JP6627228B2 - Copper-containing particles, conductor-forming composition, method for producing conductor, conductor and device - Google Patents
Copper-containing particles, conductor-forming composition, method for producing conductor, conductor and device Download PDFInfo
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- JP6627228B2 JP6627228B2 JP2015038205A JP2015038205A JP6627228B2 JP 6627228 B2 JP6627228 B2 JP 6627228B2 JP 2015038205 A JP2015038205 A JP 2015038205A JP 2015038205 A JP2015038205 A JP 2015038205A JP 6627228 B2 JP6627228 B2 JP 6627228B2
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- Prior art keywords
- copper
- conductor
- containing particles
- particles
- major axis
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 200
- 229910052802 copper Inorganic materials 0.000 title claims description 195
- 239000010949 copper Substances 0.000 title claims description 195
- 239000002245 particle Substances 0.000 title claims description 176
- 239000004020 conductor Substances 0.000 title claims description 55
- 239000000203 mixture Substances 0.000 title claims description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 46
- 239000000126 substance Substances 0.000 claims description 22
- 239000007771 core particle Substances 0.000 claims description 17
- 239000002612 dispersion medium Substances 0.000 claims description 7
- 239000011246 composite particle Substances 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 43
- 229930195729 fatty acid Natural products 0.000 description 43
- 239000000194 fatty acid Substances 0.000 description 43
- 150000004665 fatty acids Chemical class 0.000 description 43
- 150000003973 alkyl amines Chemical class 0.000 description 38
- 150000001875 compounds Chemical class 0.000 description 36
- 230000001603 reducing effect Effects 0.000 description 35
- 125000004432 carbon atom Chemical group C* 0.000 description 24
- 238000000034 method Methods 0.000 description 24
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 21
- 150000002430 hydrocarbons Chemical group 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002923 metal particle Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- -1 salt compound Chemical class 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 239000012691 Cu precursor Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- BWVZAZPLUTUBKD-UHFFFAOYSA-N 3-(5,6,6-Trimethylbicyclo[2.2.1]hept-1-yl)cyclohexanol Chemical compound CC1(C)C(C)C2CC1CC2C1CCCC(O)C1 BWVZAZPLUTUBKD-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 4
- 239000005750 Copper hydroxide Substances 0.000 description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910001956 copper hydroxide Inorganic materials 0.000 description 4
- HZULDDWVCRWYCB-UHFFFAOYSA-L copper;nonanoate Chemical compound [Cu+2].CCCCCCCCC([O-])=O.CCCCCCCCC([O-])=O HZULDDWVCRWYCB-UHFFFAOYSA-L 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
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- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
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- 235000003441 saturated fatty acids Nutrition 0.000 description 4
- 229940116411 terpineol Drugs 0.000 description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
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- 239000011248 coating agent Substances 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 150000002429 hydrazines Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
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- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005263 alkylenediamine group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
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Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Description
本発明は、銅含有粒子、導体形成組成物、導体の製造方法、導体及び装置に関する。 The present invention relates to a copper-containing particle, a conductor-forming composition, a method for producing a conductor, a conductor, and an apparatus.
金属パターンの形成方法として、銅等の金属粒子を含むインク、ペースト等の導電材料をインクジェット印刷、スクリーン印刷等により基材上に付与する工程と、導電材料を加熱して金属粒子を融着させ、導電性を発現させる導体化工程とを含む、いわゆるプリンテッドエレクトロニクス法が知られている。導電材料に含まれる金属粒子としては、金属の酸化を抑制して保存性を高めるために表面に被覆材としての有機物を付着させたものが知られている。 As a method of forming a metal pattern, an ink containing metal particles such as copper, a step of applying a conductive material such as a paste on a substrate by inkjet printing, screen printing, and the like, and heating the conductive material to fuse the metal particles There is known a so-called printed electronics method, which includes a step of forming a conductive layer to exhibit conductivity. As the metal particles contained in the conductive material, those in which an organic substance as a coating material is adhered to the surface in order to suppress the oxidation of the metal and enhance the preservability are known.
特許文献１には、低温で融着でき、良好な導電性を発現する有機物で被覆された銅粒子及びその製造方法が記載されている。特許文献１に記載の銅粒子は、シュウ酸銅等の銅前駆体とヒドラジン等の還元性化合物とを混合して複合化合物を得る工程と、前記複合化合物をアルキルアミンの存在下で加熱する工程とを有する方法によって製造されるものである。特許文献１の実施例では、作製した銅粒子を含むインクをアルゴン雰囲気中、６０℃／分で３００℃まで昇温して３０分保持することで導体化を達成している。特許文献２には、特許文献１に記載の方法において、銅前駆体として脂肪酸銅を用いる銅粒子の製造方法が記載されている。特許文献２の実施例には、得られた銅粒子の薄膜が２００℃の加熱で導体化したと記載されている。 Patent Literature 1 discloses copper particles coated with an organic substance that can be fused at a low temperature and exhibit good conductivity, and a method for producing the same. The copper particles described in Patent Document 1 are obtained by mixing a copper precursor such as copper oxalate and a reducing compound such as hydrazine to obtain a composite compound, and heating the composite compound in the presence of an alkylamine. And a method having the following. In the example of Patent Literature 1, conductorization is achieved by raising the temperature of the produced ink containing copper particles to 300 ° C. at a rate of 60 ° C./min in an argon atmosphere for 30 minutes. Patent Document 2 describes a method for producing copper particles using fatty acid copper as a copper precursor in the method described in Patent Document 1. The example of Patent Document 2 describes that the obtained thin film of copper particles was made conductive by heating at 200 ° C.
近年、生産効率の向上、使用する基材の種類の多様化等を背景として、より低温（例えば、１５０℃以下）での金属粒子の融着を可能にする技術の開発が求められている。そこで、特許文献１及び特許文献２に記載されている温度よりも更に低い温度で融着できる金属粒子及びそれを用いた導体化方法の開発が求められている。 In recent years, with the background of improvement in production efficiency, diversification of types of base materials to be used, and the like, development of a technology that enables fusion of metal particles at a lower temperature (for example, 150 ° C. or lower) has been required. Therefore, there is a demand for the development of metal particles that can be fused at a lower temperature than those described in Patent Documents 1 and 2 and a method for converting the particles into a conductor using the metal particles.
本発明は上記課題に鑑み、低温での導体化能に優れる銅含有粒子、前記銅含有粒子を含む導体形成組成物、低温で実施可能な導体の製造方法、低温で製造可能な導体、及び前記導体を含む装置を提供することを目的とする。 In view of the above problems, the present invention provides copper-containing particles having excellent conductorability at a low temperature, a conductor-forming composition containing the copper-containing particles, a method for producing a conductor that can be carried out at a low temperature, a conductor that can be produced at a low temperature, and It is an object to provide a device including a conductor.
上記課題を解決するための手段は、以下のとおりである。
＜１＞銅を含むコア粒子と、前記コア粒子の表面の少なくとも一部に存在する有機物と、を有し、長軸の長さが５０ｎｍ以下である銅含有粒子の割合が８０個％以下である銅含有粒子。
＜２＞長軸の長さが７０ｎｍ以上である銅含有粒子の割合が２０個％以上である＜１＞に記載の銅含有粒子。
＜３＞長軸の長さの平均値が４０ｎｍ以上である＜１＞又は＜２＞のいずれか１項に記載の銅含有粒子。
＜４＞長軸の長さの平均値が３００ｎｍ以下である＜１＞〜＜３＞のいずれか１項に記載の銅含有粒子。
＜５＞長軸の長さが５ｎｍ〜５０ｎｍ以下である第一の銅含有粒子の少なくとも１個と、第一の銅含有粒子より長軸が長く、かつ、長軸の長さが３０ｎｍ〜３００ｎｍである第二の銅含有粒子の少なくとも１個と、から形成される複合粒子を含む＜１＞〜＜４＞のいずれか１項に記載の銅含有粒子。
＜６＞＜１＞〜＜５＞のいずれか１項に記載の銅含有粒子と、分散媒と、を含む導体形成組成物。
＜７＞＜６＞に記載の導体形成組成物を加熱する工程を有する導体の製造方法。
＜８＞＜１＞〜＜５＞のいずれか１項に記載の銅含有粒子が融着した構造を有する導体。
＜９＞＜７＞に記載の導体を含む装置。
The means for solving the above problems are as follows.
<1> The ratio of copper-containing particles having copper-containing core particles and an organic substance present on at least a part of the surface of the core particles and having a major axis length of 50 nm or less is 80% by weight or less. Certain copper-containing particles.
<2> The copper-containing particle according to <1>, wherein the proportion of the copper-containing particle having a major axis length of 70 nm or more is 20% or more.
<3> The copper-containing particle according to any one of <1> or <2>, wherein the average value of the length of the long axis is 40 nm or more.
<4> The copper-containing particle according to any one of <1> to <3>, wherein the average value of the length of the long axis is 300 nm or less.
<5> At least one first copper-containing particle having a major axis length of 5 nm to 50 nm or less, and a major axis longer than the first copper-containing particle, and a major axis length of 30 nm to 300 nm. The copper-containing particles according to any one of <1> to <4>, wherein the copper-containing particles include composite particles formed from at least one of the second copper-containing particles.
<6> A conductor-forming composition comprising the copper-containing particles according to any one of <1> to <5> and a dispersion medium.
<7> A method for producing a conductor, comprising a step of heating the conductor-forming composition according to <6>.
<8> A conductor having a structure in which the copper-containing particles according to any one of <1> to <5> are fused.
<9> An apparatus including the conductor according to <7>.
本発明によれば、低温での導体化能に優れる銅含有粒子、前記銅含有粒子を含む導体形成組成物、低温で実施可能な導体の製造方法、低温で製造可能な導体、及び前記導体を含む装置を提供することができる。 According to the present invention, copper-containing particles having excellent conductorability at low temperatures, a conductor-forming composition containing the copper-containing particles, a method for producing a conductor that can be carried out at a low temperature, a conductor that can be produced at a low temperature, and the conductor An apparatus can be provided that includes:
以下、本発明を実施するための形態について詳細に説明する。但し、本発明は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合、原理的に明らかに必須であると考えられる場合等を除き、必須ではない。数値及びその範囲についても同様であり、本発明を制限するものではない。 Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified, and unless it is deemed essential in principle. The same applies to numerical values and ranges thereof, and does not limit the present invention.
