JP5049568B2 - Method for producing metal dispersion - Google Patents
Method for producing metal dispersion Download PDFInfo
- Publication number
- JP5049568B2 JP5049568B2 JP2006317726A JP2006317726A JP5049568B2 JP 5049568 B2 JP5049568 B2 JP 5049568B2 JP 2006317726 A JP2006317726 A JP 2006317726A JP 2006317726 A JP2006317726 A JP 2006317726A JP 5049568 B2 JP5049568 B2 JP 5049568B2
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- JP
- Japan
- Prior art keywords
- metal
- acid
- particles
- weight
- metal particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052751 metal Inorganic materials 0.000 title claims description 65
- 239000002184 metal Substances 0.000 title claims description 65
- 239000006185 dispersion Substances 0.000 title claims description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000002923 metal particle Substances 0.000 claims description 57
- 239000002245 particle Substances 0.000 claims description 47
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 29
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical compound OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 21
- 229910052709 silver Inorganic materials 0.000 claims description 18
- 239000004332 silver Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 38
- 239000002904 solvent Substances 0.000 description 32
- 239000000084 colloidal system Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 18
- -1 mercaptocarboxylic acid ester Chemical class 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 150000002736 metal compounds Chemical class 0.000 description 15
- 239000000463 material Substances 0.000 description 13
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- 239000003973 paint Substances 0.000 description 4
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- 238000006722 reduction reaction Methods 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- 241000208125 Nicotiana Species 0.000 description 2
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
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- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
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- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
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- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
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- 241000894007 species Species 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- ACTRVOBWPAIOHC-UHFFFAOYSA-N succimer Chemical compound OC(=O)C(S)C(S)C(O)=O ACTRVOBWPAIOHC-UHFFFAOYSA-N 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
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- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Colloid Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Description
本発明は、金属粒子を配合した金属分散液の製造方法に関する。また、その金属分散液に配合する金属粒子の製造方法に関する。 The present invention relates to a method for producing a metal dispersion containing metal particles. Moreover, it is related with the manufacturing method of the metal particle mix | blended with the metal dispersion liquid.
金属粒子を配合した金属分散液は、金属粒子を溶媒に分散し、必要に応じてバインダーや分散剤、粘度調整剤などの添加剤を更に配合した、一般にコーティング剤、塗料、ペースト、インキなどの組成物を含む総称である。このような金属分散液は、その金属粒子の性質を活用して、例えば電気的導通を確保するため、あるいは帯電防止、電磁波遮蔽又は金属光沢を付与するためなどの種々の用途に用いられている。しかも、近年になって、配合する金属粒子として、平均粒子径が１〜１００ｎｍ程度の金属コロイド粒子が用いられるようになり、その用途は多方面に拡大している。具体的には、金属コロイド粒子の高い導電性を活用して、ブラウン管、液晶ディスプレイ等の透明性部材の電磁波遮蔽に適用されている。また、ナノマテリアルである金属コロイド粒子を用いて、微細な電極、回路配線パターンを形成する技術が提案されている。これは、金属コロイド粒子を配合した金属分散液を、スクリーン印刷、インクジェット印刷等の手法で基板上に電極や回路配線のパターンを塗布した後、比較的低温で加熱して金属コロイド粒子を融着させるもので、特に、プリント配線基板の製造に応用されつつある。更に、金属コロイド粒子は穏やかな加熱条件下においても容易に粒子の融着が進行し金属光沢が発現するため、簡便な鏡面の作製技術が、意匠・装飾用途において注目されている。このような金属分散液としては、例えば、金属コロイドの粒子表面に予めメルカプトカルボン酸を付着させた後、メルカプトカルボン酸エステルを付着させたもの、更に、その後、メルカプトカルボン酸エステルを加水分解させてカルボキシル化した金属コロイド粒子を用いたものが知られている（特許文献１参照）。 Metal dispersions containing metal particles are generally dispersed in a solvent, and further added with additives such as binders, dispersants, and viscosity modifiers as needed. Generally, coating agents, paints, pastes, inks, etc. A generic term that includes the composition. Such metal dispersions are used in various applications, for example, to ensure electrical continuity, or to provide antistatic properties, electromagnetic wave shielding, or metallic luster by utilizing the properties of the metal particles. . Moreover, in recent years, metal colloidal particles having an average particle diameter of about 1 to 100 nm have been used as the metal particles to be blended, and their uses are expanding in various fields. Specifically, it is applied to electromagnetic wave shielding of transparent members such as cathode ray tubes and liquid crystal displays by utilizing the high conductivity of metal colloid particles. In addition, a technique for forming fine electrodes and circuit wiring patterns using metal colloidal particles, which are nanomaterials, has been proposed. This is because metal colloid particles mixed with metal colloid particles are applied to electrodes and circuit wiring patterns on the substrate by screen printing, ink jet printing, etc., and then heated at a relatively low temperature to fuse the metal colloid particles. In particular, it is being applied to the manufacture of printed wiring boards. Furthermore, since metal colloidal particles are easily fused even under mild heating conditions to develop a metallic luster, a simple mirror surface preparation technique is attracting attention in design and decoration applications. As such a metal dispersion, for example, a mercaptocarboxylic acid is previously attached to the particle surface of a metal colloid and then a mercaptocarboxylic acid ester is attached, and then the mercaptocarboxylic acid ester is hydrolyzed. One using carboxylated metal colloidal particles is known (see Patent Document 1).
特許文献１に記載の技術では、保護剤として用いるメルカプトカルボン酸の付着層の密度と付着効率を向上させ、保護効果をより高めることを目的としているので、金属コロイド粒子を水性溶媒中に分散させると、粒子表面のメルカプトカルボン酸やメルカプトカルボン酸エステルが加水分解した生成物が解離して電気的に非常に強い陰性を示し、水のような極めて誘電率の大きい溶媒には、優れた分散安定性が得られるが、アルコール類のような極性溶媒では十分な分散安定性が得られ難い。水性溶媒では表面張力が大きいため用いることのできる塗装機がスピンコーターなどの一部の機器に限定されてしまい、このため、水性溶媒に表面張力の小さい非水溶媒を添加して塗装性の改良を図っているが十分ではない。また、バインダー成分等を配合する場合には、水性溶媒に溶解し易いバインダー成分等を用いる必要があるなど種類の制限を生じ易い。
そこで、広範囲の塗装方法に適用できるアルコール溶媒中で分散安定性に優れた金属分散液が求められており、また、バインダー成分等の配合量を任意に設計し易くするためにも、高濃度の金属分散液が求められている。
The technique described in Patent Document 1 aims to improve the density and adhesion efficiency of the adhesion layer of mercaptocarboxylic acid used as a protective agent, and to further enhance the protective effect, so that the metal colloid particles are dispersed in an aqueous solvent. The product of hydrolysis of mercaptocarboxylic acid and mercaptocarboxylic acid ester on the particle surface is dissociated and shows a very strong negative effect. Excellent dispersion stability is achieved in solvents with extremely high dielectric constants such as water. However, it is difficult to obtain sufficient dispersion stability with polar solvents such as alcohols. Since the surface tension of aqueous solvents is large, the coating machines that can be used are limited to some devices such as spin coaters. For this reason, nonaqueous solvents with low surface tension are added to aqueous solvents to improve paintability. Is not enough. In addition, when a binder component or the like is blended, there is a tendency to limit the types, for example, it is necessary to use a binder component that is easily dissolved in an aqueous solvent.
