WO2009157393A1 - Encre électriquement conductrice pour impression en transparence - Google Patents

Encre électriquement conductrice pour impression en transparence Download PDF

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Publication number
WO2009157393A1
WO2009157393A1 PCT/JP2009/061278 JP2009061278W WO2009157393A1 WO 2009157393 A1 WO2009157393 A1 WO 2009157393A1 JP 2009061278 W JP2009061278 W JP 2009061278W WO 2009157393 A1 WO2009157393 A1 WO 2009157393A1
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WIPO (PCT)
Prior art keywords
conductive ink
dispersion
ink
polymer compound
metal
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PCT/JP2009/061278
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English (en)
Japanese (ja)
Inventor
竜 小池
俊裕 海老根
直 義原
康弘 千手
宏 五十住
正紀 笠井
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Dic株式会社
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Publication of WO2009157393A1 publication Critical patent/WO2009157393A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature

Definitions

  • the present invention relates to a conductive ink suitable for reversal printing, which can be used appropriately for manufacturing electronic devices.
  • Transistors are widely used as important electronic elements constituting televisions and computer equipment, and are currently manufactured using inorganic materials such as silicon as the main material.
  • inorganic materials such as silicon as the main material.
  • an organic transistor using an organic substance as a member of such a transistor has attracted attention.
  • Organic transistors are soft and flexible, and have the advantage that raw materials can be produced at a low price when considered per unit area, and are indispensable components for the realization of ubiquitous era, that is, flexible and low-cost terminals. It is believed that.
  • a general element structure of an organic transistor is shown in FIG. In this, this invention relates to the electroconductive ink for forming an electrode layer especially.
  • a conductive ink containing silver particles having an average particle diameter of 5 ⁇ m or less is known for reversal printing (see, for example, Patent Document 3).
  • the reverse printing method is effective in forming a precise pattern, in order to form an electronic element by providing a conductive film on the substrate, not only the conductivity and resolution of the ink film, but also the substrate in the printing process. No conductive ink having sufficient functions suitable for the reversal printing method, such as extension of the transferable time, is obtained.
  • the dispersion containing the metal of a nano particle size is known as an electroconductive material (for example, refer patent document 4), the electroconductive ink which has the function suitable for the reversal printing method is obtained. Absent.
  • An object of the present invention is to provide a conductive ink for reversal printing that has not only the conductivity and resolution of an ink film, but also functions such as extending the transferable time to a substrate in the printing process.
  • the present invention for solving the above-mentioned problems is a metal nanoparticle comprising a polyalkyleneimine chain (a), a dispersion of a polymer compound (X) having a hydrophilic segment (b), and metal nanoparticles (Y).
  • a conductive ink for reversal printing comprising a dispersion (A), a surface energy adjusting agent (B), a release agent (C), a fast-drying organic solvent (D), and a slow-drying organic solvent (E) I will provide a.
  • the conductive ink for reversal printing according to the present invention has not only the conductivity and resolution of the ink film, but also functions such as extending the transferable time to the substrate in the printing process.
  • the conductive ink for reverse printing of the present invention is a metal containing a polyalkyleneimine chain (a), a dispersion of a polymer compound (X) having a hydrophilic segment (b), and metal nanoparticles (Y).
  • a conductive ink for reverse printing containing a nanoparticle dispersion (A), a surface energy adjusting agent (B), a release agent (C), a fast-drying organic solvent (D), and a slow-drying organic solvent (E).
  • the conductive ink for reversal printing of the present invention can further contain water as a solvent.
  • a melamine resin can be added as a resin component.
  • Reverse printing is a printing method that transfers ink to a substrate to be printed in the following steps. That is, first, an ink coating film having a uniform thickness is formed on the surface of the blanket by an ink coating apparatus. Next, the surface of the blanket on which the uniform ink coating film is formed is pressed against and brought into contact with the relief plate on which the printing pattern is formed, and the surface of the ink coating on the surface of the blanket is brought into contact with the convex surface of the relief printing plate. A part is attached and transferred. Thereby, a printing pattern (image) is formed on the ink coating film remaining on the surface of the blanket.
  • the blanket in this state is pressed against the surface of the printing substrate made of a glass plate, a plastic sheet, etc., and the ink coating film remaining on the blanket is transferred, and the ink coating transferred onto the printing substrate is transferred.
  • a printed matter is obtained by firing the film.