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の目的が達成されれば、本用語に含まれる。また本明細書において「〜」を用いて示された数値範囲は、「〜」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。また、本明細書において組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の物質の合計量を意味する。また、本明細書において組成物中の各成分の粒子径は、組成物中に各成分に該当する粒子が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。本明細書において「膜」との語は、平面図として観察したときに、全面に形成されている形状の構成に加え、一部に形成されている形状の構成も包含される。 In the present specification, the term “step” is included in the term as well as an independent step, even if it cannot be clearly distinguished from other steps as long as the purpose of the step is achieved. In this specification, a numerical range indicated by using “to” indicates a range including numerical values described before and after “to” as a minimum value and a maximum value, respectively. In addition, in the present specification, the content of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, the plurality of substances present in the composition Means the total amount of Further, in the present specification, the particle diameter of each component in the composition, when there are a plurality of types of particles corresponding to each component in the composition, unless otherwise specified, the plurality of types of particles present in the composition Mean the value for a mixture of In this specification, the term “film” includes, when observed as a plan view, the configuration of a partly formed shape in addition to the configuration of a part formed over the entire surface.
本明細書において「導体化」とは、金属含有粒子を融着させて導体に変化させることをいう。「導体」とは、導電性を有する物体をいい、より具体的には体積抵抗率が３００μΩ・ｃｍ以下である物体をいう。「個％」は、個数基準の割合（百分率）を意味する。 In the present specification, “conducting” means that the metal-containing particles are fused to be converted into a conductor. The “conductor” refers to an object having conductivity, and more specifically, an object having a volume resistivity of 300 μΩ · cm or less. “Unit%” means a ratio (percentage) based on the number.
＜銅含有粒子＞
本発明の銅含有粒子は、銅を含むコア粒子と、前記コア粒子の表面の少なくとも一部に存在する有機物と、を有し、長軸の長さが５０ｎｍ以下である銅含有粒子の割合が８０個％以下である。本発明において銅含有粒子の長軸とは、銅含有粒子に外接し、互いに平行である二平面の間の距離が最大となるように選ばれる二平面間の距離を意味する。本明細書において長軸の長さが５０ｎｍ以下である銅含有粒子の割合は、無作為に選択される２００個の銅含有粒子中に占める割合である。例えば、長軸の長さが５０ｎｍ以下である銅含有粒子が２００個中に１６０個である場合は、長軸の長さが５０ｎｍ以下である銅含有粒子の割合は８０個％である。
<Copper-containing particles>
The copper-containing particle of the present invention has a core particle containing copper and an organic substance present on at least a part of the surface of the core particle, and the proportion of the copper-containing particle having a major axis length of 50 nm or less is included. It is 80% or less. In the present invention, the major axis of the copper-containing particle means a distance between two planes circumscribing the copper-containing particle and selected so that the distance between the two parallel planes is maximized. In the present specification, the proportion of the copper-containing particles having a major axis length of 50 nm or less is the proportion of 200 randomly selected copper-containing particles. For example, when the number of copper-containing particles having a major axis length of 50 nm or less is 160 out of 200, the percentage of the copper-containing particles having a major axis length of 50 nm or less is 80%.
本発明の銅含有粒子は上記構成であることにより、低温（例えば、１５０℃）での導体化能に優れている。すなわち、本発明の銅含有粒子は、銅を含有するコア粒子の表面の少なくとも一部に存在する有機物が保護材としての役割を果たし、コア粒子の酸化を抑制する。このため、大気中での長期保存後も低温での良好な融着性が維持される。なお、この有機物は銅含有粒子を融着させて導体を製造する際の加熱により熱分解して消失する。 The copper-containing particles of the present invention, having the above-described structure, are excellent in a conductive ability at a low temperature (for example, 150 ° C.). That is, in the copper-containing particles of the present invention, an organic substance present on at least a part of the surface of the copper-containing core particles serves as a protective material, and suppresses oxidation of the core particles. Therefore, even after long-term storage in the atmosphere, good fusion property at low temperatures is maintained. The organic matter is thermally decomposed and disappears by heating when the copper-containing particles are fused to produce a conductor.
更に、本発明の銅含有粒子は、長軸の長さが５０ｎｍ以下である銅含有粒子（以下、小径粒子ともいう）の割合が８０個％以下であることで、低温での導体化能に優れている。 Furthermore, the copper-containing particles of the present invention have a low-conductivity at a low temperature because the proportion of copper-containing particles having a major axis length of 50 nm or less (hereinafter also referred to as small particles) is 80% or less. Are better.
銅含有粒子中の小径粒子の割合が８０個％以下であると低温での導体化能に優れる理由は明らかではないが、本発明者らは次のように考えている。銅含有粒子中における長軸の長さが５０ｎｍを超える粒子（以下、大径粒子ともいう）は主に導電性の機能を担い、長軸の長さが５０ｎｍ以下である小径粒子は溶融により大径粒子同士を結合して導電パスを形成する機能を担う。銅含有粒子中の小径粒子の数が多すぎると、大径粒子の数が不十分となり良好な導体が形成されない傾向にある。本発明では、銅含有粒子中の小径粒子の割合が適切な範囲内にあることで、低温での良好な導体の形成が可能となっている。 It is not clear why the ratio of small-diameter particles in the copper-containing particles is 80% by weight or less, which is why the conductorability at low temperatures is excellent. However, the present inventors consider as follows. Particles having a major axis length of more than 50 nm (hereinafter also referred to as large-diameter particles) in the copper-containing particles mainly have a conductive function, and small-diameter particles having a major axis length of 50 nm or less are large due to melting. It has a function of forming a conductive path by combining the diameter particles. If the number of small-diameter particles in the copper-containing particles is too large, the number of large-diameter particles will be insufficient and a good conductor will not be formed. In the present invention, when the ratio of the small-diameter particles in the copper-containing particles is within an appropriate range, it is possible to form a good conductor at a low temperature.
特許文献１及び特許文献２には、銅粒子の平均粒径が５０ｎｍ以下であり、更には平均粒径が２０ｎｍであると記載されている。また、特許文献２には、実施例で得られた銅粒子中に粒子径が１０ｎｍ以下の銅粒子と、粒子径が１００〜２００ｎｍの銅粒子とが混在していたと記載されている。しかしながら、いずれの特許文献にも銅粒子全体に占める小径粒子の割合に関する具体的な記載はなく、小径粒子の割合と導体化能との関係を示唆する記載もない。 Patent Documents 1 and 2 describe that the average particle size of the copper particles is 50 nm or less, and that the average particle size is 20 nm. Patent Document 2 describes that copper particles having a particle diameter of 10 nm or less and copper particles having a particle diameter of 100 to 200 nm were mixed in the copper particles obtained in the examples. However, none of the patent documents specifically describes the ratio of the small-diameter particles to the entire copper particles, and does not suggest a relationship between the ratio of the small-diameter particles and the conductive property.
低温での導体化能の観点からは、長軸の長さが５０ｎｍ以下である銅含有粒子の割合が７５個％以下であることが好ましく、７０個％以下であることがより好ましく、６５個％以下であることが更に好ましい。 From the viewpoint of the ability to be conductive at low temperatures, the proportion of the copper-containing particles having a major axis length of 50 nm or less is preferably 75% or less, more preferably 70% or less, and 65% or less. % Is more preferable.
低温での導体化能の観点からは、長軸の長さが５０ｎｍ以下である銅含有粒子の割合が５５個％以上であることが好ましく、５８個％以上であることがより好ましく、６０個％以上であることが更に好ましい。 From the viewpoint of low-temperature conductive property, the proportion of the copper-containing particles having a major axis length of 50 nm or less is preferably 55% or more, more preferably 58% or more, and 60% or more. % Is more preferable.
低温での導体化能の観点からは、長軸の長さが７０ｎｍ以上である粒子の割合が２０個％以上であることが好ましく、３０個％以上であることがより好ましく、３５個％以上であることが更に好ましい。本明細書において長軸の長さが７０ｎｍ以上である銅含有粒子の割合は、無作為に選択される２００個の銅含有粒子に占める割合である。 From the viewpoint of low-temperature conductivity, the proportion of particles having a major axis length of 70 nm or more is preferably 20% or more, more preferably 30% or more, and 35% or more. Is more preferable. In the present specification, the ratio of the copper-containing particles having a major axis length of 70 nm or more is a ratio of 200 copper-containing particles selected at random.
低温での導体化能の観点からは、長軸の長さの平均値が４０ｎｍ以上であることが好ましく、５０ｎｍ以上であることがより好ましく、６０ｎｍ以上であることが更に好ましく、８０ｎｍ以上であることが更に好ましい。本明細書において長軸の長さの平均値は、無作為に選択される２００個の銅含有粒子について測定した長軸の長さの算術平均値である。 From the viewpoint of low-temperature conductivity, the average value of the length of the major axis is preferably 40 nm or more, more preferably 50 nm or more, still more preferably 60 nm or more, and more preferably 80 nm or more. Is more preferable. In this specification, the average value of the length of the major axis is the arithmetic average value of the length of the major axis measured for 200 randomly selected copper-containing particles.
低温での導体化能の観点からは、長軸の長さの平均値が３００ｎｍ以下であることが好ましく、２００ｎｍ以下であることがより好ましく、１５０ｎｍ以下であることが更に好ましい。 From the viewpoint of the ability to be conductive at low temperatures, the average value of the length of the major axis is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less.
低温での導体化能の観点からは、長軸の長さが最長である銅含有粒子（以下、最大径粒子ともいう）の長軸の長さが３５０ｎｍ以下であることが好ましく、３００ｎｍ以下であることがより好ましく、２５０ｎｍ以下であることが更に好ましい。本明細書において最大径粒子の長軸の長さは、無作為に選択される２００個の銅含有粒子中で長軸の長さが最長である銅含有粒子の長軸の長さである。 From the viewpoint of the ability to be conductive at low temperatures, the length of the major axis of the copper-containing particles having the longest major axis (hereinafter, also referred to as the maximum diameter particle) is preferably 350 nm or less, and more preferably 300 nm or less. More preferably, it is more preferably 250 nm or less. In this specification, the major axis length of the largest particle is the major axis length of the copper-containing particle having the longest major axis length among 200 randomly selected copper-containing particles.
