WO2021029359A1 - Conductivity improving agent - Google Patents

Abstract

The present invention provides a composition that includes an organic phosphorous compound and is for improving the conductivity of a conductive polymer including a metal component. The present invention also provides: a conductive material that includes a polymer matrix, metal, and an organic phosphorous compound; and a production method therefor. The present invention also provides a sintering promoter for metal components, that includes an organic phosphorous compound.

Description

Conductivity improver

The present disclosure relates to a composition for improving the conductivity of a conductive polymer. More specifically, the present invention relates to a conductivity improver containing an organic phosphorus compound.

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:

によって表される化合物であり、式中、
Ｒ^１は、水素原子またはメチル基であり、
Ｒ^２は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基である、
上記項のいずれか一項に記載の組成物。
（項１２ａ）Ｒ^１は、水素原子である、上記項のいずれか一項に記載の組成物。
（項１２ｂ）Ｒ^２は、水素原子、または置換もしくは非置換アルキル基である、上記項のいずれか一項に記載の組成物。
（項１２ｃ）Ｒ^２は、水素原子、または置換もしくは非置換Ｃ_１～６アルキル基である、上記項のいずれか一項に記載の組成物。
（項１２ｄ）Ｒ^２は、エチルである、上記項のいずれか一項に記載の組成物。
（項１３）有機リン化合物を含む、金属系成分用の焼結促進剤。
（項１４）上記項に記載の１つまたは複数の特徴を含む、上記項のいずれか一項に記載の焼結促進剤。
（項１５）ポリマーマトリクスと、金属と、有機リン化合物とを含む、導電材。
（項１６）前記有機リン化合物が、３価リンを含む、上記項のいずれか一項に記載の導電材。
（項１７）前記有機リン化合物が、アルキル、シクロアルキルまたはアリールで置換されたホスフィンである、上記項のいずれか一項に記載の導電材。
（項１７ａ）前記有機リン化合物が、トリブチルホスフィン、トリオクチルホスフィン、トリフェニルホスフィン、トリ（ｏ－トリル）ホスフィン、シクロヘキシルジフェニルホスフィン、１，２－ビス（ジフェニルホスフィノ）エタン、およびトリシクロヘキシルホスフィンからなる群より選択される１種のホスフィンまたは２種以上の組合せである、上記項のいずれか一項に記載の導電材。
（項１７ｂ）前記有機リン化合物がトリフェニルホスフィンである、上記項のいずれか一項に記載の導電材。
（項１８）前記金属が、銀、銅、金、アルミニウム、亜鉛、ニッケル、錫、および／または鉄を含む、上記項のいずれか一項に記載の導電材。
（項１８ａ）前記金属が、銀である、上記項のいずれか一項に記載の導電材。
（項１９）前記金属が、１μｍ～１００μｍの粒子径を有する粒子である、上記項のいずれか一項に記載の導電材。
（項２０）前記ポリマーマトリクスは、アクリル系ポリマー、ウレタン系ポリマー、オレフィン系ポリマー、またはエポキシ系ポリマーである、上記項のいずれか一項に記載の導電材。
（項２０ａ）前記ポリマーマトリクスは、（メタ）アクリル系ポリマーである、上記項のいずれか一項に記載の導電材。
（項２１）前記ポリマーマトリクスは、１種のモノマー成分を含むホモポリマーまたは２～３種のモノマー成分を含むコポリマーである、上記項のいずれか一項に記載の導電材。
（項２１ａ）前記ポリマーマトリクスは、ホモポリマーである、上記項のいずれか一項に記載の導電材。
（項２２）前記ポリマーマトリクスのモノマー成分が、式（１）

によって表される化合物であり、式中、
Ｒ^１は、水素原子またはメチル基であり、
Ｒ^２は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基である、
上記項のいずれか一項に記載の導電材。
（項２２ａ）Ｒ^１は、水素原子である、上記項のいずれか一項に記載の導電材。
（項２２ｂ）Ｒ^２は、水素原子、または置換もしくは非置換アルキル基である、上記項のいずれか一項に記載の導電材。
（項２２ｃ）Ｒ^２は、水素原子、または置換もしくは非置換Ｃ_１～６アルキル基である、上記項のいずれか一項に記載の導電材。
（項２２ｄ）Ｒ^２は、エチルである、上記項のいずれか一項に記載の導電材。
（項２３）前記導電材が、分散剤をさらに含む、上記項のいずれか一項に記載の導電材。
（項２４）前記分散剤は、２－（２－ブトキシエトキシ）エタノールである、上記項のいずれか一項に記載の導電材。
（項２５）上記項に記載の１つまたは複数の特徴を含む、上記項のいずれか一項に記載の導電材。
（項２６）導電材を製造する方法であって、該方法は、
ポリマーマトリクスと金属と有機リン化合物とを含む混合物を加熱して導電材を生成する工程を包含する、
方法。
（項２６ａ）金属を含む導電性ポリマーの導電率を向上させる方法であって、該方法は、ポリマーマトリクスと該金属と有機リン化合物とを含む混合物を加熱して、前記金属を含む導電性ポリマーを生成する工程を包含する、
方法。
（項２７）前記加熱の温度が８０℃～１５０℃である、上記項のいずれか一項に記載の方法。
（項２８）前記加熱の温度が１００℃～１４０℃である、上記項のいずれか一項に記載の方法。
（項２９）前記加熱の時間が１０分～５０分である、上記項のいずれか一項に記載の方法。
（項３０）加熱する前に、前記混合物に分散剤を添加する工程を含む、上記項のいずれか一項に記載の方法。
（項３１）上記項に記載の１つまたは複数の特徴を含む、上記項のいずれか一項に記載の方法。 (Item 1) A composition for improving the conductivity of a conductive polymer containing a metallic component, which contains an organic phosphorus compound.
(Item 2) The composition according to the above item, wherein the organic phosphorus compound contains trivalent phosphorus.
(Item 3) The composition according to any one of the above items, wherein the organic phosphorus compound is phosphine substituted with alkyl, cycloalkyl or aryl.
(Item 4) The organophosphorus compound is derived from tributylphosphine, trioctylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, cyclohexyldiphenylphosphine, 1,2-bis (diphenylphosphine) ethane, and tricyclohexylphosphine. The composition according to any one of the above items, which is one kind or a combination of two or more kinds of phosphine selected from the above group.
(Item 4a) The composition according to any one of the above items, wherein the organic phosphorus compound is triphenylphosphine.
(Item 5) The composition according to any one of the above items, wherein the metal-based component is a metal, a metal oxide, a metal carbide, a metal sulfide, or a combination thereof.
(Item 6) The composition according to any one of the above items, wherein the metal contains silver, copper, gold, aluminum, zinc, nickel, tin, and / or iron.
(Item 6a) The composition according to any one of the above items, wherein the metal is silver.
(Item 7) The metal oxide is one or more of oxides selected from the group consisting of alumina, tin oxide, indium oxide, zinc oxide, indium-tin oxide, and antimony-tin oxide. The composition according to any one of the above items, which is a combination.
(Item 8) The metal carbide is one or a combination of two or more carbides selected from the group consisting of tungsten carbide, titanium carbide, molybdenum carbide, tantalum carbide, niobium carbide, vanadium carbide, and zirconium carbide. The composition according to any one of the above items.
(Item 9) The composition according to any one of the above items, wherein the metallic component is particles having a particle size of 1 μm to 100 μm.
(Item 10) The composition according to any one of the above items, wherein the polymer matrix in the conductive polymer is a (meth) acrylic polymer, a urethane polymer, an olefin polymer, or an epoxy polymer.
(Item 10a) The composition according to any one of the above items, wherein the polymer matrix in the conductive polymer is a (meth) acrylic polymer.
(Item 11) The composition according to any one of the above items, wherein the polymer matrix in the conductive polymer is a homopolymer containing one kind of monomer component or a copolymer containing two or three kinds of monomer components.
(Item 11a) The composition according to any one of the above items, wherein the polymer matrix in the conductive polymer is a homopolymer.
(Item 12) The monomer component of the polymer matrix is the formula (1).