  • the metal nanoparticle dispersion (A) used in the conductive ink for reverse printing of the present invention is a dispersion of a polymer compound (X) having a polyalkyleneimine chain (a) and a hydrophilic segment (b), It is a metal nanoparticle dispersion (A) containing metal nanoparticles (Y).
  • the alkyleneimine unit in the chain can be coordinated with a metal or a metal ion. It is a polymer chain that can be immobilized.
  • the structure is a polymer having an alkyleneimine unit of a secondary amine as a main repeating unit, and may be either a linear structure or a branched structure.
  • the degree of polymerization of the polyalkyleneimine chain (a) is not particularly limited, but if it is too low, the amount of the metal nanoparticles contained in the dispersion of the polymer compound (X) and its stable retention will be reduced. If it is insufficient and if it is too high, the polymer compound (X) becomes a huge aggregate, which impedes storage stability. Therefore, in order to obtain a metal nanoparticle dispersion having superior ability to immobilize metal nanoparticles in the obtained metal nanoparticle dispersion and to prevent the dispersion from becoming too large, the polyalkyleneimine is obtained.
  • the degree of polymerization of the chain (a) is usually in the range of 1 to 10,000, preferably in the range of 3 to 3,000, and more preferably in the range of 5 to 1,000.
  • the polyalkyleneimine chain (a) can be used without particular limitation as long as it is generally commercially available or can be synthesized, but from the viewpoint of industrial availability, a polyethyleneimine chain, A polypropyleneimine chain is preferred.
  • the hydrophilic segment (b) constituting the polymer compound (X) used in the present invention has a high affinity for the solvent when the polymer compound (X) is dispersed in a hydrophilic solvent such as water. And a segment that maintains dispersion stability when a dispersion is formed. Further, when dispersed in a hydrophobic solvent, the hydrophilic segment (b) has a role of forming a core of the dispersion due to a strong associative force within the molecule or between the molecules.
  • the degree of polymerization of the hydrophilic segment (b) is not particularly limited, but when dispersed in a hydrophilic solvent, if the degree of polymerization is too low, the dispersion stability is deteriorated, and if too high, the dispersions are dispersed. There is a possibility of aggregation, and when dispersed in a hydrophobic solvent, if the degree of polymerization is too low, the associating power of the dispersion becomes poor, and if it is too high, the affinity with the solvent cannot be maintained. From these viewpoints, the degree of polymerization of the hydrophilic segment (b) is usually 1 to 10,000, preferably 3 to 3,000, and 5 to 1,000 from the viewpoint of ease of production. It is more preferable that Further, the polymerization degree in the case of a polyoxyalkylene chain is particularly preferably 5 to 500.
  • the hydrophilic segment (b) can be used without particular limitation as long as it is generally made of a commercially available or synthesizable hydrophilic polymer chain.
  • a nonionic polymer is preferable because a dispersion having excellent stability can be obtained.
  • hydrophilic segment (b) examples include polyoxyalkylene chains such as polyoxyethylene chains and polyoxypropylene chains, polymer chains composed of polyvinyl alcohols such as polyvinyl alcohol and partially saponified polyvinyl alcohol, polyhydroxyethyl acrylate, Polymer chains composed of water-soluble poly (meth) acrylic esters such as hydroxyethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, polyacetylethyleneimine, polyacetylpropyleneimine, polypropionylethyleneimine, polypropionylpropyleneimine
  • polyacylalkyleneimine chains having hydrophilic substituents such as polyacrylamide, polyisopropylacrylamide, and polyvinylpyrrolidone
  • Polymer chains composed of reacrylamides and the like can be mentioned. Among them, a dispersion having particularly excellent stability is obtained, and it is a polyoxyalkylene chain from the
  • the metal nanoparticle dispersion (A) described above includes a dispersion of a polymer compound (X) having a polyalkyleneimine chain (a), a hydrophilic segment (b), and a hydrophobic segment (c), It may be a metal nanoparticle dispersion (A) containing nanoparticles (Y).
  • the hydrophobic segment (c) constituting the polymer compound (X) used in the present invention is intermolecular or intermolecularly interlinked. Due to the strong associative force, the core of the dispersion is formed and has a role of forming a stable dispersion. Further, when dispersed in a hydrophobic solvent, the segment has a high affinity with the solvent and retains the dispersion stability when a dispersion is formed.
  • the hydrophobic segment (c) can be used without particular limitation as long as it is generally composed of a residue of a hydrophobic compound that is commercially available or can be synthesized.