低温での導体化能の観点からは、無作為に選択される２００個の粒子のうち長軸の長さが最短である銅含有粒子（以下、最小径粒子ともいう）の長軸の長さが５ｎｍ以上であることが好ましく、８ｎｍ以上であることがより好ましく、１０ｎｍ以上であることが更に好ましい。本明細書において最小径粒子の長軸の長さは、無作為に選択される２００個の銅含有粒子中で長軸の長さが最短である銅含有粒子の長軸の長さである。 From the viewpoint of the ability to be conductive at low temperatures, the length of the major axis of the copper-containing particles having the smallest major axis length (hereinafter, also referred to as “minimum diameter particles”) out of 200 randomly selected particles Is preferably at least 5 nm, more preferably at least 8 nm, even more preferably at least 10 nm. As used herein, the major axis length of the smallest particle is the major axis length of the copper-containing particle having the shortest major axis length among 200 randomly selected copper-containing particles.
銅含有粒子の長軸の長さは、例えば、後述する銅含有粒子の製造方法における原材料の種類、原材料の混合の際の温度、反応時間、反応温度、洗浄工程、洗浄溶媒等の条件を調節することによって行うことができる。銅含有粒子中の小径粒子の割合は、上述の条件を調節することによって調節してもよく、２種以上の粒子径が異なる銅含有粒子を別々に作製し、これらを所望の比率で混合することによって調節してもよい。 The length of the major axis of the copper-containing particles is adjusted, for example, by adjusting the types of raw materials in the method for producing copper-containing particles described below, the temperature at the time of mixing the raw materials, the reaction time, the reaction temperature, the washing step, the washing solvent, and the like. Can be done by doing The ratio of the small-sized particles in the copper-containing particles may be adjusted by adjusting the above-described conditions, two or more types of copper-containing particles having different particle diameters are separately prepared, and these are mixed at a desired ratio. It may be adjusted by the following.
低温での良好な導体化を促進する観点からは、本発明の銅含有粒子は長軸の長さが５ｎｍ〜５０ｎｍ以下である第一の銅含有粒子の少なくとも１個と、第一の銅含有粒子より長軸が長く、かつ、長軸の長さが３０ｎｍ〜３００ｎｍである第二の銅含有粒子の少なくとも１個と、から形成される複合粒子を含むことが好ましい。 From the viewpoint of promoting good conductivity at a low temperature, the copper-containing particles of the present invention include at least one of the first copper-containing particles having a major axis length of 5 nm to 50 nm or less, and the first copper-containing particles. It is preferable to include a composite particle formed from at least one of the second copper-containing particles having a major axis longer than the particle and having a major axis length of 30 nm to 300 nm.
本発明の銅含有粒子が複合粒子を含むことで低温での良好な導体化が促進される理由は明らかではないが、第一の銅含有粒子が第二の銅含有粒子に付着することで、第二の銅含有粒子の形状が第二の銅含有粒子単独の形状よりも複雑になり、いわゆるナノサイズ効果による融点低下が生じ、低温での融着性が促進されることが一つの要因として考えられる。 It is not clear why the copper-containing particles of the present invention promotes good conductivity at low temperatures by including the composite particles, but the first copper-containing particles adhere to the second copper-containing particles, One of the factors is that the shape of the second copper-containing particles becomes more complicated than the shape of the second copper-containing particles alone, the melting point is reduced by a so-called nano-size effect, and the fusibility at low temperatures is promoted. Conceivable.
複合粒子の形状は特に制限されない。例えば、円形度が０．７０〜０．９９であることが好ましい。円形度は、４π×Ｓ／（周囲長さ）２で表される値であり、Ｓは測定対象粒子の面積であり、周囲長さは測定対象粒子の周囲長さである。円形度は、画像処理ソフトを用いて電子顕微鏡像を解析することにより求めることができる。 The shape of the composite particles is not particularly limited. For example, the degree of circularity is preferably 0.70 to 0.99. The circularity is a value represented by 4π × S / (perimeter) 2 , where S is the area of the measurement target particle, and the perimeter is the circumference of the measurement target particle. The circularity can be determined by analyzing an electron microscope image using image processing software.
銅含有粒子の形状は特に制限されず、用途に応じて選択できる。例えば、銅含有粒子の長軸と短軸の比（長軸／短軸）であるアスペクト比は１．０〜１０．０の範囲から選択できる。銅含有粒子を分散媒等と混合したものを印刷法によって基材に付与する場合は、銅含有粒子の長軸と短軸の比（長軸／短軸）であるアスペクト比の平均値が１．５〜８．０であると混合物の粘度の調整が容易であるために好ましい。銅含有粒子の短軸とは、銅含有粒子に外接し、互いに平行である二平面の間の距離が最小となるように選ばれる二平面間の距離を意味する。銅含有粒子のアスペクト比は、電子顕微鏡による観察等の通常の方法によって調べることができる。 The shape of the copper-containing particles is not particularly limited and can be selected according to the application. For example, the aspect ratio, which is the ratio of the major axis to the minor axis (major axis / minor axis) of the copper-containing particles, can be selected from the range of 1.0 to 10.0. When a mixture of copper-containing particles and a dispersion medium or the like is applied to a substrate by a printing method, the average value of the aspect ratio, which is the ratio of the major axis to the minor axis (major axis / minor axis) of the copper-containing particles, is 1 It is preferable that the viscosity be 0.5 to 8.0 because the viscosity of the mixture can be easily adjusted. The minor axis of the copper-containing particles means the distance between the two planes circumscribing the copper-containing particles and selected so that the distance between the two parallel planes is minimized. The aspect ratio of the copper-containing particles can be determined by an ordinary method such as observation with an electron microscope.
本発明のある実施態様では、無作為に選択される２００個の粒子のアスペクト比の平均値が１．０〜８．０であることが好ましく、１．１〜６．０であることがより好ましく、１．２〜３．０であることが更に好ましい。本明細書においてアスペクト比の平均値は、無作為に選択される２００個の銅含有粒子の長軸の算術平均値と短軸の算術平均値をそれぞれ求め、得られた長軸の算術平均値を短軸の算術平均値で除して得られる値である。 In one embodiment of the present invention, the average value of the aspect ratio of 200 randomly selected particles is preferably 1.0 to 8.0, more preferably 1.1 to 6.0. It is more preferably 1.2 to 3.0. In this specification, the average value of the aspect ratio is obtained by calculating the arithmetic average of the long axis and the arithmetic average of the short axis of 200 copper-containing particles selected at random, respectively, and obtaining the arithmetic average of the long axis. Is divided by the arithmetic mean of the short axis.
銅含有粒子のアスペクト比は、例えば、後述する銅含有粒子の製造方法において使用される脂肪酸の炭素数等の条件を調節することによって行うことができる。 The aspect ratio of the copper-containing particles can be determined, for example, by adjusting conditions such as the carbon number of the fatty acid used in the method for producing copper-containing particles described below.
銅含有粒子の長軸の長さ、複合粒子の有無、円形度及びアスペクト比は、電子顕微鏡による観察等の公知の方法により測定することができる。電子顕微鏡で観察する場合の倍率は特に制限されないが、例えば２０倍〜５００００倍で行うことができる。なお、粒子径が３ｎｍ未満の銅含有粒子は測定の対象から除外する。 The length of the major axis of the copper-containing particles, the presence or absence of the composite particles, the circularity, and the aspect ratio can be measured by a known method such as observation with an electron microscope. The magnification when observing with an electron microscope is not particularly limited, but it can be, for example, 20 to 50,000 times. Note that copper-containing particles having a particle diameter of less than 3 nm are excluded from the measurement.
本発明のある実施態様では、銅を含有するコア粒子の表面の少なくとも一部に存在する有機物は、アルキルアミンに由来する物質を含む。有機物及びアルキルアミンの存在は、窒素雰囲気中で有機物が熱分解する温度以上の温度で銅含有粒子を加熱し、加熱前後の重量を比較することで確認される。アルキルアミンとしては、後述する銅含有粒子の製造方法に用いられるアルキルアミンが挙げられる。 In one embodiment of the present invention, the organic substance present on at least a part of the surface of the copper-containing core particle includes a substance derived from an alkylamine. The presence of the organic substance and the alkylamine is confirmed by heating the copper-containing particles at a temperature equal to or higher than the temperature at which the organic substance thermally decomposes in a nitrogen atmosphere and comparing the weight before and after the heating. Examples of the alkylamine include an alkylamine used in a method for producing copper-containing particles described below.
コア粒子の表面の少なくとも一部に存在する有機物は、その割合がコア粒子及び有機物の合計に対して０．１質量％〜２０質量％であることが好ましい。有機物の割合が０．１質量％以上であると、充分な耐酸化性が得られる傾向にある。有機物の割合が２０質量％以下であると、低温での融着性が良好となる傾向にある。コア粒子及び有機物の合計に対する有機物の割合は０．３質量％〜１０質量％であることがより好ましく、０．５質量％〜５質量％であることが更に好ましい。 The proportion of the organic substance present on at least a part of the surface of the core particle is preferably 0.1% by mass to 20% by mass based on the total of the core particle and the organic substance. When the proportion of the organic substance is 0.1% by mass or more, sufficient oxidation resistance tends to be obtained. When the proportion of the organic substance is 20% by mass or less, the fusibility at low temperatures tends to be improved. The ratio of the organic substance to the total of the core particles and the organic substance is more preferably 0.3% by mass to 10% by mass, and still more preferably 0.5% by mass to 5% by mass.
コア粒子は、少なくとも金属銅を含み、必要に応じてその他の物質を含んでもよい。銅以外の物質としては、金、銀、白金、錫、ニッケル等の金属又はこれらの金属元素を含む化合物、後述する脂肪酸銅、還元性化合物又はアルキルアミンに由来する有機物、酸化銅、塩化銅等を挙げることができる。導電性に優れる導体を形成する観点からは、コア粒子中の金属銅の含有率は５０質量％以上であることが好ましく、６０質量％以上であることがより好ましく、７０質量％以上であることが更に好ましい。 The core particles contain at least metallic copper, and may contain other substances as necessary. Substances other than copper include metals such as gold, silver, platinum, tin and nickel or compounds containing these metal elements, fatty acids described later, organic compounds derived from reducing compounds or alkylamines, copper oxide, copper chloride, etc. Can be mentioned. From the viewpoint of forming a conductor having excellent conductivity, the content of metallic copper in the core particles is preferably 50% by mass or more, more preferably 60% by mass or more, and preferably 70% by mass or more. Is more preferred.