Therefore, there is a demand for a metal dispersion excellent in dispersion stability in an alcohol solvent that can be applied to a wide range of coating methods, and in order to make it easy to arbitrarily design the blending amount of the binder component, etc., a high concentration There is a need for metal dispersions.
本発明者らは、上記の問題を解決すべく鋭意研究を重ねた結果、特許文献１記載の金属粒子の表面に付着したメルカプトカルボン酸及び／又はその塩を酸の存在下でアルコールと混合させるとエステル化が促進され、それによって生成したメルカプトカルボン酸エステルが有する硫黄原子が金属と強く結合し、アルキル基が外側を向いて存在するので、アルコールとの親和性が非常に高く、アルコール溶媒に分散させることができること、このものは塗装適性に優れていることなどを見出し、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors mix mercaptocarboxylic acid and / or a salt thereof attached to the surface of the metal particles described in Patent Document 1 with an alcohol in the presence of an acid. Esterification is promoted, and the sulfur atom of the mercaptocarboxylic acid ester produced thereby binds strongly to the metal, and the alkyl group is present facing outward. The present invention was completed by finding out that it can be dispersed and that it has excellent paintability.
即ち、本発明は、酸の存在下で、メルカプトカルボン酸及び／又はその塩を粒子表面に有する金属粒子とアルコールを含む溶媒とを混合して、金属粒子をアルコール溶媒に分散させることを特徴とする金属分散液の製造方法である。 That is, the present invention is characterized by mixing metal particles having mercaptocarboxylic acid and / or a salt thereof on the particle surface with a solvent containing alcohol in the presence of an acid, and dispersing the metal particles in an alcohol solvent. This is a method for producing a metal dispersion.
本発明で得られる金属分散液は、アルコール溶媒中でも金属粒子を高濃度で分散安定化させることができ、使用目的に応じて、バインダー成分等を配合して塗料、インキ、ペースト等の組成を任意に設計できる。また、塗装適性にも優れており、インキジェット塗装、スプレー塗装等広範囲の塗装方法に適用できる。
本発明の金属分散液は、電気的導通を確保する材料、帯電防止、電磁波遮蔽、金属光沢を付与する材料などに用いられ、特に、塗膜の導電性を活用したプリント配線基板等の微細電極及び回路配線パターンの形成、塗膜の鏡面を活用した意匠・装飾用途に用いられる。
The metal dispersion obtained in the present invention can disperse and stabilize metal particles at a high concentration even in an alcohol solvent. Depending on the purpose of use, the composition of paints, inks, pastes, etc. can be arbitrarily determined by adding a binder component. Can be designed. In addition, it has excellent coating suitability and can be applied to a wide range of coating methods such as ink jet coating and spray coating.
The metal dispersion of the present invention is used as a material for ensuring electrical continuity, an antistatic material, an electromagnetic wave shielding, a material that imparts a metallic luster, and the like, and in particular, a fine electrode such as a printed wiring board utilizing the conductivity of a coating film. And circuit wiring pattern formation, and design and decoration applications utilizing the mirror surface of the coating film.
本発明は、酸の存在下で、メルカプトカルボン酸及び／又はその塩を粒子表面に有する金属粒子とアルコールを含む溶媒とを混合して、金属粒子をアルコール溶媒に分散させることを特徴とする金属分散液の製造方法である。本発明で得られる金属分散液は、メルカプトカルボン酸及び／又はその塩の一部あるいは全部とアルコールとの反応によって生成したメルカプトカルボン酸エステルを有する金属粒子を配合しているので、アルコール溶媒中に分散し易く、低級アルコールを用いた場合に特に分散安定性が優れている。このため、金属粒子の濃度を高濃度に、例えば１０重量％以上にすることができ、１５重量％以上にも調整することができる。金属粒子の配合量の上限値は、使用目的に応じて適宜設定される。例えば、電極材料用途における金属粒子の配合量の上限値は、９０重量％程度が可能であり、８５重量％が好ましく、８０重量％がより好ましい。装飾用途においてはコストの面から、より低濃度の金属粒子を用いて鏡面を呈する塗膜が得られることが望ましく、その配合量は５０重量％以下であれば良く、２０重量％以下であればより好ましく、１５重量％以下であれば更に好ましい。尚、本発明の金属分散液は、一般に分散体、コーティング剤、塗料、ペースト、インキ、インクなどと称される組成物を包含する。 The present invention is a metal characterized by mixing metal particles having mercaptocarboxylic acid and / or a salt thereof on the particle surface with a solvent containing alcohol in the presence of an acid, and dispersing the metal particles in an alcohol solvent. It is a manufacturing method of a dispersion liquid. The metal dispersion obtained in the present invention contains metal particles having a mercaptocarboxylic acid ester produced by reaction of a part or all of mercaptocarboxylic acid and / or a salt thereof with an alcohol, so that the alcoholic solvent is used in an alcohol solvent. The dispersion is easy to disperse, and the dispersion stability is particularly excellent when a lower alcohol is used. For this reason, the density | concentration of a metal particle can be made into high concentration, for example, 10 weight% or more, and can also be adjusted to 15 weight% or more. The upper limit of the amount of metal particles is appropriately set according to the purpose of use. For example, the upper limit value of the amount of metal particles in the electrode material application can be about 90% by weight, preferably 85% by weight, and more preferably 80% by weight. In decorative applications, from the viewpoint of cost, it is desirable to obtain a coating film having a mirror surface using metal particles having a lower concentration. The blending amount may be 50% by weight or less, and 20% by weight or less. More preferably, it is more preferably 15% by weight or less. The metal dispersion of the present invention includes compositions generally referred to as dispersions, coating agents, paints, pastes, inks, inks and the like.