  • polystyrenes such as polystyrene, polymethylstyrene, polychloromethylstyrene, polybromomethylstyrene, polyacrylic acid methyl ester, polymethacrylic acid methyl ester, polyacrylic acid 2-ethylhexyl ester, polymethacrylic acid 2-ethylhexyl ester, etc.
  • Water-insoluble poly (meth) acrylic acid esters include such residues of the resin and polycarbonate, also a residue of a single compound or a residue of a compound obtained by previously reacting the two or more different compounds.
  • the epoxy resin is not particularly limited as long as it is commercially available or can be synthesized.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Bisphenol A novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, Naphthol-phenol co-condensed novolac type epoxy resin, Naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon form Aldehyde resin modified phenol resin type epoxy resin, a biphenyl novolak type
  • the obtained metal nanoparticle dispersion when used as a conductive paste, it is preferably a residue of a bisphenol A type epoxy resin from the viewpoint of excellent adhesion to a substrate, and the like in a hydrophilic solvent. From the viewpoint of obtaining a dispersion having a strong associative strength and excellent dispersion stability and storage stability, it is preferably a residue of a trifunctional or higher functional epoxy resin such as a naphthalene type tetrafunctional epoxy resin.
  • these epoxy resins may be used as raw materials for the polymer compound (X) as they are, and may be modified with various modifications according to the structure of the target polymer compound (X). good.
  • polyurethane can be used without particular limitation as long as it is commercially available or can be synthesized.
  • polyurethane is a polymer obtained by addition reaction of polyol and polyisocyanate.
  • the polyol include propylene glycol, neopentyl glycol, polypropylene glycol, polytetramethylene ether glycol, polyester polyol, polycaprolactone polyol, polycarbonate diol, bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyl, 3, 3 ′, 5,5′-tetramethylbiphenyl-4,4′-diol, phenol novolak, cresol novolak, propanediol, butanediol, pentanediol, n-hexanediol, cyclohexanediol, methylpentanediol, polybutadiene dipolyol, Modified from trimethylolpropane
  • polyisocyanate examples include diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, bis (isocyanate methyl) cyclohexane, hexamethylene diisocyanate, 1,5-naphthylene diisocyanate, tetramethylxylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene.
  • examples include diisocyanate, dicyclohexylmethane diisocyanate, hexamethine diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, and trimethylhexamethylene diisocyanate. These may be used alone or in admixture of two or more.
  • polypropylene glycol polypropylene glycol, bisphenol A type epoxy resin-modified polyol, etc. are used as polyols from the viewpoint of excellent adhesion to various substrates.
  • polyisocyanate hexamethylene diisocyanate, bis (isocyanate methyl) cyclohexane, and the like are preferable, and it is most preferable to use polyurethane obtained by combining these preferable raw materials.
  • these polyurethanes may be used as raw materials for the polymer compound (X) as they are, and may further be modified according to the structure of the target polymer compound (X). .
  • polycarbonates can be used without particular limitation as long as they are commercially available or can be synthesized.
  • polycarbonate is a polymer produced from a condensation reaction between bisphenol A and phosgene, diphenyl carbonate, or the like.
  • Polycarbonate is a typical example of the polycarbonates, but various carbonate-based polymers that can be produced using various raw materials exemplified by polyols that are raw materials of the polyurethanes instead of bisphenol A, which is a raw material of polycarbonates, are also available. Examples of polycarbonates can be mentioned.
  • Polycarbonates may be used as raw materials for the polymer compound (X) as they are, and may further be modified according to the structure of the target polymer compound (X).
  • hydrophobic segments (c) listed above one or more compounds selected from polystyrene, poly (meth) acrylic acid ester, epoxy resin, polyurethane, polycarbonate, and polyacylalkyleneimine having a hydrophobic substituent. Residues are comprehensively determined not only from the industrial availability and ease of handling of each compound used as a raw material, but also from the high hydrophobic associative power of the polymer compound (X). It is a preferable hydrophobic segment, and is particularly excellent in the industrial production method of the polymer compound (X), and from the viewpoint of cost, availability, etc., polystyrene, poly (meth) methyl acrylate, epoxy resins, polyurethanes. It is more preferably a residue, and most preferably a residue of epoxy resins.