銅含有粒子は、コア粒子の表面の少なくとも一部に有機物が存在しているために、大気中で保存しても銅の酸化が抑制されており、酸化物の含有率が小さい。例えば、ある実施態様では、銅含有粒子中の酸化物の含有率が５質量％以下である。銅含有粒子中の酸化物の含有率は、例えばＸＲＤ（Ｘ−ｒａｙ ｄｉｆｆｒａｃｔｉｏｎ、Ｘ線回折）によって測定することができる。 The copper-containing particles have an organic substance present on at least a part of the surface of the core particles, so that oxidation of copper is suppressed even when stored in the air, and the content of oxides is small. For example, in one embodiment, the content of the oxide in the copper-containing particles is 5% by mass or less. The content of the oxide in the copper-containing particles can be measured, for example, by XRD (X-ray diffraction, X-ray diffraction).
＜銅含有粒子の製造方法＞
銅含有粒子の製造方法は特に制限されない。例えば、銅含有粒子は脂肪酸と銅との金属塩と、還元性化合物と、アルキルアミンと、を含む組成物を加熱する工程を有する方法によって製造される。前記方法は、必要に応じて加熱工程後の遠心分離工程、洗浄工程等の工程を有していてもよい。
<Method for producing copper-containing particles>
The method for producing the copper-containing particles is not particularly limited. For example, copper-containing particles are produced by a method having a step of heating a composition containing a metal salt of a fatty acid and copper, a reducing compound, and an alkylamine. The method may include steps such as a centrifugal separation step and a washing step after the heating step, if necessary.
前記方法は、銅前駆体として、脂肪酸と銅との金属塩を使用するものである。これにより、銅前駆体としてシュウ酸銀等を用いる特許文献１に記載の方法と比較して、より沸点の低い（すなわち、分子量の小さい）アルキルアミンを反応媒として使用することが可能になると考えられる。その結果、得られる銅含有粒子においてコア粒子の表面に存在する有機物がより熱分解又は揮発しやすいものとなり、導体化を低温で実施することがより容易になると考えられる。 The above method uses a metal salt of a fatty acid and copper as a copper precursor. It is thought that this makes it possible to use an alkylamine having a lower boiling point (that is, a smaller molecular weight) as a reaction medium as compared with the method described in Patent Document 1 using silver oxalate or the like as a copper precursor. Can be As a result, it is considered that in the obtained copper-containing particles, the organic substances existing on the surface of the core particles are more easily thermally decomposed or volatilized, and it is considered that conducting the conductor at a low temperature becomes easier.
（脂肪酸）
脂肪酸は、ＲＣＯＯＨで表される１価のカルボン酸（Ｒは鎖状の炭化水素基であり、直鎖状であっても分岐を有していてもよい）である。脂肪酸は、飽和脂肪酸又は不飽和脂肪酸のいずれであってもよい。コア粒子を効率的に被覆して酸化を抑制する観点からは、直鎖状の飽和脂肪酸が好ましい。脂肪酸は１種のみでも、２種以上であってもよい。
(fatty acid)
The fatty acid is a monovalent carboxylic acid represented by RCOOH (R is a chain hydrocarbon group, which may be linear or branched). Fatty acids may be either saturated or unsaturated fatty acids. From the viewpoint of efficiently covering the core particles and suppressing oxidation, linear saturated fatty acids are preferred. The fatty acid may be only one kind or two or more kinds.
脂肪酸の炭素数は、９以下であることが好ましい。炭素数が９以下である飽和脂肪酸としては、酢酸（炭素数２）、プロピオン酸（炭素数３）、酪酸及びイソ酪酸（炭素数４）、吉草酸及びイソ吉草酸（炭素数５）、カプロン酸（炭素数６）、エナント酸及びイソエナント酸（炭素数７）、カプリル酸及びイソカプリル酸及びイソカプロン酸（炭素数８）、ノナン酸及びイソノナン酸（炭素数９）等を挙げることができる。炭素数が９以下である不飽和脂肪酸としては、上記の飽和脂肪酸の炭化水素基中に１つ以上の二重結合を有するものを挙げることができる。 The fatty acid preferably has 9 or less carbon atoms. Saturated fatty acids having 9 or less carbon atoms include acetic acid (2 carbon atoms), propionic acid (3 carbon atoms), butyric acid and isobutyric acid (4 carbon atoms), valeric acid and isovaleric acid (5 carbon atoms), and capron Acid (C6), enanthic acid and isoenanthic acid (C7), caprylic acid, isocaprylic acid and isocaproic acid (C8), nonanoic acid and isononanoic acid (C9) and the like can be mentioned. Examples of the unsaturated fatty acids having 9 or less carbon atoms include those having one or more double bonds in the hydrocarbon group of the above-mentioned saturated fatty acids.
脂肪酸の種類は、銅含有粒子の分散媒への分散性、融着性等の性質に影響しうる。このため、銅含有粒子の用途に応じて脂肪酸の種類を選択することが好ましい。粒子形状の均一化の観点からは、炭素数が５〜９である脂肪酸と、炭素数が４以下である脂肪酸とを併用することが好ましい。例えば、炭素数が９であるノナン酸と、炭素数が２である酢酸とを併用することが好ましい。炭素数が５〜９である脂肪酸と炭素数が４以下である脂肪酸とを併用する場合の比率は、特に制限されない。 The type of the fatty acid can affect properties such as the dispersibility of the copper-containing particles in the dispersion medium and the fusibility. For this reason, it is preferable to select the type of fatty acid according to the use of the copper-containing particles. From the viewpoint of uniformizing the particle shape, it is preferable to use a fatty acid having 5 to 9 carbon atoms and a fatty acid having 4 or less carbon atoms in combination. For example, it is preferable to use nonanoic acid having 9 carbon atoms and acetic acid having 2 carbon atoms in combination. The ratio in the case of using a fatty acid having 5 to 9 carbon atoms and a fatty acid having 4 or less carbon atoms in combination is not particularly limited.
脂肪酸と銅との塩化合物（脂肪酸銅）を得る方法は特に制限されない。例えば、水酸化銅と脂肪酸とを溶媒中で混合することで得てもよく、市販されている脂肪酸銅を用いてもよい。あるいは、水酸化銅、脂肪酸及び還元性化合物を溶媒中で混合することで、脂肪酸銅の生成と、脂肪酸銅と還元性化合物との間で形成される錯体の生成とを同じ工程中で行ってもよい。 The method for obtaining the salt compound of fatty acid and copper (fatty acid copper) is not particularly limited. For example, it may be obtained by mixing copper hydroxide and a fatty acid in a solvent, or commercially available fatty acid copper may be used. Alternatively, by mixing copper hydroxide, a fatty acid and a reducing compound in a solvent, the production of a fatty acid copper and the production of a complex formed between the fatty acid copper and the reducing compound are performed in the same step. Is also good.
（還元性化合物）
還元性化合物は、脂肪酸銅と混合した際に両化合物間で錯体等の複合化合物を形成すると考えられる。これにより、還元性化合物が脂肪酸銅中の銅イオンに対する電子のドナーとなり、銅イオンの還元が生じやすくなり、錯体を形成していない状態の脂肪酸銅よりも自発的な熱分解による銅原子の遊離が生じやすくなると考えられる。還元性化合物は１種を単独で用いても、２種以上を併用してもよい。
(Reducing compound)
The reducing compound is considered to form a complex compound such as a complex between both compounds when mixed with the fatty acid copper. As a result, the reducing compound becomes an electron donor for the copper ions in the fatty acid copper, and the copper ions are easily reduced, and the copper atoms are liberated by spontaneous thermal decomposition more than the uncomplexed fatty acid copper. Is likely to occur. One reducing compound may be used alone, or two or more reducing compounds may be used in combination.
還元性化合物として具体的には、ヒドラジン、ヒドラジン誘導体、塩酸ヒドラジン、硫酸ヒドラジン、抱水ヒドラジン等のヒドラジン化合物、ヒドロキシルアミン、ヒドロキシルアミン誘導体等のヒドロキシルアミン化合物、水素化ホウ素ナトリウム、亜硫酸ナトリウム、亜硫酸水素ナトリウム、チオ硫酸ナトリウム、次亜リン酸ナトリウム等のナトリウム化合物などを挙げることができる。 Specific examples of the reducing compound include hydrazine, hydrazine derivatives, hydrazine hydrochloride, hydrazine sulfate, hydrazine hydrate, and other hydrazine compounds, hydroxylamine, hydroxylamine compounds such as hydroxylamine derivatives, sodium borohydride, sodium sulfite, and hydrogen sulfite. Examples thereof include sodium compounds such as sodium, sodium thiosulfate, and sodium hypophosphite.
脂肪酸銅中の銅原子に対して配位結合を形成しやすい、脂肪酸銅の構造を維持した状態で錯体を形成しやすい等の観点からは、アミノ基を有する還元性化合物が好ましい。アミノ基を有する還元性化合物としては、ヒドラジン及びその誘導体、ヒドロキシルアミン及びその誘導体等を挙げることができる。 A reducing compound having an amino group is preferable from the viewpoint that a coordination bond is easily formed with a copper atom in the fatty acid copper and that a complex is easily formed while maintaining the structure of the fatty acid copper. Examples of the reducing compound having an amino group include hydrazine and its derivatives, hydroxylamine and its derivatives, and the like.
脂肪酸銅、還元性化合物及びアルキルアミンを含む組成物を加熱する工程（以下では加熱工程ともいう）における加熱温度を低くする（例えば、１５０℃以下）観点からは、アルキルアミンの蒸発又は分解を生じない温度範囲において銅原子の還元及び遊離を生じる錯体を形成可能な還元性化合物を選択することが好ましい。このような還元性化合物としては、ヒドラジン及びその誘導体、ヒドロキシルアミン及びその誘導体等を挙げることができる。これらの還元性化合物は、骨格を成す窒素原子が銅原子との配位結合を形成して錯体を形成することができる。また、これらの還元性化合物は一般にアルキルアミンと比較して還元力が強いため、生成した錯体が比較的穏和な条件で自発的な分解を生じ、銅原子の還元及び遊離が生じる傾向にある。 From the viewpoint of lowering the heating temperature (for example, 150 ° C. or lower) in the step of heating the composition containing the fatty acid copper, the reducing compound, and the alkylamine (hereinafter also referred to as a heating step), evaporation or decomposition of the alkylamine occurs. It is preferable to select a reducing compound capable of forming a complex that causes the reduction and release of a copper atom in a temperature range that does not exist. Examples of such a reducing compound include hydrazine and its derivatives, hydroxylamine and its derivatives, and the like. In these reducing compounds, a nitrogen atom constituting a skeleton forms a coordination bond with a copper atom to form a complex. In addition, since these reducing compounds generally have a stronger reducing power than alkylamines, the resulting complexes tend to undergo spontaneous decomposition under relatively mild conditions, resulting in the reduction and release of copper atoms.