It is a compound represented by, and in the formula,
R ¹ is a hydrogen atom or a methyl group and
R ² is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted non-aryl heterocycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. ,
The composition according to any one of the above items.
(Item 12a) The composition according to any one of the above items, wherein R ¹ is a hydrogen atom.
(Item 12b) The composition according to any one of the above items, wherein R ² is a hydrogen atom or a substituted or unsubstituted alkyl group.
(Item 12c) The composition according to any one of the above items, wherein R ² is a hydrogen atom or a substituted or unsubstituted C _{1 to 6} alkyl group.
(Section 12d) R ² is ethyl, A composition according to any one of the above items.
(Item 13) A sintering accelerator for metallic components containing an organic phosphorus compound.
(Item 14) The sintering accelerator according to any one of the above items, which comprises one or more of the characteristics described in the above item.
(Item 15) A conductive material containing a polymer matrix, a metal, and an organic phosphorus compound.
(Item 16) The conductive material according to any one of the above items, wherein the organic phosphorus compound contains trivalent phosphorus.
(Item 17) The conductive material according to any one of the above items, wherein the organic phosphorus compound is phosphine substituted with alkyl, cycloalkyl or aryl.
(Item 17a) The organophosphorus compound is derived from tributylphosphine, trioctylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, cyclohexyldiphenylphosphine, 1,2-bis (diphenylphosphine) ethane, and tricyclohexylphosphine. The conductive material according to any one of the above items, which is one kind of phosphine or a combination of two or more kinds selected from the above group.
(Item 17b) The conductive material according to any one of the above items, wherein the organic phosphorus compound is triphenylphosphine.
(Item 18) The conductive material according to any one of the above items, wherein the metal contains silver, copper, gold, aluminum, zinc, nickel, tin, and / or iron.
(Item 18a) The conductive material according to any one of the above items, wherein the metal is silver.
Item 19. The conductive material according to any one of the above items, wherein the metal is particles having a particle size of 1 μm to 100 μm.
(Item 20) The conductive material according to any one of the above items, wherein the polymer matrix is an acrylic polymer, a urethane polymer, an olefin polymer, or an epoxy polymer.
(Item 20a) The conductive material according to any one of the above items, wherein the polymer matrix is a (meth) acrylic polymer.
(Item 21) The conductive material according to any one of the above items, wherein the polymer matrix is a homopolymer containing one kind of monomer component or a copolymer containing two or three kinds of monomer components.
(Item 21a) The conductive material according to any one of the above items, wherein the polymer matrix is a homopolymer.
(Item 22) The monomer component of the polymer matrix is the formula (1).

It is a compound represented by, and in the formula,
R ¹ is a hydrogen atom or a methyl group and
R ² is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted non-aryl heterocycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. ,
The conductive material according to any one of the above items.
(Item 22a) The conductive material according to any one of the above items, wherein R ¹ is a hydrogen atom.
(Item 22b) The conductive material according to any one of the above items, wherein R ² is a hydrogen atom or a substituted or unsubstituted alkyl group.
(Item 22c) The conductive material according to any one of the above items, wherein R ² is a hydrogen atom or a substituted or unsubstituted C _{1 to 6} alkyl group.
(Item 22d) The conductive material according to any one of the above items, wherein R ² is ethyl.
(Item 23) The conductive material according to any one of the above items, wherein the conductive material further contains a dispersant.
(Item 24) The conductive material according to any one of the above items, wherein the dispersant is 2- (2-butoxyethoxy) ethanol.
(Item 25) The conductive material according to any one of the above items, which comprises one or more features according to the above item.
(Item 26) A method for producing a conductive material, wherein the method is
Including the step of heating a mixture containing a polymer matrix, a metal and an organophosphorus compound to form a conductive material.
Method.
(Item 26a) A method for improving the conductivity of a conductive polymer containing a metal, wherein the method heats a polymer matrix and a mixture containing the metal and an organic phosphorus compound to heat the conductive polymer containing the metal. Including the process of producing
Method.
(Item 27) The method according to any one of the above items, wherein the heating temperature is 80 ° C. to 150 ° C.
(Item 28) The method according to any one of the above items, wherein the heating temperature is 100 ° C. to 140 ° C.
(Item 29) The method according to any one of the above items, wherein the heating time is 10 to 50 minutes.
(Item 30) The method according to any one of the above items, which comprises a step of adding a dispersant to the mixture before heating.
(Item 31) The method according to any one of the above items, which comprises one or more of the features described in the above item.

The disclosure also provides, for example:

によって表される化合物であり、式中、
Ｒ^１は、水素原子またはメチル基であり、
Ｒ^２は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基である、
先行する項のいずれか一項に記載の組成物。
（項Ａ１２ｂ）Ｒ^１は、水素原子である、上記項のいずれか一項に記載の組成物。
（項Ａ１２ｃ）Ｒ^２は、水素原子、または置換もしくは非置換アルキル基である、上記項のいずれか一項に記載の組成物。
（項Ａ１２ｄ）Ｒ^２は、水素原子、または置換もしくは非置換Ｃ_１～６アルキル基である、上記項のいずれか一項に記載の組成物。
（項Ａ１２ｅ）Ｒ^２は、エチルである、上記項のいずれか一項に記載の組成物。
（項Ａ１３）有機リン化合物を含む、金属系成分用の焼結促進剤。
（項Ａ１４）先行する項に記載の１つまたは複数の特徴を含む、先行する項のいずれか一項に記載の焼結促進剤。
（項Ａ１５）ポリマーマトリクスと、金属と、有機リン化合物とを含む、導電材。
（項Ａ１６）前記有機リン化合物が、３価リンを含む、先行する項のいずれか一項に記載の導電材。
（項Ａ１７ａ）前記有機リン化合物が、アルキル、シクロアルキルまたはアリールで置換されたホスフィンである、先行する項のいずれか一項に記載の導電材。
（項Ａ１７ｂ）前記有機リン化合物が、トリブチルホスフィン、トリオクチルホスフィン、トリフェニルホスフィン、トリ（ｏ－トリル）ホスフィン、シクロヘキシルジフェニルホスフィン、１，２－ビス（ジフェニルホスフィノ）エタン、およびトリシクロヘキシルホスフィンからなる群より選択される１種のホスフィンまたは２種以上の組合せである、上記項のいずれか一項に記載の導電材。
（項Ａ１７ｃ）前記有機リン化合物がトリフェニルホスフィンである、上記項のいずれか一項に記載の導電材。
（項Ａ１８）前記金属が、銀、銅、金、アルミニウム、亜鉛、ニッケル、錫、および／または鉄を含む、先行する項のいずれか一項に記載の導電材。
（項Ａ１８ａ）前記金属が、銀である、上記項のいずれか一項に記載の導電材。
（項Ａ１９）前記金属が、１μｍ～１００μｍの粒子径を有する粒子である、先行する項のいずれか一項に記載の導電材。
（項Ａ２０ａ）前記ポリマーマトリクスは、アクリル系ポリマー、ウレタン系ポリマー、オレフィン系ポリマー、エポキシ系ポリマー、またはスチレン・ブタジエン系ポリマーである、先行する項のいずれか一項に記載の導電材。
（項Ａ２０ｂ）前記ポリマーマトリクスは、（メタ）アクリル系ポリマーである、上記項のいずれか一項に記載の導電材。
（項Ａ２１ａ）前記ポリマーマトリクスは、１種のモノマー成分を含むホモポリマーまたは２～３種のモノマー成分を含むコポリマーである、先行する項のいずれか一項に記載の導電材。
（項Ａ２１ｂ）前記ポリマーマトリクスは、ホモポリマーである、上記項のいずれか一項に記載の導電材。
（項Ａ２２ａ）前記ポリマーマトリクスのモノマー成分が、式（１）

によって表される化合物であり、式中、
Ｒ^１は、水素原子またはメチル基であり、
Ｒ^２は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基である、
先行する項のいずれか一項に記載の導電材。
（項Ａ２２ｂ）Ｒ^１は、水素原子である、上記項のいずれか一項に記載の導電材。
（項Ａ２２ｃ）Ｒ^２は、水素原子、または置換もしくは非置換アルキル基である、上記項のいずれか一項に記載の導電材。
（項Ａ２２ｄ）Ｒ^２は、水素原子、または置換もしくは非置換Ｃ_１～６アルキル基である、上記項のいずれか一項に記載の導電材。
（項Ａ２２ｅ）Ｒ^２は、エチルである、上記項のいずれか一項に記載の導電材。
（項Ａ２３）前記導電材が、分散剤をさらに含む、先行する項のいずれか一項に記載の導電材。
（項Ａ２４）前記分散剤は、２－（２－ブトキシエトキシ）エタノールである、先行する項のいずれか一項に記載の導電材。
（項Ａ２５）先行する項に記載の１つまたは複数の特徴を含む、先行する項のいずれか一項に記載の導電材。
（項Ａ２６ａ）導電材を製造する方法であって、該方法は、
ポリマーマトリクスと金属と有機リン化合物とを含む混合物を加熱して導電材を生成する工程を包含する、
方法。
（項Ａ２６ｂ）金属を含む導電性ポリマーの導電率を向上させる方法であって、該方法は、ポリマーマトリクスと該金属と有機リン化合物とを含む混合物を加熱して、前記金属を含む導電性ポリマーを生成する工程を包含する、
方法。
（項Ａ２７）前記加熱の温度が８０℃～１５０℃である、先行する項のいずれか一項に記載の方法。
（項Ａ２８）前記加熱の温度が１００℃～１４０℃である、先行する項のいずれか一項に記載の方法。
（項Ａ２９）前記加熱の時間が１０分～５０分である、先行する項のいずれか一項に記載の方法。
（項Ａ３０）加熱する前に、前記混合物に分散剤を添加する工程を含む、先行する項のいずれか一項に記載の方法。
（項Ａ３１）先行する項に記載の１つまたは複数の特徴を含む、先行する項のいずれか一項に記載の方法。 (Item A1) A composition for improving the conductivity of a conductive polymer containing a metallic component, which contains an organic phosphorus compound.
(Item A2) The composition according to the preceding item, wherein the organic phosphorus compound contains trivalent phosphorus.
(Item A3) The composition according to any one of the preceding items, wherein the organic phosphorus compound is phosphine substituted with an alkyl, cycloalkyl or aryl.
(Item A4a) The organophosphorus compound is derived from tributylphosphine, trioctylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, cyclohexyldiphenylphosphine, 1,2-bis (diphenylphosphine) ethane, and tricyclohexylphosphine. The composition according to any one of the preceding paragraphs, which is one or a combination of two or more of phosphines selected from the group.
(Item A4b) The composition according to any one of the above items, wherein the organic phosphorus compound is triphenylphosphine.
(Item A5) The composition according to any one of the preceding items, wherein the metal-based component is a metal, a metal oxide, a metal carbide, a metal sulfide, or a combination thereof.
(Item A6a) The composition according to any one of the preceding items, wherein the metal comprises silver, copper, gold, aluminum, zinc, nickel, tin, and / or iron.
(Item A6b) The composition according to any one of the above items, wherein the metal is silver.
(Item A7) The metal oxide is one or more of oxides selected from the group consisting of alumina, tin oxide, indium oxide, zinc oxide, indium-tin oxide, and antimony-tin oxide. The composition according to any one of the preceding paragraphs, which is a combination.
(Item A8) The metal carbide is one or a combination of two or more carbides selected from the group consisting of tungsten carbide, titanium carbide, molybdenum carbide, tantalum carbide, niobium carbide, vanadium carbide, and zirconium carbide. The composition according to any one of the preceding paragraphs.
(Item A9) The composition according to any one of the preceding items, wherein the metallic component is particles having a particle size of 1 μm to 100 μm.
(Item A10a) The polymer matrix in the conductive polymer is a (meth) acrylic polymer, a urethane polymer, an olefin polymer, an epoxy polymer, or a styrene-butadiene polymer, any one of the preceding items. The composition according to.
(Item A10b) The composition according to any one of the above items, wherein the polymer matrix in the conductive polymer is a (meth) acrylic polymer.
(Item A11a) The composition according to any one of the preceding items, wherein the polymer matrix in the conductive polymer is a homopolymer containing one monomer component or a copolymer containing two or three monomer components. ..
(Item A11b) The composition according to any one of the above items, wherein the polymer matrix in the conductive polymer is a homopolymer.
(Item A12a) The monomer component of the polymer matrix is the formula (1).