本発明の具体的な実施形態としては、例えば、前記金属粒子と必要量のアルコールを含む溶媒及び酸を混合し、必要に応じて固液分離し洗浄した後、得られた金属粒子を前記と同種又は異種のアルコールを含む溶媒に混合して分散させて行うこともでき、また、均一に反応させられるので、メルカプトカルボン酸及び／又はその塩を有する金属粒子をアルコールを含む溶媒と酸の混合液に混合して分散させる方法か、前記金属粒子をアルコールを含む溶媒に混合した後、酸を添加して分散させる方法が好ましい。アルコールを含む溶媒又は混合液への混合方法としては湿式混合機あるいは混練機を用い、例えば、撹拌機、らせん型混合機、リボン型混合機、流動化型混合機等の固定型混合機、円筒型混合機、双子円筒型混合機等の回転型混合機などを用いることができる。また、混合の前に必要に応じて、圧縮粉砕型、衝撃圧縮粉砕型、せん断粉砕型、摩擦粉砕型等の粉砕機を用いて、金属粒子を粉砕しても良く、また、粉砕機を用いて粉砕と同時に混合しても良い。粉砕機としては例えば、サンドミル、ボールミル、ビーズミル、コロイドミル等の湿式粉砕機を好適に用いることができる。分散が不足している場合には必要に応じて、超音波分散機等の分散機を用いても良い。混合温度には特に制限は無いが、加熱下で反応を行う場合、アルコールが蒸発し難いように、用いるアルコールの沸点以下の温度で行うのが好ましい。メルカプトカルボン酸及び／又はその塩は金属粒子１００重量部に対し、０．０１〜５０重量部程度の範囲で存在していれば、所望の効果が得られるので好ましく、更に好ましい範囲は０．０５〜２０重量部程度である。また、酸は金属粒子１００重量部に対し、０．１〜１０重量部の範囲で用いるとエステル化が生じ易いので好ましく、更に好ましくは０．５〜５重量部の範囲で用いる。また、アルコールと混合した後の金属粒子を洗浄する場合は、混合後に金属粒子を固液分離して洗浄し、アルコールを含む溶媒に分散させても良い。 As a specific embodiment of the present invention, for example, the metal particles are mixed with a solvent containing a necessary amount of alcohol and an acid, and after solid-liquid separation and washing as necessary, the obtained metal particles are It can also be carried out by mixing and dispersing in a solvent containing the same kind or different kinds of alcohol, and since it can be reacted uniformly, the metal particles having mercaptocarboxylic acid and / or its salt are mixed with the solvent containing acid and the acid. A method of mixing and dispersing in a liquid or a method of adding and dispersing an acid after mixing the metal particles in a solvent containing alcohol is preferable. As a method of mixing into a solvent or mixed solution containing alcohol, a wet mixer or a kneader is used. For example, a stirrer, a spiral mixer, a ribbon mixer, a stationary mixer such as a fluidized mixer, a cylinder, etc. A rotary mixer such as a type mixer or a twin cylinder type mixer can be used. Further, before mixing, the metal particles may be pulverized using a pulverizer such as a compression pulverization mold, an impact compression pulverization mold, a shear pulverization mold, or a friction pulverization mold, if necessary. And may be mixed simultaneously with pulverization. As the pulverizer, for example, a wet pulverizer such as a sand mill, a ball mill, a bead mill, or a colloid mill can be suitably used. If the dispersion is insufficient, a disperser such as an ultrasonic disperser may be used as necessary. Although there is no restriction | limiting in particular in mixing temperature, When reacting under a heating, it is preferable to carry out at the temperature below the boiling point of the alcohol used so that alcohol may not evaporate easily. The mercaptocarboxylic acid and / or the salt thereof is preferably present in an amount of about 0.01 to 50 parts by weight with respect to 100 parts by weight of the metal particles because a desired effect can be obtained, and a more preferable range is 0.05. About 20 parts by weight. Further, the acid is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the metal particles because esterification is likely to occur, and more preferably in the range of 0.5 to 5 parts by weight. Moreover, when wash | cleaning the metal particle after mixing with alcohol, after mixing, a metal particle may be solid-liquid-separated and wash | cleaned, and you may make it disperse | distribute to the solvent containing alcohol.
次に、本発明の製法で用いる各成分について説明する。
（１）金属粒子
本発明で用いる金属粒子は、その構成成分、粒子径等には特に制限はなく、用途に応じて適宜選択することができる。構成成分としては、１種の金属であっても、合金にしたり積層するなど２種以上の金属で構成されても良い。その金属成分としては周期表VIII族（鉄、コバルト、ニッケル、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、白金）及びＩＢ族（銅、銀、金）からなる群より選ばれる少なくとも１種であれば、導電性が高いので好ましく、中でも銀、金、白金、パラジウム、銅は特に導電性が高くより好ましく、電極、回路配線パターン形成用の金属分散液に用いるには、導電性とコストのバランスから銀又は銅が特に好ましい。また、金属粒子には、製法上不可避の酸素、異種金属等の不純物を含有していても良く、あるいは、金属粒子の急激な酸化防止のために必要に応じて予め酸素、金属酸化物やメルカプトカルボン酸以外の有機化合物などが含まれていても良い。金属粒子の粒子径は、入手し易いことから１ｎｍ〜１０μｍ程度の平均粒子径を有する金属粒子を適宜用いるのが好ましく、１ｎｍ〜１μｍ程度の平均粒子径の金属粒子がより好ましく、多方面の用途に用いることができることから１〜１００ｎｍ程度の平均粒子径を有する金属コロイド粒子が更に好ましく、より微細な電極、回路配線パターンを得るためには、５〜５０ｎｍの範囲の平均粒子径を有する金属コロイド粒子を用いるのが更に好ましい。本発明では１種の金属粒子を用いても良いし、２種以上の金属粒子を混合して用いても良く、例えば平均粒子径が異なる２種以上の金属粒子、構成成分が異なる２種以上の金属粒子を混合して用いても良い。
Next, each component used by the manufacturing method of this invention is demonstrated.
(1) Metal particles The metal particles used in the present invention are not particularly limited in terms of their constituent components, particle diameter, etc., and can be appropriately selected according to the intended use. The constituent component may be one kind of metal or may be composed of two or more kinds of metals such as an alloy or a laminate. If the metal component is at least one selected from the group consisting of group VIII (iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum) and group IB (copper, silver, gold) as the metal component In particular, silver, gold, platinum, palladium, and copper are more preferable because of their high conductivity. Silver, gold, platinum, palladium, and copper are particularly preferable because of their high conductivity. For use in metal dispersions for forming electrodes and circuit wiring patterns, the balance between conductivity and cost is preferable. Silver or copper is particularly preferred. In addition, the metal particles may contain impurities such as oxygen and foreign metals that are unavoidable in the manufacturing process, or in advance, oxygen, metal oxides and mercapto as necessary to prevent rapid oxidation of the metal particles. Organic compounds other than carboxylic acid may be contained. Since the particle size of the metal particles is easily available, it is preferable to appropriately use metal particles having an average particle size of about 1 nm to 10 μm, more preferably metal particles having an average particle size of about 1 nm to 1 μm, and various uses. Metal colloid particles having an average particle diameter of about 1 to 100 nm are more preferable, and in order to obtain finer electrodes and circuit wiring patterns, metal colloids having an average particle diameter in the range of 5 to 50 nm. More preferably, particles are used. In the present invention, one kind of metal particles may be used, or two or more kinds of metal particles may be mixed and used. For example, two or more kinds of metal particles having different average particle diameters, two or more kinds having different constituent components. These metal particles may be mixed and used.