  • the degree of polymerization of the hydrophobic segment (c) is not particularly limited, but when dispersed in a hydrophilic solvent, the dispersion stability deteriorates if it is too low, and the dispersion aggregates if it is too high. In the case of dispersing in a hydrophobic solvent, if the dispersion is too low, the dispersibility of the dispersion becomes poor, and if it is too high, the affinity with the solvent cannot be maintained. From these viewpoints, the polymerization degree of the hydrophobic segment (c) is usually from 1 to 10,000, such as polystyrenes, poly (meth) acrylic acid esters, polyacylalkyleneimines having a hydrophobic substituent, and the like.
  • the degree of polymerization is usually 1 to 50, preferably 1 to 30, and particularly 1 to 20. Is preferred.
  • the production method of the polymer compound (X) used in the present invention is not particularly limited.
  • branched polyalkyleneimine chain a commercially available or synthesized one can be suitably used as described above.
  • the synthesis of the branched polyalkyleneimine chain may be carried out by various methods, and is not particularly limited, but generally includes a method of ring-opening polymerization of ethyleneimine using an acid catalyst. Since the end of the branched polyethyleneimine is a primary amine, if the hydrophilic segment has a functional group that reacts with the primary amine, it can be reacted successively or simultaneously in the present invention. A polymer compound that can be used can be synthesized. The functional group that reacts with the primary amine is not particularly limited.
  • An acid chloride etc. are mentioned.
  • a carboxyl group, an isocyanate group, a tosyl group, an epoxy group, and a glycidyl group are advantageous in terms of production, such as reactivity and ease of handling, and are preferred functional groups.
  • a functional group that reacts directly with the primary amine it can be any functional group that can react with the primary amine by performing various treatments. For example, it has a hydroxyl group. Alternatively, this may be reacted with a polyethyleneimine chain by a method such as glycidylation. Further, after the primary amine of the branched polyalkyleneamine chain is converted to other functional groups capable of reacting with the functional group of the hydrophilic segment, these are reacted to give a polymer compound (X ) Can also be synthesized.
  • a typical synthesis example of the polymer compound (X) will be described.
  • (I) A commercially available product is used as the branched polyalkyleneimine, and a tosyl derivative of polyethylene glycol monomethyl ether is used as the hydrophilic polymer.
  • the hydrophilic polymer can be obtained, for example, by reacting polyethylene glycol monomethyl ether and tosyl chloride in a polar solvent in the presence of pyridine. Further, when a hydrophobic polymer is used, an epoxy resin having an epoxy group at the terminal is used as the hydrophobic polymer.
  • polyethyleneimine is dissolved in a polar solvent and reacted with a tosyl derivative of polyethylene glycol monomethyl ether at 100 ° C. in the presence of a base such as potassium carbonate to obtain a compound having polyethylene glycol and a polyethyleneimine structure.
  • a polymer compound having a polyethylene glycol-polyethyleneimine-epoxy resin structure can be obtained by synthesizing and then adding an epoxy resin in a mixed solvent of acetone and methanol and reacting at 60 ° C.
  • the proportion of each component in the polymer compound (X) used in the present invention is, for example, in the case of a branched polyalkyleneimine chain, and in the case of a ternary system, the branched polyalkyleneimine chain (a-1),
  • the polymerization degree ratio (a-1) :( b) :( c) of the polymer constituting the chain of each component of the hydrophilic segment (b) and the hydrophobic segment (c) is not particularly limited. Is generally in the range of 5,000: 5 to 5,000,000: 1 to 5,000,000, from the viewpoint of excellent associative force, dispersion stability and storage stability of the obtained metal nanoparticle dispersion, In particular, 5000: 25 to 400,000: 5 to 1,000,000 is preferable.
  • the range of the ratio is more preferably 25 to 200,000, and when polystyrenes, poly (meth) acrylic acid esters, polyacylalkyleneimines having a hydrophobic substituent, and the like are used for the hydrophobic segment (c), the range of the ratio is more preferably 15 to 1,000,000. When a compound composed of a residue of a resin such as epoxy resins, polyurethane and polycarbonate is used, the range of the ratio is more preferably 5 to 20,000.
  • the proportion of each component in the polymer compound (X) used in the present invention is, for example, in the case of a linear polyalkyleneimine chain and in the case of a ternary system, a linear polyalkyleneimine chain (a-2 ), Ratio (a-2) :( b) :( c) of the degree of polymerization of the polymer constituting the chain of each component of the hydrophilic segment (b) and the hydrophobic segment (c) is particularly limited However, it is usually in the range of 5,000: 5 to 5,000,000: 1 to 5,000,000 because the metal nanoparticle dispersion obtained is excellent in associative force, dispersion stability and storage stability. In particular, 5,000: 80 to 1,000,000: 10 to 50,000 are preferable.