It is a compound represented by, and in the formula,
R ¹ is a hydrogen atom or a methyl group and
R ² is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted non-aryl heterocycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. ,
The composition according to any one of the preceding paragraphs.
(Item A12b) The composition according to any one of the above items, wherein R ¹ is a hydrogen atom.
(Item A12c) The composition according to any one of the above items, wherein R ² is a hydrogen atom or a substituted or unsubstituted alkyl group.
(Item A12d) The composition according to any one of the above items, wherein R ² is a hydrogen atom or a substituted or unsubstituted C _{1 to 6} alkyl group.
(Section A12E) ^{R 2} is ethyl, A composition according to any one of the above items.
(Item A13) A sintering accelerator for metallic components containing an organic phosphorus compound.
(Item A14) The sintering accelerator according to any one of the preceding items, which comprises one or more of the characteristics described in the preceding item.
(Item A15) A conductive material containing a polymer matrix, a metal, and an organic phosphorus compound.
(Item A16) The conductive material according to any one of the preceding items, wherein the organic phosphorus compound contains trivalent phosphorus.
(Item A17a) The conductive material according to any one of the preceding items, wherein the organic phosphorus compound is phosphine substituted with alkyl, cycloalkyl or aryl.
(Item A17b) The organophosphorus compound is derived from tributylphosphine, trioctylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, cyclohexyldiphenylphosphine, 1,2-bis (diphenylphosphine) ethane, and tricyclohexylphosphine. The conductive material according to any one of the above items, which is one kind of phosphine or a combination of two or more kinds selected from the above group.
(Item A17c) The conductive material according to any one of the above items, wherein the organic phosphorus compound is triphenylphosphine.
(Item A18) The conductive material according to any one of the preceding items, wherein the metal contains silver, copper, gold, aluminum, zinc, nickel, tin, and / or iron.
(Item A18a) The conductive material according to any one of the above items, wherein the metal is silver.
(Item A19) The conductive material according to any one of the preceding items, wherein the metal is particles having a particle size of 1 μm to 100 μm.
(Item A20a) The conductive material according to any one of the preceding items, wherein the polymer matrix is an acrylic polymer, a urethane polymer, an olefin polymer, an epoxy polymer, or a styrene-butadiene polymer.
(Item A20b) The conductive material according to any one of the above items, wherein the polymer matrix is a (meth) acrylic polymer.
(Item A21a) The conductive material according to any one of the preceding items, wherein the polymer matrix is a homopolymer containing one kind of monomer component or a copolymer containing two or three kinds of monomer components.
(Item A21b) The conductive material according to any one of the above items, wherein the polymer matrix is a homopolymer.
(Item A22a) The monomer component of the polymer matrix is the formula (1).

It is a compound represented by, and in the formula,
R ¹ is a hydrogen atom or a methyl group and
R ² is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted non-aryl heterocycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. ,
The conductive material according to any one of the preceding items.
(Item A22b) The conductive material according to any one of the above items, wherein R ¹ is a hydrogen atom.
(Item A22c) The conductive material according to any one of the above items, wherein R ² is a hydrogen atom or a substituted or unsubstituted alkyl group.
(Item A22d) The conductive material according to any one of the above items, wherein R ² is a hydrogen atom or a substituted or unsubstituted C _{1 to 6} alkyl group.
(Item A22e) The conductive material according to any one of the above items, wherein R ² is ethyl.
(Item A23) The conductive material according to any one of the preceding items, wherein the conductive material further contains a dispersant.
(Item A24) The conductive material according to any one of the preceding items, wherein the dispersant is 2- (2-butoxyethoxy) ethanol.
(Item A25) 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 A26a) A method for producing a conductive material, wherein the method is
Including the step of heating a mixture containing a polymer matrix, a metal and an organophosphorus compound to form a conductive material.
Method.
(Item A26b) A method for improving the conductivity of a conductive polymer containing a metal, wherein the method heats a polymer matrix and a mixture containing the metal and an organic phosphorus compound to heat the conductive polymer containing the metal. Including the process of producing
Method.
(Item A27) The method according to any one of the preceding items, wherein the heating temperature is 80 ° C. to 150 ° C.
(Item A28) The method according to any one of the preceding items, wherein the heating temperature is 100 ° C. to 140 ° C.
(Item A29) The method according to any one of the preceding items, wherein the heating time is 10 to 50 minutes.
(Item A30) The method according to any one of the preceding items, which comprises a step of adding a dispersant to the mixture before heating.
(Item A31) The method according to any one of the preceding items, which comprises one or more of the features described in the preceding item.

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.

"Phosphine" as used herein is a trivalent phosphorus compound represented by R 3 _P, wherein each R is independently hydrogen or optionally substituted, any alkyl, cycloalkyl, aryl , Non-aryl heterocycloalkyl, heteroaryl and the like.

As used herein, the term "organophosphorus compound" is used in the usual sense in the art and is a general term for organic compounds containing phosphorus, such as those in which a phosphorus atom is directly bonded to a carbon atom and a phosphoric acid ester. Some are bonded, and organic compounds containing a carbon-phosphorus bond are generally used. As the organic phosphorus compound, a compound containing trivalent phosphorus is typically used, and examples thereof include, but are not limited to, phosphine substituted with alkyl, cycloalkyl or aryl, and examples thereof include tributylphosphine and tri. One or more phosphines selected from the group consisting of octylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, cyclohexyldiphenylphosphine, 1,2-bis (diphenylphosphine) ethane, and tricyclohexylphosphine. Combinations of, especially triphosphine and the like can be used.

As used herein, "improving conductivity" means that when a component of the present disclosure is added to a conductive component or a conductive material, the conductivity is significantly increased as compared with that before the addition, for example. Conductivity at least about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80% , About 85%, about 90%, about 95%, about 99% improvement, which can also be expressed by a decrease in volume resistivity. 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.

As used herein, the term "lowering the sintering temperature" means the same or smaller when the components of the present disclosure are added to the conductive component or the conductive material, even when heated at a lower temperature than when not added. It means that the volume resistivity can be achieved. For example, the sintering temperature is at least about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15. %, About 20%, About 25%, About 30%, About 35%, About 40%, About 45%, About 50%, About 55%, About 60%, About 65%, About 70%, About 75%, It means to reduce by about 80%, about 85%, about 90%, about 95%, and about 99%.

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". The polymer matrix may be a homopolymer containing one kind of monomer component or a copolymer containing two or three kinds of monomer components, and a (meth) acrylic polymer or the like can be used.

によって表される化合物であって、式中、Ｒ^１は、水素原子またはメチル基であり、Ｒ^２は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基である、化合物であってもよい。 For example, the monomer component of the polymer matrix is the formula (1).

In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted compound. It may be a compound which is a non-aryl heterocycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

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.) or a combination thereof.

In the present specification, the "metal component" includes a metal or an alloy. Examples of the metal may be silver, copper, gold, aluminum, zinc, nickel, tin, and / or iron.

Examples of the metal oxide include alumina, tin oxide, indium oxide, zinc oxide, indium-tin oxide, and antimony-tin oxide.

Examples of the metal carbide include tungsten carbide, titanium carbide, molybdenum carbide, tantalum carbide, niobium carbide, vanadium carbide, zirconium carbide and the like.