金属粒子は、公知の方法を用いて製造することができ、例えば、（１）金属を真空中で蒸発させて、気相中から金属粒子を凝結させる方法、（２）金属化合物溶液に還元剤を添加して、液相中から金属粒子を析出させる方法などを用いることができ、（２）の方法では廉価に金属コロイド粒子が得られるため、より好ましい方法である。（２）の方法において、金属粒子を製造するための原料である金属化合物は、例えば、前記金属の塩化物、硫酸塩、硝酸塩、炭酸塩等を用いることができる。金属化合物を溶解する溶媒には、水又はアルコール等の有機溶媒、あるいはこれら２種以上の混合溶媒を用いることができる。金属化合物の溶媒中の濃度は、金属化合物が溶解する範囲であれば特に制約はないが、工業的には５ミリモル／リットル以上とすることが好ましい。金属化合物が水に難溶のものであれば、金属成分と可溶性の錯体を形成する塩素イオンやアンモニア等を含む化合物を加えて用いることもできる。 The metal particles can be produced using a known method. For example, (1) a method in which a metal is evaporated in a vacuum to condense the metal particles from a gas phase, and (2) a reducing agent is added to the metal compound solution. Can be used to precipitate metal particles from the liquid phase, and the method (2) is more preferable because metal colloidal particles can be obtained at low cost. In the method (2), as the metal compound that is a raw material for producing metal particles, for example, the metal chloride, sulfate, nitrate, carbonate and the like can be used. As a solvent for dissolving the metal compound, an organic solvent such as water or alcohol, or a mixed solvent of two or more of these can be used. The concentration of the metal compound in the solvent is not particularly limited as long as the metal compound can be dissolved, but is preferably 5 mmol / liter or more industrially. If the metal compound is hardly soluble in water, a compound containing chlorine ions, ammonia, or the like that forms a soluble complex with the metal component can be added and used.
液相での反応に用いる還元剤としては公知のものを用いることができ、例えば、（１）ヒドラジン又はその水和物、（２）ヒドラジン系化合物（例えば、塩酸ヒドラジン、硫酸ヒドラジン等）、（３）アルデヒド類（（ａ）脂肪族アルデヒド類（例えば、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ブチルアルデヒド、イソブチルアルデヒド等）、（ｂ）芳香族アルデヒド類（例えば、ベンズアルデヒド等）、（ｃ）複素環式アルデヒド類等）、（４）アミン類（（ａ）１級アミン類（例えば、ブチルアミン、エチルアミン、プロピルアミン、エチレンジアミン等）、（ｂ）２級アミン類（例えば、ジブチルアミン、ジエチルアミン、ジプロピルアミン等）、（ｃ）３級アミン類（例えば、トリブチルアミン、トリエチルアミン、トリプロピルアミン等）等）、（５）アミノアルデヒド類（例えば、アミノアセトアルデヒド等）、（６）アルカノールアミン類（例えば、エタノールアミン、ジエタノールアミン、トリエタノールアミン等）、（７）還元糖（例えば、ショ糖、トレパース、マルトース、ラクトース等）、（８）水素化合物（例えば、水素化ホウ素ナトリウム等）、（９）低次無機酸素酸（例えば、亜硫酸、亜硝酸、次亜硝酸、亜リン酸、次亜リン酸等）及びその水化物（例えば、亜硫酸水素）又はそれらの塩（例えば、ナトリウム等のアルカリ金属塩）等が挙げられ、これらを１種又は２種以上を用いても良い。還元反応は任意の温度で行うことができ、水性溶媒中で行う場合には、５〜９０℃の範囲の温度であれば、反応が進み易いので好ましい。還元剤の添加量は金属に還元できる範囲であれば適宜設定することができ、金属化合物１モルに対して、０．２〜５０モルであることが好ましい。添加量が０．２モル未満では還元反応が十分に進行し難いため好ましくなく、５０モルを超えると生成した金属粒子の分散が不安定になり易いため好ましくない。 As the reducing agent used in the reaction in the liquid phase, known ones can be used. For example, (1) hydrazine or a hydrate thereof, (2) hydrazine compounds (for example, hydrazine hydrochloride, hydrazine sulfate, etc.), ( 3) Aldehydes ((a) aliphatic aldehydes (eg, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, etc.), (b) aromatic aldehydes (eg, benzaldehyde, etc.), (c) heterocyclic Aldehydes), (4) amines ((a) primary amines (eg, butylamine, ethylamine, propylamine, ethylenediamine), (b) secondary amines (eg, dibutylamine, diethylamine, dipropylamine) Etc.), (c) tertiary amines (for example, tributylamine, triethyl) (5) aminoaldehydes (for example, aminoacetaldehyde), (6) alkanolamines (for example, ethanolamine, diethanolamine, triethanolamine, etc.), (7) reducing sugar ( (E.g., sucrose, treperth, maltose, lactose, etc.), (8) hydrogen compounds (e.g., sodium borohydride, etc.), (9) low-order inorganic oxygen acids (e.g., sulfurous acid, nitrous acid, hyponitrous acid, phosphorous) Acid, hypophosphorous acid, etc.) and hydrates thereof (for example, hydrogen sulfite) or salts thereof (for example, alkali metal salts such as sodium), etc., and these may be used alone or in combination. . The reduction reaction can be carried out at any temperature, and when carried out in an aqueous solvent, a temperature in the range of 5 to 90 ° C. is preferred because the reaction can proceed easily. The addition amount of the reducing agent can be appropriately set as long as it can be reduced to a metal, and is preferably 0.2 to 50 mol with respect to 1 mol of the metal compound. If the addition amount is less than 0.2 mol, it is not preferable because the reduction reaction is unlikely to proceed sufficiently.