ヒドラジン又はヒドロキシルアミンの代わりにこれらの誘導体から好適なものを選択することで、脂肪酸銅との反応性を調節することができ、所望の条件で自発分解を生じる錯体を生成することができる。ヒドラジン誘導体としては、メチルヒドラジン、エチルヒドラジン、ｎ−プロピルヒドラジン、イソプロピルヒドラジン、ｎ−ブチルヒドラジン、イソブチルヒドラジン、ｓｅｃ−ブチルヒドラジン、ｔ−ブチルヒドラジン、ｎ−ペンチルヒドラジン、イソペンチルヒドラジン、ｎｅｏ−ペンチルヒドラジン、ｔ−ペンチルヒドラジン、ｎ−ヘキシルヒドラジン、イソヘキシルヒドラジン、ｎ−ヘプチルヒドラジン、ｎ−オクチルヒドラジン、ｎ−ノニルヒドラジン、ｎ−デシルヒドラジン、ｎ−ウンデシルヒドラジン、ｎ−ドデシルヒドラジン、シクロヘキシルヒドラジン、フェニルヒドラジン、４−メチルフェニルヒドラジン、ベンジルヒドラジン、２−フェニルエチルヒドラジン、２−ヒドラジノエタノール、アセトヒドラジン等を挙げることができる。ヒドロキシルアミンの誘導体としては、Ｎ，Ｎ−ジ（スルホエチル）ヒドロキシルアミン、モノメチルヒドロキシルアミン、ジメチルヒドロキシルアミン、モノエチルヒドロキシルアミン、ジエチルヒドロキシルアミン、Ｎ，Ｎ−ジ（カルボキシエチル）ヒドロキシルアミン等を挙げることができる。 By selecting a suitable derivative from these derivatives instead of hydrazine or hydroxylamine, the reactivity with the fatty acid copper can be adjusted, and a complex that undergoes spontaneous decomposition under desired conditions can be produced. As the hydrazine derivative, methylhydrazine, ethylhydrazine, n-propylhydrazine, isopropylhydrazine, n-butylhydrazine, isobutylhydrazine, sec-butylhydrazine, t-butylhydrazine, n-pentylhydrazine, isopentylhydrazine, neo-pentylhydrazine , T-pentylhydrazine, n-hexylhydrazine, isohexylhydrazine, n-heptylhydrazine, n-octylhydrazine, n-nonylhydrazine, n-decylhydrazine, n-undecylhydrazine, n-dodecylhydrazine, cyclohexylhydrazine, phenyl Hydrazine, 4-methylphenylhydrazine, benzylhydrazine, 2-phenylethylhydrazine, 2-hydrazinoethanol, acetohydrazine and the like. Rukoto can. Examples of hydroxylamine derivatives include N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, and N, N-di (carboxyethyl) hydroxylamine. Can be.
脂肪酸銅に含まれる銅と還元性化合物の比率は、所望の錯体が形成される条件であれば特に制限されない。例えば、前記比率（銅：還元性化合物）はモル基準で１：１〜１：４の範囲とすることができ、１：１〜１：３の範囲とすることが好ましく、１：１〜１：２の範囲とすることがより好ましい。 The ratio of copper and the reducing compound contained in the fatty acid copper is not particularly limited as long as a desired complex is formed. For example, the ratio (copper: reducing compound) can be in a range of 1: 1 to 1: 4 on a molar basis, preferably in a range of 1: 1 to 1: 3, and 1: 1 to 1 : 2 is more preferable.
（アルキルアミン）
アルキルアミンは、脂肪酸銅と還元性化合物とから形成される錯体の分解反応の反応媒として機能すると考えられる。更に、還元性化合物の還元作用によって生じるプロトンを捕捉し、反応溶液が酸性に傾いて銅原子が酸化されることを抑制すると考えられる。
(Alkylamine)
The alkylamine is considered to function as a reaction medium for a decomposition reaction of a complex formed from the fatty acid copper and the reducing compound. Furthermore, it is considered that the proton generated by the reducing action of the reducing compound is trapped, and the oxidation of the copper atom due to the acidity of the reaction solution is suppressed.
アルキルアミンはＲＮＨ２（Ｒは炭化水素基であり、環状又は分岐状であってもよい）で表される１級アミン、Ｒ１Ｒ２ＮＨ（Ｒ１及びＲ２は同じであっても異なっていてもよい炭化水素基であり、環状又は分岐状であってもよい）で表される２級アミン、炭化水素鎖に２つのアミノ基が置換したアルキレンジアミン等を意味する。アルキルアミンは、１つ以上の二重結合を有していてもよく、酸素、ケイ素、窒素、イオウ、リン等の原子を有していてもよい。アルキルアミンは、１種のみであっても２種以上であってもよい。 The alkylamine is a primary amine represented by RNH 2 (R is a hydrocarbon group and may be cyclic or branched), and R 1 R 2 NH (R 1 and R 2 are the same or different. Hydrocarbon group, which may be cyclic or branched), alkylene diamine in which two amino groups are substituted on a hydrocarbon chain, and the like. The alkylamine may have one or more double bonds, and may have atoms such as oxygen, silicon, nitrogen, sulfur, phosphorus and the like. The alkylamine may be one kind alone or two or more kinds.
アルキルアミンの炭化水素基の炭素数は、７以下であることが好ましい。アルキルアミンの炭化水素基の炭素数が７以下であると、銅含有粒子を融着させて導体を形成するための加熱の際にアルキルアミンが熱分解しやすく、良好な導体化が達成できる傾向にある。アルキルアミンの炭化水素基の炭素数は６以下であることがより好ましく、３以上であることが更に好ましい。 The hydrocarbon group of the alkylamine preferably has 7 or less carbon atoms. When the carbon number of the hydrocarbon group of the alkylamine is 7 or less, the alkylamine is liable to be thermally decomposed at the time of heating to form a conductor by fusing the copper-containing particles, and a good conductor can be achieved. It is in. The hydrocarbon group of the alkylamine preferably has 6 or less carbon atoms, and more preferably 3 or more carbon atoms.
１級アミンとして具体的には、エチルアミン、２−エトキシエチルアミン、プロピルアミン、ブチルアミン、イソブチルアミン、ペンチルアミン、イソペンチルアミン、ヘキシルアミン、シクロヘキシルアミン、ヘプチルアミン、オクチルアミン、ノニルアミン、デシルアミン、ドデシルアミン、ヘキサデシルアミン、オレイルアミン、３−メトキシプロピルアミン、３−エトキシプロピルアミン等を挙げることができる。 Specific examples of the primary amine include ethylamine, 2-ethoxyethylamine, propylamine, butylamine, isobutylamine, pentylamine, isopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, Hexadecylamine, oleylamine, 3-methoxypropylamine, 3-ethoxypropylamine and the like can be mentioned.
２級アミンとして具体的には、ジエチルアミン、ジプロピルアミン、ジブチルアミン、エチルプロピルアミン、エチルペンチルアミン、ジブチルアミン、ジペンチルアミン、ジヘキシルアミン等を挙げることができる。 Specific examples of the secondary amine include diethylamine, dipropylamine, dibutylamine, ethylpropylamine, ethylpentylamine, dibutylamine, dipentylamine, and dihexylamine.
アルキレンジアミンとして具体的には、エチレンジアミン、Ｎ，Ｎ−ジメチルエチレンジアミン、Ｎ，Ｎ’−ジメチルエチレンジアミン、Ｎ，Ｎ−ジエチルエチレンジアミン、Ｎ，Ｎ’−ジエチルエチレンジアミン、１，３−プロパンジアミン、２，２−ジメチル−１，３−プロパンジアミン、Ｎ，Ｎ−ジメチル−１，３−ジアミノプロパン、Ｎ，Ｎ’−ジメチル−１，３−ジアミノプロパン、Ｎ，Ｎ−ジエチル−１，３−ジアミノプロパン、１，４−ジアミノブタン、１，５−ジアミノ−２−メチルペンタン、１，６−ジアミノへキサン、Ｎ，Ｎ’−ジメチル−１，６−ジアミノへキサン、１，７−ジアミノヘプタン、１，８−ジアミノオクタン、１，９−ジアミノノナン、１，１２−ジアミノドデカン等を挙げることができる。 Specific examples of the alkylenediamine include ethylenediamine, N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, N, N-diethylethylenediamine, N, N′-diethylethylenediamine, 1,3-propanediamine, and 2,2. -Dimethyl-1,3-propanediamine, N, N-dimethyl-1,3-diaminopropane, N, N′-dimethyl-1,3-diaminopropane, N, N-diethyl-1,3-diaminopropane, 1,4-diaminobutane, 1,5-diamino-2-methylpentane, 1,6-diaminohexane, N, N′-dimethyl-1,6-diaminohexane, 1,7-diaminoheptane, 1, Examples thereof include 8-diaminooctane, 1,9-diaminononane, and 1,12-diaminododecane.
アルキルアミンは、炭化水素基の炭素数が７以下であるアルキルアミンの少なくとも１種を含むことが好ましい。これにより、低温での融着性により優れる銅含有粒子を製造することができる。アルキルアミンは１種単独で用いても、２種以上を併用してよい。アルキルアミンは、炭化水素基の炭素数が７以下であるアルキルアミンと、炭化水素基の炭素数が８以上のアルキルアミンと、を含んでもよい。炭化水素基の炭素数が７以下であるアルキルアミンと炭化水素基の炭素数が８以上のアルキルアミンとを併用する場合、アルキルアミン全体に占める炭化水素基の炭素数が７以下であるアルキルアミンの割合は５０質量％以上であることが好ましく、６０質量％以上であることがより好ましく、７０質量％以上であることが更に好ましい。 The alkylamine preferably contains at least one alkylamine having a hydrocarbon group having 7 or less carbon atoms. This makes it possible to produce copper-containing particles that are more excellent in low-temperature fusibility. The alkylamines may be used alone or in combination of two or more. The alkylamine may include an alkylamine having a hydrocarbon group of 7 or less carbon atoms and an alkylamine having a hydrocarbon group of 8 or more carbon atoms. When an alkylamine having 7 or less carbon atoms in the hydrocarbon group and an alkylamine having 8 or more carbon atoms in the hydrocarbon group are used in combination, the alkylamine having 7 or less carbon atoms in the hydrocarbon group in the whole alkylamine is used. Is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more.