In the present specification, the "particle size" or "particle size" of the metal-based component is used interchangeably, means an average particle size d50, and can be measured by a commercially available laser diffraction type particle size distribution measuring device or the like. it can. The particle size is also applied to the case of a shape that is not spherical, and if it is other than spherical, it means the particle size when converted to spherical. The shape other than the spherical shape may be any shape such as a reptile shape or a needle shape.

As used herein, the term "conductive polymer" includes, among the polymers, those having conductivity and those having conductivity as a whole when mixed with other components, preferably having a resistivity of 1. 0 x 10 ^-3 Ω · cm or less. A typical example of a conductive polymer is a mixture of a polymer matrix and a metallic component. The conductive polymer is sometimes referred to as a conductive polymer composition.

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".

In the present specification, the "urethane-based polymer" refers to a polymer having a urethane bond (-OC (= O) NH-). A typical example is that obtained by reacting a polyol with diisocyanate. Urethane-based polymers may also be referred to herein as "urethane-based resins" or "urethane resins."

In the present specification, the "olefin polymer" is a polymer produced by polymerizing a hydrocarbon monomer (typically an alkene) having one or more double bonds. Specific examples include polyethylene, polypropylene, polystyrene and the like. Olefin polymers may also be referred to herein as "olefinic resins" or "olefinic resins."

In the present specification, the "epoxy polymer" refers to a thermosetting resin that can be cured by forming a cross-linked network with epoxy groups remaining in the polymer. Epoxy-based polymers include prepolymers before cross-linking networking and resins obtained by thermosetting a mixture of prepolymer and curing agent. Epoxy polymers may also be referred to herein as "epoxy resins" or "epoxy resins."

In the present specification, the "styrene-butadiene polymer" is a copolymer produced by copolymerizing a styrene-based monomer and a butadiene-based monomer. The styrene-butadiene polymer may be referred to as a "styrene-butadiene resin" or a "styrene-butadiene resin" in the present specification.

As used herein, the term "substitutable number" means the maximum number of hydrogens that can be substituted when hydrogen of a certain group is substituted with a substituent, provided that the resulting group is chemically stable. To do.

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 a trifluoromethyl group, a trifluoroethyl group (2,2,2-trifluoroethyl group, etc.), a perfluoroethyl group, and a trifluoro group. n-propyl group, tetrafluoropropyl group (2,2,3,3-tetrafluoropropyl group, etc.), perfluoro n-propyl group, trifluoroisopropyl group, perfluoroisopropyl group, trifluoro n-butyl group, perfluoro n- Butyl group, trifluoroisobutyl group, perfluoroisobutyl group, trifluorotert-butyl group, perfluorotert-butyl group, trifluoron-pentyl group, octafluoropentyl group (2,2,3,3,4,4,5) , 5-Octafluoropentyl group, etc.), perfluoro n-pentyl group, trifluoro n-hexyl group, perfluoro n-hexyl group, etc., but the present disclosure is not limited to such examples. Examples of the haloalkyl group having 1 to 8 carbon atoms (C _1-8 haloalkyl group) include C _1-6 haloalkyl group, undecafluoro n-heptyl group, perfluoro n-heptyl group, and tridecafluorooctyl group (3,3, 4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group, etc.), perfluoron-octyl group, etc., but the present disclosure is limited to such examples. It is not limited.

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 hexamethyleneiminyl group, a thiazolidinyl group and a tetrahydrofuranyl group. Examples thereof include a tetrahydropyridinyl group, a tetrahydropyranyl group, a 1,3-dioxolanyl group, a 1,3-dioxanyl group, a 1,4-dioxanyl group, etc., but the present disclosure is not limited to such examples. Absent. The group also includes a heterocyclic group having a crosslinked structure.

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 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, styrene-based monomers, butadiene-based monomers, urethane-based monomers, amide-based monomers, ester-based monomers, ether-based monomers, imide-based monomers, and amide-. Formed by polymerization of imide-based monomer, carbonate-based monomer, acetal-based monomer, sulfone-based monomer, phenylene sulfide-based monomer, ether ether ketone-based monomer, silicone-based monomer, and AES resin, diallyl phthalate resin, ABS resin, silicone resin, etc. Monomer to be mentioned.

In the present specification, "firing" refers to a process of molding a raw material powder, heating it, shrinking and densifying it, and obtaining a sintered body having a certain shape and strength.

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 "sintering accelerator" refers to a substance that lowers the temperature required to achieve sintering by interacting with a metallic component as compared with before its addition.

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 of the conductive polymer provided in the present disclosure contains an organic phosphorus compound.

(Conductive component targeted by the conductivity improver)
The conductive component that can be targeted by the conductivity improver of the present disclosure may be any substance as long as it is a substance that promotes adsorption and diffusion, and a typical component includes any metal-based component. Although it is not desired to be bound by theory, since the components of the present disclosure have an action of adsorption and diffusion, if it is a metallic component, the conductivity is increased by the action of increasing the contacts of the conductive components by adsorption and diffusion. This is because it is thought to improve.

The conductive component that can be targeted by the conductivity improver of the present disclosure is preferably a metal component. I do not want to be bound by the theory, but in the case of metal components, if there are molecules in the system that interact with the metal components, the molecules will be adsorbed on the metal surface and the amount of metal that can interact with the adsorbed part will be. It is also considered that the dissociation of the fine particles increases the amount of metal fine particles present in the system, and the number of contacts increases, so that the conductivity is improved.

More preferably, silver, copper, gold, aluminum, zinc, nickel, tin, iron and the like are targeted, and even more preferably silver is targeted.

(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 illuminated by the light source used in the examples or test 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 required by mixing two or more specific monomers under appropriate polymerization conditions. It can be produced by polymerizing with an appropriate additive such as a polymerization initiator. Then, the conductive material of the present disclosure can be produced by mixing the conductive component and any other component with this polymer matrix and heating the polymer matrix. The polymer will be described in detail below with details such as individual components and specific production conditions.

によって表される化合物であり、式中、Ｒ^１は、水素原子またはメチル基であり、
Ｒ^２は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基である。 In one aspect, the present disclosure relates to a method of producing a homopolymer containing one monomer component or a copolymer containing two to three monomer components as a polymer matrix. In a typical embodiment, the monomer component of the polymer matrix is of formula (1).

In the formula, R ¹ is a hydrogen atom or a methyl group, and is a compound represented by.
R ² is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted non-aryl heterocycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. ..

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 monomer component used in the present disclosure may be commercially available from a manufacturer exemplified in Examples or Test Examples, and is prepared according to a method well known to those skilled in the art. You may.

(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 (meth) acrylic monomer with ultraviolet rays 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, undecane, limonene, 3-methoxy-3-methyl-1-butanol, octanol, and 2-ethyl-1-hexanol.

(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.

The conductive material of the present disclosure is obtained by mixing one or more specific monomers and polymerizing them under appropriate polymerization conditions using appropriate additives such as a polymerization initiator as necessary. , Can be manufactured. The individual components and specific manufacturing conditions will be described in detail below.