金属化合物と還元剤の混合液のｐＨを８〜１４の範囲に調整すると、金属化合物が溶媒中に均一に分散し、還元反応が生じ易いので好ましい。更に好ましいｐＨの範囲は８〜１３であり、８〜１２であれば一層好ましい。具体的には、例えば、金属化合物を含む溶媒のｐＨを調整した後、金属化合物を還元しても良く、あるいは、還元剤を混合した後、ｐＨを調整しても良い。ｐＨ調整には、例えば、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム等のアルカリ金属又はアルカリ土類金属の水酸化物や炭酸塩、アンモニア等のアンモニウム化合物、アミン類等の塩基性化合物を用いることができる。このようにして得られた金属粒子は、溶媒のｐＨを５以下にすると容易に凝集するので、吸引ろ過、沈降分離等の比較的簡単な操作でろ別できる。より好ましいｐＨの範囲は０〜５である。ろ別した金属コロイド粒子は常法により洗浄することができ、可溶性塩類や残存する還元剤を十分に除去できる。ｐＨ調整には、例えば、塩酸、硫酸、硝酸等の無機酸、ギ酸、酢酸、プロピオン酸等の有機酸等の酸性化合物を用いることができる。 It is preferable to adjust the pH of the mixed solution of the metal compound and the reducing agent to a range of 8 to 14 because the metal compound is uniformly dispersed in the solvent and a reduction reaction is likely to occur. A more preferable pH range is 8 to 13, and 8 to 12 is more preferable. Specifically, for example, the metal compound may be reduced after adjusting the pH of the solvent containing the metal compound, or the pH may be adjusted after mixing the reducing agent. For pH adjustment, for example, a basic compound such as an alkali metal or alkaline earth metal hydroxide or carbonate such as sodium hydroxide, potassium hydroxide or calcium hydroxide, an ammonium compound such as ammonia, or an amine is used. be able to. Since the metal particles obtained in this way easily aggregate when the pH of the solvent is 5 or less, they can be separated by a relatively simple operation such as suction filtration or sedimentation separation. A more preferable pH range is 0-5. The colloidal metal colloid particles can be washed by a conventional method, and soluble salts and remaining reducing agent can be sufficiently removed. For pH adjustment, for example, an inorganic compound such as hydrochloric acid, sulfuric acid or nitric acid, or an acidic compound such as organic acid such as formic acid, acetic acid or propionic acid can be used.
（２）メルカプトカルボン酸及び／又はその塩
メルカプトカルボン酸及び／又はその塩は、分子内に硫黄元素とカルボキシル基とを含む有機化合物である。本発明では前述のように、この硫黄元素が金属粒子と化学結合しているものと考えられるが、メルカプトカルボン酸及び／又はその塩が金属粒子表面に吸着又は沈着した状態にあっても良く、一部が化学結合し残部が吸着、沈着した状態でも良い。電極や配線パターンの形成に用いる場合は、低分子量のものを用いると熱分解し易く、形成後の電極、配線パターン中に残留し難いので好ましく、分子量が２００以下であれば好ましく、１８０以下であればいっそう好ましい。そのようなメルカプトカルボン酸として、例えば、メルカプトプロピオン酸（分子量１０６）、メルカプト酢酸（同９２）、チオジプロピオン酸（同１７８）、メルカプトコハク酸（同１４９）、ジメルカプトコハク酸（同１８０）、チオジグリコール酸（同１５０）、システイン（同１２１）等が挙げられ、これらから選ばれる１種又は２種以上を用いることができる。中でも、メルカプトプロピオン酸の効果が高く好ましい。また、メルカプトカルボン酸の塩としては、例えば、アルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アミン塩等が挙げられ、これらから選ばれる１種又は２種以上を用いることができる。
(2) Mercaptocarboxylic acid and / or salt thereof Mercaptocarboxylic acid and / or salt thereof is an organic compound containing a sulfur element and a carboxyl group in the molecule. In the present invention, as described above, it is considered that this sulfur element is chemically bonded to the metal particles, but the mercaptocarboxylic acid and / or salt thereof may be adsorbed or deposited on the surface of the metal particles, A state in which a part is chemically bonded and the remaining part is adsorbed and deposited may be used. When used for the formation of electrodes and wiring patterns, it is preferable that a low molecular weight material is used because it is easily thermally decomposed and hardly remains in the formed electrode and wiring pattern. The molecular weight is preferably 200 or less, and 180 or less. If there is more, it is more preferable. Examples of such mercaptocarboxylic acids include mercaptopropionic acid (molecular weight 106), mercaptoacetic acid (92), thiodipropionic acid (178), mercaptosuccinic acid (149), dimercaptosuccinic acid (180). Thiodiglycolic acid (150) and cysteine (121), and one or more selected from these can be used. Among these, mercaptopropionic acid is highly effective and preferable. Examples of the salt of mercaptocarboxylic acid include alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, and the like, and one or more selected from these can be used.
金属粒子の表面にメルカプトカルボン酸及び／又はその塩を予め存在させるには、金属粒子を分散した溶媒中にメルカプトカルボン酸及び／又はその塩を添加し混合するか、あるいは、前記の金属化合物と還元剤とを液相中で反応させる際にメルカプトカルボン酸及び／又はその塩を存在させても製造することができる。後者の方法では還元反応の際にメルカプトカルボン酸及び／又はその塩が存在しており、より高度に分散した金属粒子が得られ、特に微細な金属コロイド粒子が得られるため好ましい方法である。このことから、金属化合物とメルカプトカルボン酸及び／又はその塩とを溶媒に溶解した溶液と還元剤とを混合して還元する方法、金属化合物とメルカプトカルボン酸及び／又はその塩とを溶媒に溶解した溶液に還元剤を添加して還元する方法などがより好ましい方法である。 In order for the mercaptocarboxylic acid and / or salt thereof to be present in advance on the surface of the metal particles, the mercaptocarboxylic acid and / or salt thereof is added to and mixed with the solvent in which the metal particles are dispersed, or When the reducing agent is reacted in the liquid phase, it can be produced even in the presence of mercaptocarboxylic acid and / or a salt thereof. The latter method is preferred because mercaptocarboxylic acid and / or a salt thereof is present during the reduction reaction, and more highly dispersed metal particles can be obtained, and particularly fine metal colloid particles can be obtained. Therefore, a method of reducing by mixing a solution in which a metal compound and mercaptocarboxylic acid and / or a salt thereof are dissolved in a solvent and a reducing agent, and a metal compound and mercaptocarboxylic acid and / or a salt thereof are dissolved in the solvent. A method of reducing the solution by adding a reducing agent is a more preferable method.
