second (meth) acrylic monomer has the formula (2).

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 not a fluorinated alkyl group,
The mixture according to any one of claims 22 to 25.