(Explanation of conductive components)
The essential conductive component in the present disclosure is a metal-based component (including a conductive whisker such as zinc oxide and potassium titanate, and a conductive metal oxide such as titanium oxide), preferably a metal component, and more. Preferred are metal particles such as copper, gold, nickel, tin, aluminum, zinc, iron and silver. As the conductive component in the present disclosure, for example, natural graphite such as scaly graphite, graphite such as artificial graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, etc. are used together with the metallic component. Carbon-based materials such as carbon black, graphite, carbon nanotubes, and fullerene; conductive fibers such as carbon fibers and metal fibers; carbon fluoride; organic conductive materials such as polyphenylene derivatives may be used. In the present disclosure, each of the essential conductive components may be used alone, or two or more of these conductive components may be used in combination, including at least one essential conductive component.

The solid content of the conductive component in the total solid content of the polymer matrix and the conductive component cannot be unconditionally determined because it differs depending on the type of the conductive component and the like, but it is usually excellent in workability and moldability, and also. From the viewpoint of obtaining a conductive film having excellent flexibility and extensibility, it is preferably 1% by mass or more, and from the viewpoint of obtaining a conductive film having excellent workability and moldability and excellent flexibility and extensibility. It is preferably 100% by mass or less.

Examples of carbon nanotubes include single-wall carbon nanotubes having a hollow cylindrical structure in which one sheet of graphite (graphene sheet) is rolled into a cylinder, and multi-walls having a structure in which a plurality of single-wall carbon nanotubes having different diameters are concentrically laminated. Examples thereof include carbon nanotubes, single-wall carbon nanotubes manufactured by the super-growth method, carbon nanocones having a conical and closed end of the single-wall carbon nanotubes, and carbon nanotubes containing fullerenes inside. Is not limited to such examples. Each of these carbon nanotubes may be used alone, or two or more types may be used in combination. 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 polymer of the present disclosure is used in, for example, sensors, wirings, electrodes, substrates, power generating elements, speakers, microphones, noise cancellers, transducers, artificial muscles, small pumps, medical instruments and the like used in actuators, industrial robots and the like. It can be suitably used as a conductive film that can be suitably used and as a raw material for the conductive film.

(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, the present disclosure provides a composition for improving the conductivity of a conductive polymer containing a metallic component, which contains an organic phosphorus compound.

In one specific embodiment, it was confirmed that the addition of phosphine caused sintering at a low temperature (120 ° C.), which was not conventionally sintered. Although not bound by theory, in this embodiment, it is considered that the sintering of the metal particles inside was promoted because the decrease in the resistance value change was further confirmed as the amount of phosphine added increased. .. Further, it is considered that the larger the amount of phosphine added, the smaller the number of contacts of the filler, but it was found by the present disclosure that there is no significant change in the conductivity. When the energy of the system during heating was calculated, it was most stable when the distance between the phosphine molecule and the silver atom was close enough to interact, so a large amount of fine particles were generated due to the adsorption diffusion effect. It is thought that this is because the contacts are made.

In one embodiment, the organophosphorus compound comprises trivalent phosphorus.

In one embodiment, the organophosphorus compound is phosphine substituted with alkyl, cycloalkyl or aryl.

In one embodiment, the organophosphorus compounds are tributylphosphine, trioctylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, cyclohexyldiphenylphosphine, 1,2-bis (diphenylphosphino) ethane, and tricyclohexyl. One or a combination of two or more phosphines selected from the group consisting of phosphines.

In one embodiment, the organophosphorus compound is triphenylphosphine.

In one embodiment, the metal-based component is a metal, a metal oxide, a metal carbide, a metal sulfide, or a combination thereof.

In one embodiment, the metal comprises silver, copper, gold, aluminum, zinc, tin, nickel, and / or iron.

In one embodiment, the metal is silver.

In one embodiment, the metal oxide is one or two oxides selected from the group consisting of alumina, tin oxide, indium oxide, zinc oxide, indium-tin oxide, and antimony-tin oxide. The above combination.

In one embodiment, the metal carbide is one or more combinations of carbides selected from the group consisting of tungsten carbide, titanium carbide, molybdenum carbide, tantalum carbide, niobium carbide, vanadium carbide, and zirconium carbide. is there.

In another embodiment, the metal-based component is a particle having a particle diameter of 1 μm to 100 μm. The metallic component is preferably a particle having a particle diameter of 90 μm or less, 80 μm or less, 70 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, 10 μm or less, 5 μm or less, and 0. 01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, 0.6 μm or more, 0.7 μm or more, 0.8 μm or more, 0. It can be 9 μm or more, 1 μm or more, 1.5 μm or more, 2 μm or more, 2.5 μm or more, 3 μm or more, and the like. The metal-based component is more preferably particles having a particle size of 1 μm to 50 μm, further preferably 1 μm to 10 μm, and even more preferably 1 μm to 10 μm. The shape of the particles is not particularly limited, and examples thereof include spherical, scaly, and needle-shaped shapes.

In one embodiment, the polymer matrix in the conductive polymer is a (meth) acrylic polymer, a urethane polymer, an olefin polymer, or an epoxy polymer.

In one embodiment, the polymer matrix in the conductive polymer is a (meth) acrylic polymer, a urethane polymer, an olefin polymer, an epoxy polymer, or a styrene-butadiene polymer.

In one embodiment, the polymer matrix in the conductive polymer is a (meth) acrylic polymer.

In one embodiment, the polymer matrix in the conductive polymer is a homopolymer containing one monomer component or a copolymer containing two to three monomer components.

In one embodiment, the polymer matrix in the conductive polymer is a homopolymer.

によって表される化合物であり、式中、Ｒ^１は、水素原子またはメチル基であり、Ｒ^２は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基である。 In one embodiment, the monomer component of the polymer matrix is of formula (1).

In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted non-substituted compound. Aryl heterocycloalkyl groups, substituted or unsubstituted aryl groups, or substituted or unsubstituted heteroaryl groups.

In one embodiment, R ¹ is a hydrogen atom. In another embodiment, R ¹ is a methyl group.

In one embodiment, R ² is a hydrogen atom, or a substituted or unsubstituted alkyl group.

In one embodiment, R ² is a hydrogen atom, or a substituted or unsubstituted C _1-6 alkyl group.

In one embodiment, R ² is ethyl.

(Sintering accelerator)
In one aspect, the present disclosure provides sintering accelerators for metallic components, including organophosphorus compounds.

In one specific aspect, the present disclosure provides sintering accelerators for metallic components, including triarylphosphine. As a preferred embodiment of the sintering accelerator, any embodiment described in the present specification or a combination thereof can be utilized, and any of the embodiments described in the section (Use for improving conductivity) in the present specification. One or a combination of a plurality of embodiments of the above can be applied.

Although we do not want to be bound by theory, the interaction between metallic components (eg, silver particles) and organic molecules (eg, triphenylphosphine) lowers the surface energy of the metallic components and external energy. It is considered that sintering is promoted because it is easily affected by (heat energy due to sintering).