  • the degree of polymerization of the linear polyalkyleneimine chain is 5000
  • the range of the ratio is more preferably 80 to 500,000
  • the epoxy resin residue as the hydrophobic segment (c) is more preferably 10 to 50,000.
  • the metal species of the metal nanoparticles (Y) constituting the metal nanoparticle dispersion (A) are not limited as long as the metal or ion can coordinate with the branched polyalkyleneimine chain (a-1).
  • a metal species such as a transition metal-based metal compound can be used.
  • ionic transition metals are preferable, and transition metals such as copper, silver, gold, nickel, palladium, platinum, and cobalt are more preferable.
  • the metal nanoparticle (Y) which comprises a metal nanoparticle dispersion (A) may be one type, or may be two or more types.
  • transition metals silver, gold, palladium, and platinum are particularly preferable because the metal ions are spontaneously reduced at room temperature or in a heated state after coordination with polyethyleneimine.
  • silver, gold, and platinum are the most preferred transition metals in terms of ease of reduction reaction and ease of handling.
  • the content of the metal nanoparticles (Y) in the metal nanoparticle dispersion (A) is not particularly limited, but if the content is too small, the characteristics of the metal nanoparticles in the dispersion are difficult to appear, If the amount is too large, the relative weight of the metal nanoparticles in the dispersion increases, and the viewpoint that the metal nanoparticle dispersion is expected to settle due to the balance between the relative weight and the dispersion holding power of the dispersion is high. From the viewpoint of reducing ability and coordination ability due to the alkyleneimine unit in the molecular compound (X), the content of the metal nanoparticles (Y) is the total number of nitrogen atoms forming the polyalkyleneimine chain (a).
  • the metal nanoparticles (Y) are usually in the range of 1 to 20,000 mol, preferably in the range of 1 to 10,000 mol, particularly in the production method described later, 50 ⁇ 7,000mol when used in combination, if no combination of reducing agent is preferably 5 ⁇ 70 mol.
  • the content of the polymer compound (X) is preferably in the range of 1 to 5% by mass, particularly preferably 3 to 5% by mass, based on the metal nanoparticles (Y).
  • the particle diameter of the metal nanoparticles (Y) constituting the metal nanoparticle dispersion (A) is not particularly limited, but for the metal nanoparticle dispersion to have higher dispersion stability,
  • the particle diameter of the metal nanoparticles (Y) constituting the metal nanoparticle dispersion of the invention is preferably fine particles of 1 to 50 nm, and more preferably in the range of 5 to 30 nm.
  • a metal salt or a metal ion solution is added to a medium in which a compound having a polyalkyleneimine chain and a hydrophilic segment is dispersed, and the metal ion is reduced. It is characterized by being stabilized as metal nanoparticles.
  • the metal nanoparticle dispersion produced in this way is excellent in dispersion stability and storage characteristics, and has the ability as various metal-containing functional dispersions such as color development, catalyst, and electrical function of the metal nanoparticles. ing.
  • the metal ion that can be used here may be a water-soluble metal compound, such as a salt of a metal cation and a counter anion, or a metal that is contained in the counter anion, etc.
  • a metal ion having a metal species can be preferably used.
  • metal ions of silver, gold, palladium, and platinum are coordinated to polyethyleneimine, and then spontaneously reduced at room temperature or in a heated state, thereby producing nonionic metal nanoparticles. It is preferable because it is converted to.
  • a metal nanoparticle dispersion can also be formed by passing through the process of making it.
  • reducing agents can be used as the reducing agent, and the reducing agent is not particularly limited. It is preferable to select the reducing agent depending on the intended use of the resulting metal nanoparticle dispersion, the metal species to be contained, and the like. .
  • Examples of reducing agents that can be used include boron compounds such as hydrogen, sodium borohydride, ammonium borohydride, alcohols such as methanol, ethanol, propanol, isopropyl alcohol, ethylene glycol, and propylene glycol, formaldehyde, acetaldehyde, Aldehydes such as propionaldehyde, acids such as ascorbic acid, citric acid, sodium citrate, propylamine, butylamine, diethylamine, dipropylamine, dimethylethylamine, triethylamine, ethylenediamine, triethylenetetramine, methylaminoethanol, dimethylaminoethanol, Examples include amines such as triethanolamine, and hydrazines such as hydrazine and hydrazine carbonate.