脂肪酸銅に含まれる銅とアルキルアミンの比率は、所望の銅含有粒子が得られる条件であれば特に制限されない。例えば、前記比率（銅：アルキルアミン）はモル基準で１：１〜１：８の範囲とすることができ、１：１〜１：６の範囲とすることが好ましく、１：１〜１：４の範囲とすることがより好ましい。 The ratio of copper to alkylamine contained in the fatty acid copper is not particularly limited as long as desired copper-containing particles are obtained. For example, the ratio (copper: alkylamine) can be in a range of 1: 1 to 1: 8 on a molar basis, preferably in a range of 1: 1 to 1: 6, and 1: 1 to 1: 1. More preferably, it is in the range of 4.
（加熱工程）
脂肪酸銅、還元性化合物及びアルキルアミンを含む組成物を加熱する工程を実施するための方法は特に制限されない。例えば、脂肪酸銅と還元性化合物とを溶媒に混合した後にアルキルアミンを添加して加熱する方法、脂肪酸銅とアルキルアミンとを溶媒と混合した後に更に還元性化合物を添加して加熱する方法、脂肪酸銅の出発物質である水酸化銅、脂肪酸、還元性化合物及びアルキルアミンを溶媒に混合して加熱する方法、脂肪酸銅とアルキルアミンとを溶媒に混合した後に還元性化合物を添加して加熱する方法等を挙げることができる。
(Heating process)
The method for performing the step of heating the composition containing the fatty acid copper, the reducing compound, and the alkylamine is not particularly limited. For example, a method in which a fatty acid copper and a reducing compound are mixed in a solvent and then an alkylamine is added thereto, followed by heating, a method in which the fatty acid copper and the alkylamine are mixed with a solvent and then a reducing compound is further added and heated, A method in which copper hydroxide as a starting material of copper, a fatty acid, a reducing compound and an alkylamine are mixed in a solvent and heated, and a method in which a fatty acid copper and an alkylamine are mixed in a solvent and then a reducing compound is added and heated. And the like.
加熱工程は、銅前駆体として炭素数が９以下である脂肪酸銅を用いることにより、比較的低温で行うことができる。例えば、１５０℃以下で行うことができ、１３０℃以下で行うことが好ましく、１００℃以下で行うことがより好ましい。 The heating step can be performed at a relatively low temperature by using a fatty acid copper having 9 or less carbon atoms as a copper precursor. For example, the heat treatment can be performed at 150 ° C. or lower, preferably at 130 ° C. or lower, and more preferably at 100 ° C. or lower.
脂肪酸銅、還元性化合物及びアルキルアミンを含む組成物は、更に溶媒を含んでもよい。脂肪酸銅と還元性化合物による錯体の形成を促進する観点からは、極性溶媒を含むことが好ましい。ここで極性溶媒とは、２５℃で水に溶解する溶媒を意味し、アルコールであることが好ましい。アルコールを用いることで錯体の形成が促進される傾向にある。その理由は明らかではないが、固体である脂肪酸銅を溶解させながら水溶性である還元性化合物との接触が促進されるためと考えられる。溶媒は１種を単独で用いても、２種以上を併用してもよい。 The composition comprising the fatty acid copper, the reducing compound and the alkylamine may further contain a solvent. It is preferable to contain a polar solvent from the viewpoint of promoting the formation of a complex between the fatty acid copper and the reducing compound. Here, the polar solvent means a solvent that dissolves in water at 25 ° C., and is preferably an alcohol. The use of alcohol tends to promote complex formation. Although the reason is not clear, it is considered that the contact with the water-soluble reducing compound is promoted while dissolving the solid fatty acid copper. One type of solvent may be used alone, or two or more types may be used in combination.
２５℃で水に溶解するアルコールとしては、炭素数が１〜８であり、分子中に水酸基を１つ有するアルコールを挙げることができる。このようなアルコールとしては、直鎖状のアルキルアルコール、フェノール、分子内にエーテル結合を有する炭化水素の水素原子を水酸基で置換したもの等を挙げることができる。より強い極性を発現する観点からは、分子中に水酸基を２個以上含むアルコールも好ましく用いられる。また、製造される銅含有粒子の用途に応じてイオウ原子、リン原子、ケイ素原子等を含むアルコールを用いてもよい。 Examples of the alcohol soluble in water at 25 ° C. include an alcohol having 1 to 8 carbon atoms and having one hydroxyl group in the molecule. Examples of such alcohols include linear alkyl alcohols, phenols, and alcohols in which the hydrogen atom of a hydrocarbon having an ether bond in the molecule is substituted with a hydroxyl group. From the viewpoint of expressing stronger polarity, alcohols containing two or more hydroxyl groups in the molecule are also preferably used. Further, an alcohol containing a sulfur atom, a phosphorus atom, a silicon atom or the like may be used depending on the use of the copper-containing particles to be produced.
アルコールとして具体的には、メタノール、エタノール、１−プロパノール、２−プロパノール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、アリルアルコール、ベンジルアルコール、ピナコール、プロピレングリコール、メントール、カテコール、ヒドロキノン、サリチルアルコール、グリセリン、ペンタエリスリトール、スクロース、グルコース、キシリトール、メトキシエタノール、トリエチレングリコールモノメチルエーテル、エチレングリコール、トリエチレングリコール、テトラエチレングリコール、ペンタエチレングリコール等を挙げることができる。 Specific examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, butanol, pentanol, hexanol, heptanol, octanol, allyl alcohol, benzyl alcohol, pinacol, propylene glycol, menthol, catechol, hydroquinone, salicyl alcohol, Examples include glycerin, pentaerythritol, sucrose, glucose, xylitol, methoxyethanol, triethylene glycol monomethyl ether, ethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, and the like.
アルコールのうち、水に対する溶解度が極めて大きいメタノール、エタノール、１−プロパノール及び２−プロパノールが好ましく、１−プロパノール及び２−プロパノールがより好ましく、１−プロパノールが更に好ましい。 Among alcohols, methanol, ethanol, 1-propanol and 2-propanol, which have extremely high solubility in water, are preferred, 1-propanol and 2-propanol are more preferred, and 1-propanol is even more preferred.
＜導体形成組成物＞
本発明の導体形成組成物は、本発明の銅含有粒子と、分散媒とを含む。本発明の導体形成組成物は、低温での導体化能に優れる本発明の銅含有粒子を含むため、低温での導体化が可能である。導体形成組成物としては、導電塗料、導電ペースト、導電インク等が挙げられる。
<Conductor-forming composition>
The conductor forming composition of the present invention includes the copper-containing particles of the present invention and a dispersion medium. Since the conductor-forming composition of the present invention contains the copper-containing particles of the present invention, which has excellent low-temperature conductive properties, it can be converted to a low-temperature conductive material. Examples of the conductor forming composition include a conductive paint, a conductive paste, and a conductive ink.
導体形成組成物に含まれる銅含有粒子の形状は特に制限されない。具体的には、球状、長粒状、扁平状、繊維状等を挙げることができ、銅含有粒子の用途にあわせて選択できる。導体形成組成物を印刷法に適用する場合は、銅含有粒子の形状は球状又は長粒状であることが好ましい。 The shape of the copper-containing particles contained in the conductor-forming composition is not particularly limited. Specific examples include spherical, long, flat, and fibrous shapes, which can be selected according to the use of the copper-containing particles. When the conductor forming composition is applied to a printing method, the shape of the copper-containing particles is preferably spherical or long.
分散媒の種類は特に制限されず、導体形成組成物の用途に応じて一般に用いられる有機溶媒から選択でき、１種単独で用いても、２種以上を併用してもよい。導体形成組成物を印刷法に適用する場合は、導体形成組成物の粘度コントロールの観点から、テルピネオール、イソボルニルシクロヘキサノール、ジヒドロターピネオール及びジヒドロターピネオールアセテートからなる群より選択される少なくとも１種を含むことが好ましい。 The type of the dispersion medium is not particularly limited, and can be selected from commonly used organic solvents according to the application of the conductor-forming composition, and may be used alone or in combination of two or more. When the conductor forming composition is applied to a printing method, from the viewpoint of controlling the viscosity of the conductor forming composition, it contains at least one selected from the group consisting of terpineol, isobornylcyclohexanol, dihydroterpineol, and dihydroterpineol acetate. Is preferred.
導体形成組成物の粘度は特に制限されず、導体形成組成物の使用方法に応じて選択できる。例えば、導体形成組成物をスクリーン印刷法に適用する場合は、粘度が０．１Ｐａ・ｓ〜３０Ｐａ・ｓであることが好ましく、１Ｐａ・ｓ〜３０Ｐａ・ｓであることがより好ましい。導体形成組成物をインクジェット印刷法に適用する場合は、使用するインクジェットヘッドの規格にもよるが、粘度が０．１ｍＰａ・ｓ〜３０ｍＰａ・ｓであることが好ましく、５ｍＰａ・ｓ〜２０ｍＰａ・ｓであることがより好ましい。 The viscosity of the conductor-forming composition is not particularly limited, and can be selected according to the method of using the conductor-forming composition. For example, when the conductor forming composition is applied to a screen printing method, the viscosity is preferably 0.1 Pa · s to 30 Pa · s, and more preferably 1 Pa · s to 30 Pa · s. When the conductor-forming composition is applied to the inkjet printing method, the viscosity is preferably 0.1 mPa · s to 30 mPa · s, and preferably 5 mPa · s to 20 mPa · s, depending on the specification of the inkjet head to be used. More preferably, there is.
導体形成組成物は、必要に応じて銅含有粒子及び分散媒以外の成分を含んでもよい。このような成分としては、シランカップリング剤、高分子化合物、ラジカル開始剤、還元剤等が挙げられる。 The conductor-forming composition may contain components other than the copper-containing particles and the dispersion medium as necessary. Examples of such components include a silane coupling agent, a polymer compound, a radical initiator, and a reducing agent.
＜導体の製造方法＞
本発明の導体の製造方法は、本発明の導体形成組成物を加熱する工程（加熱工程）を有する。加熱工程では、導体形成組成物に含まれる銅含有粒子の表面の有機物を熱分解させ、かつ、銅含有粒子を融着させる。本発明の導体形成組成物は低温での導体化が可能であるため、２００℃以下、好ましくは１５０℃以下の温度で加熱工程を行うことができる。
<Manufacturing method of conductor>
The method for producing a conductor of the present invention includes a step of heating the conductor-forming composition of the present invention (heating step). In the heating step, the organic matter on the surface of the copper-containing particles contained in the conductor-forming composition is thermally decomposed and the copper-containing particles are fused. Since the conductor-forming composition of the present invention can be converted to a conductor at a low temperature, the heating step can be performed at a temperature of 200 ° C or lower, preferably 150 ° C or lower.