（３）酸
酸は、本発明ではメルカプトカルボン酸及び／又はその塩とアルコールとの反応を促進させる働きをするもので、無機酸、有機酸のいずれも用いることができ、１００％濃度での酸度関数(Ｈ０)が−５以下の強酸が好ましい。そのような強酸としては、例えば、硫酸（Ｈ０＝−１１．９）、硝酸（Ｈ０＝−６．３）、弗酸（Ｈ０＝−１０．２）、トリフルオロメタンスルホン酸（Ｈ０＝−１４．９）等が挙げられる。中でも、硫酸及び／又は硝酸の効果が高く好ましい。
(3) Acid In the present invention, the acid serves to promote the reaction between the mercaptocarboxylic acid and / or its salt and the alcohol, and either an inorganic acid or an organic acid can be used. A strong acid having an acidity function (H 0 ) of −5 or less is preferred. Examples of such strong acids include sulfuric acid (H 0 = −11.9), nitric acid (H 0 = −6.3), hydrofluoric acid (H 0 = −10.2), trifluoromethanesulfonic acid (H 0). = -14.9) and the like. Among them, the effect of sulfuric acid and / or nitric acid is high and preferable.
（４）アルコール
アルコールとしては金属粒子を分散するものであればどのようなものでも使用できるが、メルカプトカルボン酸及び／又はその塩との反応を行い得るものが好ましく、反応性が高い低級アルコールがより好ましく、これが有するアルキル基の炭素数が６以下であれば、優れた分散安定性の金属分散液が得られ易いのでより好ましく、直鎖状、分枝状、環状等の種々の構造様態を制限無く用いることができる。中でも、メタノール及び／又はエタノールは効果が大きく、好ましい低級アルコールである。また、エステル化反応後に固液分離して改めて分散させる際に用いるアルコールを含む溶媒としては、エステル化反応と同種のアルコール又は異種のアルコールを用いることができるが、同種のアルコールを用いるのが金属粒子の分散安定性を保持できるため好ましい。また、本発明の効果を損ねない範囲でなら、他の溶媒を含んでも良い。但し、アルコールに水が含まれていると、生成したメルカプトカルボン酸エステルが、経時的に加水分解が進行してメルカプトカルボン酸に戻り、分散安定性が低下してしまうので、水分が５％以下のものを用いるのが好ましい。
(4) Alcohol Any alcohol can be used as long as it can disperse metal particles. However, alcohol capable of reacting with mercaptocarboxylic acid and / or a salt thereof is preferable. More preferably, if the alkyl group it has has 6 or less carbon atoms, it is more preferable because a metal dispersion having excellent dispersion stability is easily obtained, and various structural modes such as linear, branched and cyclic are preferred. Can be used without limitation. Among these, methanol and / or ethanol have a large effect and are preferable lower alcohols. In addition, as the solvent containing alcohol used for solid-liquid separation after the esterification reaction and redispersing, the same kind of alcohol or different kind of alcohol as in the esterification reaction can be used. This is preferable because the dispersion stability of the particles can be maintained. Moreover, as long as the effect of this invention is not impaired, another solvent may be included. However, if the alcohol contains water, the generated mercaptocarboxylic acid ester will be hydrolyzed over time and returned to mercaptocarboxylic acid, resulting in a decrease in dispersion stability. Are preferably used.
前記のように製造された金属分散液には、前記の金属粒子、アルコールの他に、バインダー、増粘剤、可塑剤、防カビ剤、分散剤等を、必要に応じて適宜配合することもできる。バインダーは、塗布物と基材との密着性を一層向上させることができる。バインダーとしては、溶解型、エマルジョン型、コロイダルディスパージョン型等を制限なく用いることができる。また、バインダーの樹脂種としては、アクリル樹脂、アルキド樹脂、ポリエステル樹脂、メラミン樹脂、ウレタン樹脂等を制限無く用いることができる。バインダー成分の配合量は、金属粒子１００重量部に対し０．０１〜１０重量部程度の範囲が好ましく、より好ましい範囲は０．０１〜８重量部程度であり、０．０１〜５重量部程度であれば更に好ましい。 In addition to the metal particles and alcohol, the metal dispersion prepared as described above may be appropriately mixed with a binder, a thickener, a plasticizer, an antifungal agent, a dispersant, and the like as necessary. it can. The binder can further improve the adhesion between the coated material and the substrate. As the binder, a dissolution type, an emulsion type, a colloidal dispersion type and the like can be used without limitation. Moreover, as a resin seed | species of a binder, an acrylic resin, an alkyd resin, a polyester resin, a melamine resin, a urethane resin etc. can be used without a restriction | limiting. The blending amount of the binder component is preferably in the range of about 0.01 to 10 parts by weight, more preferably in the range of about 0.01 to 8 parts by weight, and about 0.01 to 5 parts by weight with respect to 100 parts by weight of the metal particles. If it is more preferable.
次に、本発明で得られた金属分散液を用いた電極等について説明する。
電極、回路配線パターンは、前記金属分散液を、例えば、スクリーン印刷、インクジェット印刷等の方法により、基板に塗布した後、塗布物を適当な温度で加熱焼成して得られる。また、塗膜は、前記金属分散液を、例えば、スピンコート、ロールコート、スプレーコート、刷毛塗り等の方法により、基材に塗布し乾燥して得られる。あるいは、スクリーン印刷やインクジェット印刷などの印刷方法や転写方法を用いて塗膜を形成することもできる。
Next, an electrode using the metal dispersion obtained in the present invention will be described.
An electrode and a circuit wiring pattern are obtained by applying the metal dispersion liquid to a substrate by a method such as screen printing or ink jet printing, and then heating and baking the applied material at an appropriate temperature. Moreover, a coating film is obtained by apply | coating the said metal dispersion liquid to a base material by methods, such as spin coating, roll coating, spray coating, and brush coating, and drying. Or a coating film can also be formed using printing methods, such as screen printing and inkjet printing, and a transfer method.