  • sodium borohydride, ascorbic acid, sodium citrate, methylaminoethanol, dimethylaminoethanol and the like are more preferable from the viewpoint of industrial availability and handling
  • the surface energy adjusting agent (B) is added to make the surface energy of the ink composition smaller than the surface energy on the blanket surface so that the ink composition can be uniformly and satisfactorily applied to the blanket surface in reverse printing. It is also a thing.
  • the concentration of the surface energy adjusting agent in the ink composition is 0.03 to 5.0% by mass, preferably 0.03% by mass or more, more preferably 0.09% by mass or more, and 0 More preferably, the content is 15% by mass. Thereby, the smoothness of the coated film improves at the time of ink coating to a blanket, and a more uniform coating film is obtained.
  • the concentration of the surface energy adjusting agent in the ink composition is less than 0.03% by mass, ink repelling on the blanket may occur, the ink coating film may not be uniform, and unevenness and streaks may occur.
  • the concentration of the surface energy adjusting agent in the ink composition exceeds 5.0% by mass, the surface energy adjusting agent in the ink coating film is transferred to the printing substrate and the ink coating film after being transferred onto the printing substrate. This causes an inconvenience that interferes with the adhesiveness, and this is also not preferable.
  • a fluorine-based surfactant or a silicone-based surfactant can be used. In the ink composition of the present invention, one or more of these surfactants are used.
  • Specific examples of the surface energy adjusting agent include, as a fluorosurfactant, Megafac F-470, Megafac F-472, Megafac F-484, Megafac TF-1159, Megafac TF-1303 (and above).
  • a silicone-based surfactant BYK-307, BYK-333, BYK-345, BYK-349, BYK-375, BYK-378 (above, trade names Bic Chemie) Company).
  • Silicone oil is preferable as the release agent (C) used in the conductive ink for reverse printing of the present invention.
  • One or more of these silicone oils are used in the ink composition of the present invention.
  • the specific release agent is KF-96 series (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) , SH28PA (trade name, manufactured by Toray Dow Chemical Co., Ltd.) and Granol series (trade name, manufactured by Kyoei Co., Ltd.).
  • the fast-drying organic solvent (D) used in the conductive ink for reverse printing of the present invention refers to an organic solvent having a solubility parameter of 11 or more and a vapor pressure at 20 ° C. of 30 mmHg or more.
  • the quick-drying organic solvent any one or more of an ester solvent, an alcohol solvent, an ether solvent and a hydrocarbon solvent having the above-described characteristics is used.
  • This quick-drying organic solvent is used when the ink film is formed on the blanket so that the ink composition has good fluidity, and then in the atmosphere until it is imaged on the relief printing plate.
  • the ink viscosity is increased by volatilization or absorption by a blanket, and is blended so as to have the optimum viscosity, tackiness and cohesion for imaging.
  • the solubility parameter is 11 or more and the vapor pressure at 20 ° C. is 30 mmHg or more.
  • the conductive ink for reversal printing of the present invention does not contain a quick-drying organic solvent, the ink coating on the blanket will not dry sufficiently, and the ink coating will transfer to portions other than the relief plate, resulting in a good image on the blanket. This is not preferable because a defect such as not being formed occurs.
  • These fast-drying organic solvents are selected according to the solubility of the vehicle and the affinity for the metal nanoparticle dispersion, and the following solvents are used as examples.
  • ester solvents ethyl acetate, normal propyl acetate, isopropyl acetate, alcohol solvents as methanol, ethanol, 1-propanol, 2-propanol, hydrocarbon solvents as pentane, hexane, cyclohexane, methylcyclohexane, toluene, xylene Etc. These may also be a mixture of each system and a plurality of systems.
  • ether solvents include diethyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, 1,3-dioxolane and the like. Of these, isopropyl acetate, ethanol and 2-propanol are preferable in view of their evaporation rate and surface tension.
  • the slow-drying organic solvent (E) used for the conductive ink for reverse printing of the present invention is any of ester solvents, alcohol solvents, ether solvents and hydrocarbon solvents whose vapor pressure at 20 ° C. is less than 30 mmHg. One or more are used.