The sintering accelerator of the present disclosure may be used for the above-mentioned firing, such as when manufacturing a molded product by powder metallurgy or manufacturing a sintered alloy.

(Conductive material)
In one aspect, the present disclosure provides a conductive material comprising the polymer matrix of the present disclosure, a metal, and an organophosphorus compound.

Since the conductive material of the present disclosure is intended to be coated on an elastomer or a substrate, it is preferable that the heating temperature is lower. The mixture of silver microparticles and acrylic copolymer required heat treatment at 180 ° C., but the resin composition and silver particles were changed by adding a triphenylphosphine solution to the mixture of polymer matrix and metal. It is possible to perform heat treatment at a lower temperature than the conventional one without doing so.

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.

In one embodiment, the organophosphorus compound comprises trivalent phosphorus.

In one embodiment, the organophosphorus compound is phosphine substituted with alkyl, cycloalkyl or aryl.

In one embodiment, the organophosphorus compounds are tributylphosphine, trioctylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, cyclohexyldiphenylphosphine, 1,2-bis (diphenylphosphino) ethane, and tricyclohexyl. One type of phosphine or a combination of two or more types selected from the group consisting of phosphine.

In one embodiment, the organophosphorus compound is triphenylphosphine.

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 metal is a particle having a particle size of 1 μm to 100 μm.

In one embodiment, the polymer matrix is an acrylic polymer, a urethane polymer, an olefin polymer, or an epoxy polymer.

In one embodiment, the polymer matrix is an acrylic polymer, a urethane polymer, an olefin polymer, an epoxy polymer, or a styrene-butadiene polymer.

In one embodiment, the polymer matrix is a (meth) acrylic polymer or a styrene-butadiene polymer. In one embodiment, the polymer matrix is a (meth) acrylic polymer. In one embodiment, the polymer matrix is a styrene-butadiene polymer.

In one embodiment, the polymer matrix is a homopolymer containing one monomer component or a copolymer containing two to three monomer components.

In one embodiment, the polymer matrix is a homopolymer.

によって表される化合物であり、式中、Ｒ^１は、水素原子またはメチル基であり、Ｒ^２は、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換シクロアルキル基、置換もしくは非置換非アリールヘテロシクロアルキル基、置換もしくは非置換アリール基、または置換もしくは非置換ヘテロアリール基である。 In one embodiment, the monomer component of the polymer matrix is of formula (1).

In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted non-substituted compound. Aryl heterocycloalkyl groups, substituted or unsubstituted aryl groups, or substituted or unsubstituted heteroaryl groups.

In one embodiment, R ¹ is a hydrogen atom. In another embodiment, R ¹ is a methyl group.

In one embodiment, R ² is a hydrogen atom, or a substituted or unsubstituted alkyl group.

In one embodiment, R ² is a hydrogen atom, or a substituted or unsubstituted C _1-6 alkyl group.

In one embodiment, R ² is ethyl.

In one embodiment, the conductive material further comprises a dispersant.

In one embodiment, the dispersant is 2- (2-butoxyethoxy) ethanol.

(Manufacturing of conductive material)
In one aspect, the present disclosure provides a method for producing the conductive materials and sintering accelerators of the present disclosure.

In a specific aspect, the present disclosure provides a method for producing a conductive material, which comprises a step of heating a mixture containing a polymer matrix, a metal and an organophosphorus compound to produce a conductive material.
The method comprises heating a mixture of the polymer matrix with the metal and an organophosphorus compound to produce a conductive polymer containing the metal. 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 one embodiment, the heating temperature is 80 ° C. to 150 ° C., preferably 100 ° C. to 140 ° C.

In one embodiment, the heating time is 10 to 50 minutes.

In another embodiment, the method comprises adding a dispersant to the mixture prior to heating.

(Note)
As used herein, "or" is used when "at least one" of the matters listed in the text can be adopted. The same applies to "or". When specified as "within the range of two values" in the present specification, the range also includes the two values themselves.

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. The present disclosure will be described below based on Test Examples, but the above description and the following Test Examples are provided for purposes of illustration only and not for the purpose of limiting this disclosure. Therefore, the scope of the present disclosure is not limited to the embodiments, examples, or test examples specifically described in the present specification, but is limited only by the scope of claims.

[Test example]
Test examples are described below. The handling of organisms used in the following test examples complied with the standards set by the regulatory agency, if necessary. Specifically, as the reagents, the products described in Examples or Test Examples were used, but equivalent products of other manufacturers (Sigma-Aldrich, etc.) can be substituted.

(Preparation of polymer matrix)
<Test Example 1>
A polymerization initiator by mixing ethyl acrylate (EA, 10.00 g) with 2,4,6-trimethylbenzoyldiphenylphosphine oxide (0.0123 g, manufactured by BASF, trade name: Irgacure TPO) as a polymerization initiator. A monomer component containing the above 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.

An acrylic resin solution was obtained by dissolving the obtained polymer (10.00 g) in toluene (90.00 g).

(Preparation of phosphine solution)
Triphenylphosphine (5.00 g) was dissolved in tetrahydrofuran (5.00 g) to obtain a phosphine solution.

(How to make a conductive film)
To the acrylic resin solution (60.00 g) obtained in Test Example 1, a silver filler (24.00 g, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., trade name AgC-A), 2- (2-butoxyethoxy) as a dispersant ) Ethanol (0.5 g) and the prepared triphenylphosphine solution (0.12 g) were added and mixed with Mazelstar manufactured by Kurabou Co., Ltd. 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 coating film was heated in an oven at 120 ° C. for 30 minutes to obtain a conductive film having a thickness of about 30 μm.

(Measurement of volume resistivity)
The obtained conductive film was cut into a length of 0.5 cm and a width of 2.00 cm, and measured by a 4-terminal method using Loresta GP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.).

(How to check the change in resistance value)
(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, the distance between the electrodes was set to 2.00 cm while the conductive film was fixed on the multimeter electrode, and the resistance value (ΩB) at that time was measured. The change in resistance value was calculated as follows.
Resistance value change = ΩB / ΩA

<Test Examples 2 and 3>
A conductive film was prepared in the same manner as in Test Example 1 except that the amount of the triphenylphosphine solution added was changed as shown in Table 1, and the change in resistance value was measured in the same manner as in Test Example 1.

<Test Example 4>
A cyclohexyldiphenylphosphine solution was prepared in the same manner as in Test Example 1 except that cyclohexyldiphenylphosphine was used instead of triphenylphosphine. A conductive film was prepared in the same manner as in Test Example 1 except that this cyclohexyldiphenylphosphine solution was used instead of the triphenylphosphine solution, and the change in resistance value was measured in the same manner as in Test Example 1.

<Test Examples 5 to 7>
A conductive film was prepared in the same manner as in Test Example 1 except that the amount of the silver filler added was changed as shown in Table 2, and the change in resistance value was measured in the same manner as in Test Example 1.