加熱工程が実施される雰囲気中の成分は特に制限されず、通常の導体の製造工程で用いられる窒素、アルゴン等から選択できる。また、水素、ギ酸等の還元性物質を、窒素等に飽和させた雰囲気中で加熱してもよい。加熱時の圧力は特に制限されないが、減圧とすることでより低温での導体化が促進される傾向にある。 The components in the atmosphere in which the heating step is performed are not particularly limited, and can be selected from nitrogen, argon, and the like used in a normal conductor manufacturing process. Further, a reducing substance such as hydrogen or formic acid may be heated in an atmosphere saturated with nitrogen or the like. The pressure at the time of heating is not particularly limited, but by reducing the pressure, there is a tendency that the formation of a conductor at a lower temperature is promoted.
加熱工程は一定の昇温速度で行っても、不規則に変化させてもよい。加熱工程の時間は特に制限されず、加熱温度、加熱雰囲気、銅含有粒子の量等を考慮して選択できる。加熱方法は特に制限されず、熱板による加熱、赤外ヒータによる加熱、パルスレーザによる加熱等を挙げることができる。 The heating step may be performed at a constant heating rate or may be changed irregularly. The time of the heating step is not particularly limited, and can be selected in consideration of the heating temperature, the heating atmosphere, the amount of the copper-containing particles, and the like. The heating method is not particularly limited, and examples thereof include heating with a hot plate, heating with an infrared heater, and heating with a pulse laser.
導体の製造方法は、必要に応じてその他の工程を有していてもよい。その他の工程としては、加熱工程前に導体形成組成物を基材に付与する工程、加熱工程前に導体形成組成物中の揮発成分の少なくとも一部を乾燥等により除去する工程、加熱工程後に還元雰囲気中で加熱により生成した酸化銅を還元する工程、加熱工程後に光焼成を行って残存成分を除去する工程、加熱工程後に得られた導体に対して荷重をかける工程等を挙げることができる。 The conductor manufacturing method may have other steps as necessary. Other steps include a step of applying the conductor-forming composition to the substrate before the heating step, a step of removing at least a part of volatile components in the conductor-forming composition by drying or the like before the heating step, and a step of reducing after the heating step. Examples include a step of reducing copper oxide generated by heating in an atmosphere, a step of performing light firing after the heating step to remove residual components, and a step of applying a load to the conductor obtained after the heating step.
＜導体＞
本発明の導体は、本発明の銅含有粒子が融着した構造を有する。導体の形状は特に制限されず、薄膜状、パターン状等を挙げることができる。本発明の導体は、種々の電子部品の配線、被膜等の形成に使用できる。特に、本発明の導体は低温で製造できるため、樹脂等の耐熱性の低い基材上に金属箔、配線パターン等を形成する用途に好適に用いられる。また、通電を目的としない装飾、印字等の用途にも好適に用いられる。
<Conductor>
The conductor of the present invention has a structure in which the copper-containing particles of the present invention are fused. The shape of the conductor is not particularly limited, and examples thereof include a thin film shape and a pattern shape. The conductor of the present invention can be used for forming wirings, coatings and the like of various electronic components. In particular, since the conductor of the present invention can be manufactured at a low temperature, it is suitably used for forming a metal foil, a wiring pattern, and the like on a substrate having low heat resistance such as a resin. Also, it is suitably used for applications such as decoration and printing which are not intended to be energized.
基材上に導体形成組成物を付与し、加熱して導体を形成する場合、基材の材質は特に制限されず、導電性を有していても有していなくてもよい。具体的には、Ｃｕ、Ａｕ、Ｐｔ、Ｐｄ、Ａｇ、Ｚｎ、Ｎｉ、Ｃｏ、Ｆｅ、Ａｌ、Ｓｎ等の金属、これら金属の合金、ＩＴＯ、ＺｎＯ、ＳｎＯ、Ｓｉ等の半導体、ガラス、黒鉛、グラファイト等のカーボン材料、樹脂、紙、これらの組み合わせなどを挙げることができる。本発明の導体は低温での加熱で得られるため、特に、耐熱性が比較的低い材質からなる基材を用いる場合に好適に適用することができる。耐熱性が比較的低い材質としては、熱可塑性樹脂が挙げられる。熱可塑性樹脂としては、ポリエチレン、ポリプロピレン、ポリメチルペンテン等のポリオレフィン樹脂、ポリカーボネート樹脂などが挙げられる。基材の形状は特に制限されず、板状、棒状、ロール状、フィルム状等であってよい。 When a conductor-forming composition is applied to a substrate and heated to form a conductor, the material of the substrate is not particularly limited and may or may not have conductivity. Specifically, metals such as Cu, Au, Pt, Pd, Ag, Zn, Ni, Co, Fe, Al, Sn, alloys of these metals, semiconductors such as ITO, ZnO, SnO, Si, glass, graphite, Examples include carbon materials such as graphite, resins, papers, and combinations thereof. Since the conductor of the present invention can be obtained by heating at a low temperature, it can be suitably applied particularly when a substrate made of a material having relatively low heat resistance is used. Examples of the material having relatively low heat resistance include a thermoplastic resin. Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, and polymethylpentene, and polycarbonate resins. The shape of the substrate is not particularly limited, and may be plate-like, rod-like, roll-like, film-like, or the like.
導体の体積抵抗率は２００μΩ・ｃｍ以下であることが好ましく、１００μΩ・ｃｍ以下であることがより好ましく、５０μΩ・ｃｍ以下であることが更に好ましく、２５μΩ・ｃｍ以下であることが特に好ましい。 The volume resistivity of the conductor is preferably 200 μΩ · cm or less, more preferably 100 μΩ · cm or less, further preferably 50 μΩ · cm or less, and particularly preferably 25 μΩ · cm or less.
本発明の導体は、種々の用途に用いることができる。具体的には、積層板、太陽電池パネル、ディスプレイ、トランジスタ、半導体パッケージ等の電子部品に使用される、電気配線、放熱膜、表面被覆膜等の部材として利用することができる。特に、本発明の装置に含まれる導体は樹脂等の基材上に形成できるため、フレキシブルな積層板、太陽電池パネル、ディスプレイ等の製造に好適である。 The conductor of the present invention can be used for various applications. Specifically, it can be used as a member such as an electric wiring, a heat dissipation film, and a surface coating film used for electronic components such as a laminate, a solar cell panel, a display, a transistor, and a semiconductor package. In particular, since the conductor included in the device of the present invention can be formed on a base material such as a resin, it is suitable for manufacturing flexible laminates, solar cell panels, displays, and the like.
＜装置＞
本発明の装置は、本発明の導体を含む。装置の種類は特に制限されない。例えば、本発明の導体からなる配線、被膜等を有する積層板、太陽電池パネル、ディスプレイ、トランジスタ及び半導体パッケージ等の電子部品が挙げられる。また、これらの電子部品を内蔵する電子機器、家電、産業用機械、輸送用機械等も本発明の装置に含まれる。
<Apparatus>
The device of the present invention includes the conductor of the present invention. The type of the device is not particularly limited. For example, electronic components such as a wiring board made of the conductor of the present invention, a laminated plate having a coating and the like, a solar cell panel, a display, a transistor, and a semiconductor package can be mentioned. Further, an electronic device, a home appliance, an industrial machine, a transport machine and the like incorporating these electronic components are also included in the apparatus of the present invention.
以下、本発明について実施例をもとに説明するが、本発明はこれらの実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples.
＜実施例１＞
［１．１］ノナン酸銅の合成
水酸化銅（関東化学株式会社、特級）９１．５ｇ（０．９４ｍｏｌ）に１−プロパノール（関東化学株式会社、特級）１５０ｍＬを加えて撹拌し、これにノナン酸（関東化学株式会社、９０％以上）３７０．９ｇ（２．３４ｍｏｌ）を加えた。得られた混合物を、セパラブルフラスコ中で９０℃、３０分間加熱撹拌した。得られた溶液を加熱したままろ過して未溶解物を除去した。その後放冷し、生成したノナン酸銅を吸引ろ過し、洗浄液が透明になるまでヘキサンで洗浄した。得られた粉体を５０℃の防爆オーブンで３時間乾燥してノナン酸銅（ＩＩ）を得た。収量は３４０ｇ（収率９６質量％）であった。
<Example 1>
[1.1] Synthesis of Copper Nonanoate To 91.5 g (0.94 mol) of copper hydroxide (Kanto Chemical Co., Ltd., special grade) was added 150 mL of 1-propanol (Kanto Chemical Co., Ltd., special grade), and the mixture was stirred. 370.9 g (2.34 mol) of nonanoic acid (Kanto Chemical Co., Ltd., 90% or more) was added. The obtained mixture was heated and stirred at 90 ° C. for 30 minutes in a separable flask. The resulting solution was filtered while heating to remove undissolved matter. Thereafter, the mixture was allowed to cool, the produced copper nonanoate was subjected to suction filtration, and washed with hexane until the washing liquid became transparent. The obtained powder was dried in an explosion-proof oven at 50 ° C. for 3 hours to obtain copper (II) nonanoate. The yield was 340 g (96% by mass).