  • This slow-drying organic solvent remains on the blanket until the imaged ink coating formed on the blanket by the relief printing is transferred onto the substrate to be printed, thereby increasing the viscosity of the ink beyond a certain level. This is used to prevent this and obtain a good image on the substrate to be printed.
  • the compounding quantity is less than 20 mass% in all the organic solvents.
  • this compounding quantity exceeds 20 mass%, volatilization of the organic solvent from a blanket will become slow, and it will become late that the swelling of a blanket becomes fixed.
  • the ink about 0.5 to 1.5% by mass is desirable.
  • These slow-drying organic solvents are selected according to the solubility of the vehicle and the affinity for the metal nanoparticle dispersion, and the following solvents are used as examples.
  • ester solvents propylene glycol monomethyl ether acetate (PGMAc), 3-methoxy-3-methyl-butyl acetate ("Solfit AC", trade name: Kuraray), ethoxyethyl propionate (EEP), alcohol solvents, 1-butanol, Diadol 135 (trade name: manufactured by Mitsubishi Rayon), 2,3-dimethyl-1,5-pentanediol (PD9 manufactured by Kyowa Hakko), 3-methoxy-3-methyl-1-butanol, 1-hexanol 1,3-butanediol, 1-pentanol, 2-methyl 1-butanol, 4-methyl-2-pentanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerin and the like.
  • Solfit AC trade name: Kuraray
  • EEP ethoxyethyl propionate
  • alcohol solvents 1-butanol
  • Diadol 135 trade name: manufactured by Mitsubishi Rayon
  • ether solvents include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether, ethylene glycol butyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, diethylene glycol butyl ether, and diethylene glycol ethyl ether. Can be mentioned.
  • hydrocarbon solvents examples include Solvesso 100, Solvesso 150 (trade name: manufactured by Exxon Chemical), and N-methylpyrrolidone. These may be a mixture of each system and a plurality of systems. Of these, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-butyl acetate, ethoxyethyl propionate, and Diadol 135 are preferable in view of their evaporation rate and surface tension.
  • the conductive ink for reversal printing of the present invention can further contain water as a solvent.
  • the conductive ink for reversal printing of the present invention can further contain a melamine resin for further improvement of adhesion.
  • the melamine resin include a non-catalytic and thermosetting function, for example, a residue contained in melamine having a methylol group or an imino group.
  • the content of the melamine resin in the ink is desirably about 0.1 to 2%. Furthermore, if intended to improve conductivity, 0.1 to 0.4% is more preferable.
  • a dispersant can be added as necessary to improve the dispersion stability of the ink.
  • the Solsperse series (trade name, manufactured by Lubrisol) and the DISPER BYK series (trade name, manufactured by Big Chemie) can be added as necessary.
  • the method for producing a conductive ink for reverse printing according to the present invention comprises a silver particle ethanol dispersion (A-1), a fast-drying organic solvent D, a slow-drying organic solvent prepared by adding silver nitrate to the polymer compound (X).
  • E, mold release agent C, and surface energy adjusting agent B can be blended and prepared according to a conventional method. Water and melamine resin can be added as necessary.
  • the precipitate was dissolved in 100 ml of chloroform and reprecipitated again by adding a mixed solvent of 150 ml of ethyl acetate and 450 ml of hexane. This was filtered and dried under reduced pressure. Each peak is assigned by 1H-NMR spectrum (2.3 to 2.7 ppm: ethylene of branched PEI, 3.3 ppm: methyl group at the PEG end, 3.6 ppm: EG chain of PEG), PEG-branched PEI structure It was confirmed that the polymer compound had The yield was 99%.
  • Example 1 A solution obtained by dissolving 20 mg of the polymer compound (X-1) having a ratio of the branched polyethyleneimine chain (a) to the hydrophilic polyethylene glycol chain (b) of 1: 3 in 2.39 g of water, obtained in Synthesis Example 1.
  • 1A a solution obtained by dissolving 20 mg of the polymer compound (X-1) having a ratio of the branched polyethyleneimine chain (a) to the hydrophilic polyethylene glycol chain (b) of 1: 3 in 2.39 g of water, obtained in Synthesis Example 1.
  • 1A a solution 1B in which 0.16 g of silver nitrate was dissolved in 1.30 g of water, and a solution 1C in which 0.12 g of sodium citrate was dissolved in 0.25 g of water were prepared. While stirring at 25 ° C., solution 1B was added to solution 1A, followed by solution 1C.