装飾物品は、基材の表面の少なくとも一部に、前記の塗膜を形成したものであって、金属粒子の金属色や光沢を基材表面に付与したものである。基材表面の全面にわたって着色し光沢を付与することができるほか、基材表面の一部分に意匠、標章、ロゴマークを形成したり、その他の文字、図形、記号を形成したりすることもできる。基材としては、金属、ガラス、セラミック、コンクリートなどの無機質材料、ゴム、プラスチック、紙、木、皮革、布、繊維などの有機質材料、無機質材料と有機質材料とを併用あるいは複合した材料を用いることができる。それらの材質の基材を使用物品に加工する前の原料基材に塗膜を形成して装飾を施すこともでき、あるいは、基材を加工した後のあらゆる物品に装飾を施すこともできる。また、それらの基材表面に予め塗装したものの表面に装飾を施すことも含まれる。
装飾を施す物品の具体例としては、（１）自動車、トラック、バスなどの輸送機器の外装、内装、バンパー、ドアノブ、サイドミラー、フロントグリル、ランプの反射板、表示機器等、
（２）テレビ、冷蔵庫、電子レンジ、パーソナルコンピューター、携帯電話、カメラなどの電化製品の外装、リモートコントロール、タッチパネル、フロントパネル等、
（３）家屋、ビル、デパート、ストアー、ショッピングモール、パチンコ店、結婚式場、葬儀場、神社仏閣などの建築物の外装、窓ガラス、玄関、表札、門扉、ドア、ドアノブ、ショーウインド、内装等、
（４）照明器具、家具、調度品、トイレ機器、仏壇仏具、仏像などの家屋設備、
（５）金物、食器などの什器、
（６）飲料水、タバコなどの自動販売機、
（７）合成洗剤、スキンケア、清涼飲料水、酒類、菓子類、食品、たばこ、医薬品などの容器、
（８）表装紙、ダンボール箱などの梱包用具、
（９）衣服、靴、鞄、メガネ、人口爪、人口毛、宝飾品などの衣装・装飾品、
（１０）野球のバット、ゴルフのクラブなどのスポーツ用品、つり具などの趣味用品、
（１１）鉛筆、色紙、ノート、年賀はがきなどの事務用品、机、椅子などの事務機器、
（１２）書籍類のカバーやオビ等、人形、ミニカーなどのおもちゃ、定期券などのカード類、ＣＤ、ＤＶＤなどの記録媒体、などが挙げられる。また、人間の爪、皮膚、眉毛、髪の毛などを基材とすることができる。
The decorative article is obtained by forming the above-mentioned coating film on at least a part of the surface of the substrate, and imparting the metal color and gloss of the metal particles to the surface of the substrate. The entire surface of the substrate can be colored to give gloss, and a design, mark, logo mark can be formed on a part of the substrate surface, and other characters, figures and symbols can be formed. . As the base material, use inorganic materials such as metals, glass, ceramics, concrete, organic materials such as rubber, plastic, paper, wood, leather, cloth, and fibers, and materials that use a combination of inorganic materials and organic materials or composite materials. Can do. The base material of those materials can be decorated by forming a coating film on the raw material base material before being processed into an article to be used, or can be decorated on any article after processing the base material. Moreover, decorating the surface of those previously coated on the substrate surface is also included.
Specific examples of articles to be decorated include (1) exterior, interior, bumper, door knob, side mirror, front grill, lamp reflector, display device, etc. of transportation equipment such as automobiles, trucks, and buses,
(2) Exteriors of electrical appliances such as TVs, refrigerators, microwave ovens, personal computers, mobile phones, cameras, remote controls, touch panels, front panels, etc.
(3) Houses, buildings, department stores, stores, shopping malls, pachinko shops, wedding halls, funeral halls, exteriors of buildings such as shrines and temples, window glass, entrances, nameplates, gates, doors, doorknobs, show windows, interiors, etc. ,
(4) Lighting equipment, furniture, furniture, toilet equipment, Buddhist altar tools, Buddhist statues and other home equipment
(5) Fixtures such as hardware and tableware,
(6) Vending machines for drinking water, tobacco, etc.
(7) Containers for synthetic detergents, skin care, soft drinks, alcoholic beverages, confectionery, food, tobacco, pharmaceuticals,
(8) Packing tools such as cover paper and cardboard boxes,
(9) Costumes and accessories such as clothes, shoes, bags, glasses, artificial nails, artificial hair, jewelry,
(10) Sports equipment such as baseball bats and golf clubs, hobby goods such as fishing equipment,
(11) Office supplies such as pencils, colored paper, notebooks, New Year postcards, desks and chairs,
(12) Books covers and covers, dolls, toys such as minicars, cards such as commuter passes, recording media such as CDs and DVDs, and the like. In addition, human nails, skin, eyebrows, hair, and the like can be used as a base material.
以下に実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例によって制限されるものではない。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
実施例１
（金属コロイド粒子の調製）
金属化合物として硝酸銀５０ｇと３−メルカプトプロピオン酸１．６ｇを純水２２０ミリリットルに溶解し、２８％アンモニア水７０ミリリットルを加え、ｐＨを１１．６に調整した。一方、２８％アンモニア水４ミリリットルを加えた２９５ミリリットルの純水に還元剤として水素化ホウ素ナトリウム２．１ｇを溶解した。両者を３０分間かけて６００ミリリットルの純水中に撹拌しながら同時に滴下し、硝酸銀を還元して、３−メルカプトプロピオン酸が表面に存在する銀コロイド粒子を溶媒中に生成させた。次いで、得られた銀コロイド粒子の溶媒を、硝酸（３０％）を用いて溶媒のｐＨを２．５に調整し、銀コロイド粒子を沈降させ、真空ろ過機で銀コロイド粒子（銀コロイド粒子１０００重量部に対し、メルカプトプロピオン酸を３重量部含む。銀コロイド粒子の平均粒子径は約１０ｎｍ）をろ別し、ろ液の比導電率が１０μＳ／ｃｍ以下になるまで水洗した後、真空乾燥機にて水分を除去し、銀コロイド粉末（Ｘ）を得た。
Example 1
(Preparation of metal colloidal particles)
As a metal compound, 50 g of silver nitrate and 1.6 g of 3-mercaptopropionic acid were dissolved in 220 ml of pure water, and 70 ml of 28% ammonia water was added to adjust the pH to 11.6. On the other hand, 2.1 g of sodium borohydride was dissolved as a reducing agent in 295 ml of pure water to which 4 ml of 28% ammonia water was added. Both were dripped simultaneously in 600 milliliters of pure water over 30 minutes, silver nitrate was reduced, and silver colloid particles having 3-mercaptopropionic acid existing on the surface were produced in the solvent. Next, the pH of the solvent of the obtained silver colloidal particles is adjusted to 2.5 using nitric acid (30%), the silver colloidal particles are settled, and the silver colloidal particles (silver colloidal particles 1000 are collected with a vacuum filter). 3 parts by weight of mercaptopropionic acid with respect to parts by weight (average particle diameter of silver colloidal particles is about 10 nm) is filtered off, washed with water until the specific conductivity of the filtrate is 10 μS / cm or less, and then vacuum-dried Water was removed with a machine to obtain silver colloidal powder (X).
（金属分散液の調製）
得られた銀コロイド粉末（Ｘ）をメタノールと硝酸の混合溶媒中（硝酸は銀コロイド粒子に対し１重量％に相当）に撹拌混合して、分散させた後、３０分間撹拌して本発明の金属分散液（銀コロイド粒子濃度：３０重量％）を得た。これを試料Ａとする。
(Preparation of metal dispersion)
The obtained silver colloidal powder (X) is stirred and mixed in a mixed solvent of methanol and nitric acid (nitric acid is equivalent to 1% by weight with respect to silver colloid particles) and dispersed, and then stirred for 30 minutes. A metal dispersion (silver colloid particle concentration: 30% by weight) was obtained. This is designated as sample A.