［１．２］銅含有粒子（大径粒子）の合成
上記で得られたノナン酸銅（ＩＩ）１５．０１ｇ（０．０４０ｍｏｌ）と酢酸銅（ＩＩ）無水物（関東化学株式会社、特級）７．２１ｇ（０．０４０ｍｏｌ）をセパラブルフラスコに入れ、１−プロパノール１０ｍＬとヘキシルアミン（東京化成工業株式会社、純度９９％）３２．１ｇ（０．３２ｍｏｌ）を添加し、オイルバス中で８０℃で加熱撹拌して溶解させた。氷浴に移し、内温が５℃になるまで冷却した後、ヒドラジン一水和物（関東化学株式会社、特級）７．７２ｍＬ（０．１６ｍｏｌ）を１−プロパノール１２ｍＬに溶解させた溶液を脂肪酸銅の溶液に加え、氷浴中で撹拌した。なお、銅：ヘキシルアミンのモル比は１：４である。次いで、オイルバス中で９０℃で加熱撹拌した。その際、発泡を伴う還元反応が進み、３０分以内で反応が終了した。セパラブルフラスコの内壁が銅光沢を呈し、溶液が暗赤色に変化した。遠心分離を９０００ｒｐｍ（回転／分）で１分間実施して固体物を得た。固形物を更にヘキサン１５ｍＬで洗浄する工程を３回繰り返し、酸残渣を除去して、銅光沢を有する銅含有粒子の粉体を含む銅ケークＡを得た。
[1.2] Synthesis of copper-containing particles (large-diameter particles) 15.01 g (0.040 mol) of copper (II) nonanoate obtained above and copper (II) acetate anhydride (Kanto Chemical Co., Ltd., special grade) Put 7.21 g (0.040 mol) in a separable flask, add 10 mL of 1-propanol and 32.1 g (0.32 mol) of hexylamine (Tokyo Kasei Kogyo Co., Ltd., purity: 99%), and add 80 ml in an oil bath. The mixture was dissolved by stirring while heating at ℃. After transferring to an ice bath and cooling until the internal temperature becomes 5 ° C., a solution obtained by dissolving 7.72 mL (0.16 mol) of hydrazine monohydrate (Kanto Chemical Co., Ltd., special grade) in 12 mL of 1-propanol is used as a fatty acid. Added to the copper solution and stirred in an ice bath. The molar ratio of copper: hexylamine is 1: 4. Next, the mixture was heated and stirred at 90 ° C. in an oil bath. At that time, the reduction reaction accompanied by foaming proceeded, and the reaction was completed within 30 minutes. The inner wall of the separable flask exhibited a copper luster, and the solution turned dark red. Centrifugation was performed at 9000 rpm (rotation / min) for 1 minute to obtain a solid. The step of further washing the solid with 15 mL of hexane was repeated three times to remove an acid residue, thereby obtaining a copper cake A containing copper-containing particles having a copper luster.
銅ケークＡ中の銅含有粒子を透過型電子顕微鏡（日本電子株式会社製、製品名：ＪＥＭ−２１００Ｆ）で観察したところ、無作為に選択される２００個の銅含有粒子の長軸の平均値は１５０ｎｍであり、長軸の長さが５０ｎｍ以下である銅含有粒子の割合は３０個％であり、長軸の長さが７０ｎｍ以上である銅含有粒子の割合は６０個％であり、最大径粒子の長軸の長さは２００ｎｍであり、アスペクト比の平均値は１．２であった。 When the copper-containing particles in the copper cake A were observed with a transmission electron microscope (manufactured by JEOL Ltd., product name: JEM-2100F), the average value of the major axes of 200 randomly selected copper-containing particles was determined. Is 150 nm, the proportion of copper-containing particles having a major axis length of 50 nm or less is 30%, the proportion of copper-containing particles having a major axis length of 70 nm or more is 60%, and The major axis length of the diameter particles was 200 nm, and the average value of the aspect ratio was 1.2.
［１．３］銅含有粒子（小径粒子）の合成
発泡を伴う還元反応を１０分以内で終了させた以外は上記［１．２］と同様にして、銅光沢を有する銅含有粒子の粉体を含む銅ケークＢを得た。
[1.3] Synthesis of copper-containing particles (small-diameter particles) Powder of copper-containing particles having copper luster in the same manner as in [1.2] above, except that the reduction reaction involving foaming was completed within 10 minutes. Was obtained.
銅ケークＢ中の銅含有粒子を透過型電子顕微鏡（日本電子株式会社製、製品名：ＪＥＭ−２１００Ｆ）で観察したところ、無作為に選択される２００個の銅含有粒子の長軸の平均値は２０ｎｍであり、長軸の長さが５０ｎｍ以下である銅含有粒子の割合は９０個％であり、長軸の長さが７０ｎｍ以上である銅含有粒子の割合は５個％であり、最大径粒子の長軸の長さは８０ｎｍであり、アスペクト比の平均値は１．２であった。 When the copper-containing particles in the copper cake B were observed with a transmission electron microscope (manufactured by JEOL Ltd., product name: JEM-2100F), the average value of the major axes of 200 randomly selected copper-containing particles was determined. Is 20 nm, the proportion of the copper-containing particles having a major axis length of 50 nm or less is 90%, and the proportion of the copper-containing particles having a major axis length of 70 nm or more is 5%. The major axis length of the diameter particles was 80 nm, and the average value of the aspect ratio was 1.2.
銅ケークＡ（３０質量部）、銅ケークＢ（３０質量部）テルピネオール（２０質量部）、及びイソボルニルシクロヘキサノール（商品名：テルソルブＭＴＰＨ、日本テルペン化学株式会社）（２０質量部）を混合して導電性組成物を調製した。得られた導電性組成物をポリエチレンナフタレート（ＰＥＮ）フィルム上に塗布し、加熱して金属銅の薄膜を形成した。加熱は、圧力５００Ｐａ窒素雰囲気のオーブン内、１４０℃で６０分間保持することによって行った。 Copper cake A (30 parts by mass), copper cake B (30 parts by mass), terpineol (20 parts by mass), and isobornylcyclohexanol (trade name: Tersolve MTPH, Nippon Terpen Chemical Co., Ltd.) (20 parts by mass) Thus, a conductive composition was prepared. The obtained conductive composition was applied on a polyethylene naphthalate (PEN) film and heated to form a metal copper thin film. The heating was carried out by holding at 140 ° C. for 60 minutes in an oven having a pressure of 500 Pa and a nitrogen atmosphere.
導電性組成物中の銅含有粒子を透過型電子顕微鏡（日本電子株式会社製、製品名：ＪＥＭ−２１００Ｆ）で観察したところ、無作為に選択される２００個の銅含有粒子の長軸の平均値は８５ｎｍであり、長軸の長さが５０ｎｍ以下である銅含有粒子の割合は６０個％であり、長軸の長さが７０ｎｍ以上である銅含有粒子の割合は３３％であり、最大径粒子の長軸の長さは２００ｎｍであり、アスペクト比の平均値は１．２であった。 When the copper-containing particles in the conductive composition were observed with a transmission electron microscope (manufactured by JEOL Ltd., product name: JEM-2100F), the average of the long axes of 200 randomly selected copper-containing particles was determined. The value was 85 nm, the proportion of copper-containing particles having a major axis length of 50 nm or less was 60%, and the proportion of copper-containing particles having a major axis length of 70 nm or more was 33%. The major axis length of the diameter particles was 200 nm, and the average value of the aspect ratio was 1.2.
＜比較例１＞
前記銅ケークＢ（６０質量部）、テルピネオール（２０質量部）、及びイソボルニルシクロヘキサノール（商品名：テルソルブＭＴＰＨ、日本テルペン化学株式会社）（２０質量部）を混合して導電性組成物を調製した。得られた導電性組成物をポリエチレンナフタレート（ＰＥＮ）フィルム上に塗布し、加熱して金属銅の薄膜を形成した。加熱は、圧力５００Ｐａ窒素雰囲気のオーブン内、１４０℃で６０分間保持することによって行った。
<Comparative Example 1>
The copper cake B (60 parts by mass), terpineol (20 parts by mass), and isobornylcyclohexanol (trade name: Tersolve MTPH, Nippon Terpen Chemical Co., Ltd.) (20 parts by mass) were mixed to form a conductive composition. Prepared. The obtained conductive composition was applied on a polyethylene naphthalate (PEN) film and heated to form a metal copper thin film. The heating was carried out by holding at 140 ° C. for 60 minutes in an oven having a pressure of 500 Pa and a nitrogen atmosphere.
（評価）
各実施例、各比較例で得られた金属銅の薄膜の体積抵抗率を、４端針面抵抗測定器で測定した面抵抗値と、非接触表面・層断面形状計測システム（ＶｅｒｔＳｃａｎ、株式会社菱化システム）で求めた膜厚とから計算した結果を、表１に示した。
(Evaluation)
The volume resistivity of the metallic copper thin film obtained in each of the examples and comparative examples was measured with a sheet resistance value measured by a four-point needle surface resistance measuring device and a non-contact surface / layer cross-sectional shape measurement system (VertScan, Inc.) Table 1 shows the results calculated from the film thickness obtained by Ryoka System).
＜実施例２＞
銅ケークＡ（１０質量部）、銅ケークＢ（３０質量部）テルピネオール（１３．３質量部）、及びイソボルニルシクロヘキサノール（商品名：テルソルブＭＴＰＨ、日本テルペン化学株式会社）（１３．３質量部）を混合して導電性組成物を調製した。得られた導電性組成物をポリエチレンナフタレート（ＰＥＮ）フィルム上に塗布し、加熱して金属銅の薄膜を形成した。加熱は、圧力５００Ｐａ窒素雰囲気のオーブン内、１４０℃で６０分間保持することによって行った。
<Example 2>
Copper cake A (10 parts by mass), copper cake B (30 parts by mass) terpineol (13.3 parts by mass), and isobornylcyclohexanol (trade name: Tersolve MTPH, Nippon Terpen Chemical Co., Ltd.) (13.3 parts by mass) Parts) were mixed to prepare a conductive composition. The obtained conductive composition was applied on a polyethylene naphthalate (PEN) film and heated to form a metal copper thin film. The heating was carried out by holding at 140 ° C. for 60 minutes in an oven having a pressure of 500 Pa and a nitrogen atmosphere.
導電性組成物中の銅含有粒子を透過型電子顕微鏡（日本電子株式会社製、製品名：ＪＥＭ−２１００Ｆ）で観察したところ、無作為に選択される２００個の銅含有粒子の長軸の平均値は５２ｎｍであり、長軸の長さが５０ｎｍ以下である銅含有粒子の割合は７５個％であり、長軸の長さが７０ｎｍ以上である銅含有粒子の割合は２３％であり、最大径粒子の長軸の長さは２００ｎｍであり、アスペクト比の平均値は１．２であった。 When the copper-containing particles in the conductive composition were observed with a transmission electron microscope (manufactured by JEOL Ltd., product name: JEM-2100F), the average of the long axes of 200 randomly selected copper-containing particles was determined. The value was 52 nm, the percentage of copper-containing particles having a major axis length of 50 nm or less was 75%, and the percentage of copper-containing particles having a major axis length of 70 nm or more was 23%. The major axis length of the diameter particles was 200 nm, and the average value of the aspect ratio was 1.2.
以上より、本発明の導電性組成物によれば、１５０℃以下の低温処理によって導電性に優れる導体を形成できることが分かる。 From the above, it can be seen that according to the conductive composition of the present invention, a conductor having excellent conductivity can be formed by a low-temperature treatment at 150 ° C. or lower.
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