<Test Example 8>
A conductive film was prepared in the same manner as in Test Example 1 except that the temperature of the heat treatment was changed to 150 ° C., and the change in resistance value was measured in the same manner as in Test Example 1.

<Test Examples 9 and 10>
A resin solution was obtained by dissolving polycycloolefin (40.00 g, manufactured by Zeon Corporation, trade name: Zeonoa) in toluene (60.00 g). Using this resin solution, a conductive film having the composition shown in Table 2 was prepared in the same manner as in each of the above test examples, and the change in resistance value was measured in the same manner as in Test Example 1.

<Test Example 11>
A styrene-butadiene block copolymer (4.00 g, JSR product name: TR2601C) was dissolved in toluene (6.00 g) to obtain a styrene-butadiene resin solution. To this styrene-butadiene resin solution (10.00 g), a silver filler (16.00 g), 2- (2-butoxyethoxy) ethanol (0.32 g) as a dispersant, and the above triphenylphosphine solution (0.8 g) are added. Then, it was mixed with a Mazel Star manufactured by Kurabou Co., Ltd. to obtain a conductive material precursor. Using the obtained conductive material precursor, a conductive film was prepared in the same manner as in each of the above test examples, and the change in resistance value was measured in the same manner as in Test Example 1.

<Test Example 12>
A conductive film was prepared in the same manner as in Test Example 11 except that the amount of the triphenylphosphine solution added was changed as shown in Table 2, and the change in resistance value was measured in the same manner as in Test Example 1.

(result)
The results of each of the above test examples are shown in Tables 1 and 2.

Comparing the particle size distribution after sintering between the system with triphenylphosphine added and the system without triphenylphosphine, the frequency is high in the range of 5 μm to 10 μm and ≦ 1 μm in the added system, and about 3 to 5 μm in the non-added system. Frequent frequency was observed in the range (data not shown).

(Note)
As described above, the present disclosure has been illustrated using the preferred embodiments of the present disclosure, but it is understood that the scope of the present disclosure should be interpreted only by the scope of claims. The present application claims priority to Japanese Patent Application No. 2019-148111 (filed on August 9, 2019), the entire contents of which are incorporated herein by reference in its entirety. The patents, patent applications and other documents cited herein should be incorporated herein by reference in their content as they are specifically described herein. Is understood.

Using the conductivity improver of the present disclosure, it is possible to provide an efficient conductive material, and it can be used in industries that require a conductive material.

The sintering accelerator of the present disclosure can be used to lower the sintering temperature of metal-based components, and can be used in industries that require sintering of metal-based components.

Claims (31)

A composition for improving the conductivity of a conductive polymer containing a metallic component, which contains an organic phosphorus compound. The composition according to claim 1, wherein the organic phosphorus compound contains trivalent phosphorus. The composition according to claim 1 or 2, wherein the organophosphorus compound is phosphine substituted with an alkyl, cycloalkyl or aryl. The organophosphorus compound is selected from the group consisting of tributylphosphine, trioctylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, cyclohexyldiphenylphosphine, 1,2-bis (diphenylphosphine) ethane, and tricyclohexylphosphine. The composition according to any one of claims 1 to 3, which is one kind or a combination of two or more kinds of phosphine. The composition according to any one of claims 1 to 4, wherein the metal-based component is a metal, a metal oxide, a metal carbide, a metal sulfide, or a combination thereof. The composition according to any one of claims 1 to 5, wherein the metal comprises silver, copper, gold, aluminum, zinc, nickel, tin, and / or iron. The metal oxide is one or a combination of two or more oxides selected from the group consisting of alumina, tin oxide, indium oxide, zinc oxide, indium-tin oxide, and antimony-tin oxide. The composition according to any one of claims 1 to 6. Claims 1 to 1, wherein the metal carbide is one or a combination of two or more carbides selected from the group consisting of tungsten carbide, titanium carbide, molybdenum carbide, tantalum carbide, niobium carbide, vanadium carbide, and zirconium carbide. The composition according to any one of 7. The composition according to any one of claims 1 to 8, wherein the metallic component is a particle having a particle diameter of 1 μm to 100 μm. The polymer matrix in the conductive polymer is any one of claims 1 to 9, wherein the polymer matrix is a (meth) acrylic polymer, a urethane polymer, an olefin polymer, an epoxy polymer, or a styrene-butadiene polymer. Composition. The composition according to any one of claims 1 to 10, wherein the polymer matrix in the conductive polymer is a homopolymer containing one kind of monomer component or a copolymer containing two or three kinds of monomer components. The monomer component of the polymer matrix is the formula (1).

It is a compound represented by, and in the formula,
R ¹ is a hydrogen atom or a methyl group and
R ² is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted non-aryl heterocycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. ,
The composition according to any one of claims 1 to 11. Sintering accelerator for metallic components, including organophosphorus compounds. The sintering accelerator according to claim 13, which comprises one or more of the features according to claims 1-12. A conductive material containing a polymer matrix, a metal, and an organic phosphorus compound. The conductive material according to claim 15, wherein the organic phosphorus compound contains trivalent phosphorus. The conductive material according to claim 15 or 16, wherein the organic phosphorus compound is phosphine substituted with an alkyl, cycloalkyl or aryl. The conductive material according to any one of claims 15 to 17, wherein the metal comprises silver, copper, gold, aluminum, zinc, nickel, tin, and / or iron. The conductive material according to any one of claims 15 to 18, wherein the metal is a particle having a particle diameter of 1 μm to 100 μm. The conductive material according to any one of claims 15 to 19, wherein the polymer matrix is an acrylic polymer, a urethane polymer, an olefin polymer, an epoxy polymer, or a styrene-butadiene polymer. The conductive material according to any one of claims 15 to 20, wherein the polymer matrix is a homopolymer containing one kind of monomer component or a copolymer containing two or three kinds of monomer components. The monomer component of the polymer matrix is the formula (1).

It is a compound represented by, and in the formula,
R ¹ is a hydrogen atom or a methyl group and
R ² is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted non-aryl heterocycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. ,
The conductive material according to any one of claims 15 to 21. The conductive material according to any one of claims 15 to 22, wherein the conductive material further contains a dispersant. The conductive material according to any one of claims 15 to 23, wherein the dispersant is 2- (2-butoxyethoxy) ethanol. The conductive material according to any one of claims 15 to 24, which comprises one or more of the features according to claims 1 to 14. It is a method of producing a conductive material, and the method is
Including the step of heating a mixture containing a polymer matrix, a metal and an organophosphorus compound to form a conductive material.
Method. 26. The method of claim 26, wherein the heating temperature is 80 ° C. to 150 ° C. The method according to claim 26 or 27, wherein the heating temperature is 100 ° C. to 140 ° C. The method according to any one of claims 26 to 28, wherein the heating time is 10 to 50 minutes. The method according to any one of claims 26 to 29, which comprises a step of adding a dispersant to the mixture before heating. The method of any one of claims 26-30, comprising one or more of the features of claims 1-25.