実施例２
実施例１において、硝酸を硫酸に替えたこと以外は同様にして調製し、本発明の金属分散液を得た。これを試料Ｂとする。
Example 2
In Example 1, it prepared similarly except having replaced nitric acid with sulfuric acid, and obtained the metal dispersion liquid of this invention. This is designated as Sample B.
参考例１
実施例１で得た銀コロイド粉末（Ｘ）をエタノールと硝酸の混合溶媒中（硝酸は銀コロイド粒子に対し１重量％に相当）に撹拌混合して、分散させた後、５０℃に加温し、３０分間撹拌して参考例の金属分散液（銀コロイド粒子濃度：３０重量％）を得た。これを試料Ｃとする。
Reference example 1
The silver colloidal powder (X) obtained in Example 1 was stirred and mixed in a mixed solvent of ethanol and nitric acid (nitric acid was equivalent to 1% by weight with respect to silver colloid particles), and then heated to 50 ° C. The mixture was stirred for 30 minutes to obtain a metal dispersion liquid (silver colloid particle concentration: 30% by weight) as a reference example . This is designated as Sample C.
比較例１
実施例１において、メタノールをメチルイソブチルケトンに替えたこと以外は同様にして調製し、比較対象の金属分散液を得た。これを試料Ｄとする。
Comparative Example 1
In Example 1, it prepared similarly except having replaced methanol with methyl isobutyl ketone, and obtained the metal dispersion liquid for comparison. This is designated as Sample D.
比較例２
（金属コロイド粒子の調製）
金属化合物として硝酸銀３９．４ｇを純水に溶解した水溶液６０ミリリットルを、表面保護剤としてクエン酸３ナトリウム２水和物２６２．８ｇ、還元剤として硫酸第一鉄７水和物１２９．２ｇを、純水８００ミリリットルに溶解した水溶液に、撹拌しながら２０分間かけて滴下し、硝酸銀を還元して、クエン酸３ナトリウムが表面に存在する銀コロイド粒子を溶媒中に生成させた。次いで、得られた銀コロイド粒子の溶媒を、遠心分離機を用いて９８０００ｍ／ｓ２で３０分間遠心分離を行い、沈降分を回収して８００ミリリットルの純水に再分散させ、更に、９８０００ｍ／ｓ２で３０分間遠心分離を行い沈降分を除去し、水性銀コロイド溶液を得た。この水性銀コロイド溶液の比導電率を測定したところ、１０μＳ／ｃｍ以下であった。得られた水性銀コロイド溶液にアセトン８００ミリリットルを添加し、銀コロイド粒子を凝集させ、再度、２９４００ｍ／ｓ２で３０分間遠心分離して沈降分を回収し、真空乾燥機にて水分を除去し、銀コロイド粉末（Ｙ）を得た。
Comparative Example 2
(Preparation of metal colloidal particles)
60 ml of an aqueous solution obtained by dissolving 39.4 g of silver nitrate as a metal compound in pure water, 262.8 g of trisodium citrate dihydrate as a surface protective agent, and 129.2 g of ferrous sulfate heptahydrate as a reducing agent, The solution was dropped into an aqueous solution dissolved in 800 ml of pure water over 20 minutes with stirring to reduce silver nitrate, and silver colloidal particles having trisodium citrate existing on the surface were generated in the solvent. Next, the obtained silver colloid particle solvent was centrifuged at 98000 m / s 2 for 30 minutes using a centrifuge, and the sediment was collected and redispersed in 800 ml of pure water. Further, 98000 m / s Centrifugation was performed at s 2 for 30 minutes to remove sediment, and an aqueous silver colloid solution was obtained. When the specific conductivity of this aqueous silver colloid solution was measured, it was 10 μS / cm or less. 800 ml of acetone is added to the obtained aqueous silver colloid solution, the silver colloid particles are aggregated, and centrifuged again at 29400 m / s 2 for 30 minutes to collect the sediment, and the water is removed with a vacuum dryer. Silver colloidal powder (Y) was obtained.
（金属分散液の調製）
前記の銀コロイド粉末（Ｙ）をメタノールと硝酸の混合溶媒中（硝酸は銀コロイド粒子に対し１重量％に相当）に撹拌混合して、分散させた後、３０分間撹拌して比較対象の金属分散液（銀コロイド粒子濃度：３０重量％）を得た。これを試料Ｅとする。
(Preparation of metal dispersion)
The above-mentioned silver colloidal powder (Y) is stirred and mixed in a mixed solvent of methanol and nitric acid (nitric acid is equivalent to 1% by weight with respect to silver colloid particles) and dispersed, and then stirred for 30 minutes to be a metal to be compared A dispersion (concentration of silver colloid particles: 30% by weight) was obtained. This is designated as Sample E.
評価１
実施例１、２、参考例１、比較例１〜２で得られた金属分散液（試料Ａ〜Ｅ）を、３日間静置した後、溶媒中の固形分濃度を測定した。固形分濃度が高い程、分散安定性に優れている。結果を表１に示す。本発明の金属分散液は、分散安定性に優れていることが判る。
Evaluation 1
The metal dispersions (samples A to E) obtained in Examples 1 and 2, Reference Example 1 and Comparative Examples 1 and 2 were allowed to stand for 3 days, and then the solid content concentration in the solvent was measured. The higher the solid content concentration, the better the dispersion stability. The results are shown in Table 1. It can be seen that the metal dispersion of the present invention is excellent in dispersion stability.
本発明で得られる金属分散液は、メタノール、エタノール等のアルコールを分散媒とし、高濃度で分散安定性に優れているので、塗料、インキ、ペースト等の組成設計を比較的自由に行え、また、塗装適性に優れ、汎用性も高い。この金属分散液は、近年活発に開発が進められている電極、回路配線パターンの形成といったナノテクノロジーの新規用途にも適用でき、また、金属光沢による意匠性、装飾性の付与などのメッキ技術の代替用途にも適用できる。 The metal dispersion obtained in the present invention uses alcohol such as methanol and ethanol as a dispersion medium, and is excellent in dispersion stability at a high concentration. Therefore, the composition design of paints, inks, pastes and the like can be performed relatively freely. Excellent paintability and versatility. This metal dispersion can also be applied to new nanotechnology applications such as the formation of electrodes and circuit wiring patterns that have been actively developed in recent years. Applicable to alternative applications.
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