  • the average particle diameter of the silver particles was 30 nm
  • the silver content in the dispersion was 29% by mass
  • the content of the polymer compound (X-1) was 1.2% by mass.
  • Example 2 Silver particle ethanol dispersion (A-1), 1.0 g, ethanol (fast drying organic solvent D) 0.33 g, 2,3-dimethyl-1,5-pentanediol (slow drying organic solvent E: manufactured by Kyowa Hakko PD9 ) 10% ethanol solution 0.59g, Silicone oil (release agent C: SH28PA manufactured by Toray Dow Chemical) 10% ethanol solution 0.30g, Fluorosurfactant (Surface energy modifier: DIC Corporation Mega Facque TF-1303) 30 g% methyl ethyl ketone (MEK) solution 0.05 g, melamine resin (Imino type melamine resin: Cymel 325 manufactured by Nihon Cydic Industries Co., Ltd.) 10 mass% ethanol solution 0.40 g Stir for minutes to prepare Example 2 ink.
  • A-1 Silver particle ethanol dispersion
  • ethanol fast drying organic solvent
  • D fast drying organic solvent
  • Example 3 Silver particle ethanol dispersion (A-1), 1.0 g, ethanol (fast drying organic solvent D) 0.80 g, glycerin (slow drying organic solvent E) 10 mass% ethanol solution 0.26 g, silicone oil (release) Agent C: 0.24 g of a 10% by mass ethanol solution (KF96-2cs) manufactured by Shin-Etsu Chemical Co., Ltd., 0.02 g of a 10% by mass ethanol solution of a silicone-based surfactant (surface energy modifier B: BYK-333 manufactured by BYK Chemie) Blended and stirred for 10 minutes to prepare Example 3 ink.
  • KF96-2cs 10% by mass ethanol solution
  • surface energy modifier B BYK-333 manufactured by BYK Chemie
  • Comparative Example 1 Ethanol solution of silver particle ethanol dispersion (A-1), 1.0 g, 1.10 g of ethanol (fast-drying organic solvent D), 10% by mass of silicone oil (release agent C: KF96-2cs manufactured by Shin-Etsu Chemical) 24 g and 0.02 g of a 10 mass% ethanol solution (surface energy adjusting agent B: BYK-333 manufactured by BYK-Chemie Co., Ltd.) were mixed and stirred for 10 minutes to prepare Comparative Example 1 ink.
  • surface energy adjusting agent B BYK-333 manufactured by BYK-Chemie Co., Ltd.
  • the pattern is formed on the blanket, it is transferred to a glass substrate after 240 seconds and the printed material is heated and baked at 180 ° C. for 30 minutes, and then the surface of the coating film is rubbed with a finger and the peelability is observed.
  • the conductive ink for reversal printing according to the present invention enables high-resolution printing particularly in combination with the printing method.
  • Applicable fields include, for example, the formation of source or drain electrodes of organic transistors.
  • high carrier injection efficiency is required at the interface between each electrode and the organic semiconductor.
  • In-air photoelectron spectroscopy can be applied as a method for evaluating the amount of impurities present on the surface of a printed material.
  • a conductive ink for reversal printing that has not only the conductivity and resolution of the ink film, but also functions such as extending the transferable time to the printed material in the printing process.
  • the ink can be widely applied to electronic devices such as organic transistors because of its high resolution and excellent conductivity.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

L’invention concerne une encre électriquement conductrice pour impression en transparence, qui est excellente à la fois en termes de conductivité du film d’encre et de résolution, et qui peut prolonger la durée pendant laquelle le transfert sur un substrat est possible lors de l’étape d’impression. L’invention concerne ainsi une encre électriquement conductrice pour impression en transparence, caractérisée en ce qu’elle comprend une dispersion de nanoparticules métalliques (A) qui contient à la fois une dispersion d’un composé polymère (X) portant une chaîne polyalkylène imine (a) et un segment hydrophile (b), et des nanoparticules métalliques (Y), un régulateur de l’énergie de surface (B), un agent de démoulage (C), un solvant organique à séchage rapide (D) et un solvant organique à séchage lent (E).
PCT/JP2009/061278 2008-06-23 2009-06-22 Encre électriquement conductrice pour impression en transparence WO2009157393A1 (fr)

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WO2012084813A1 (fr) 2010-12-21 2012-06-28 Agfa-Gevaert Dispersion comprenant des nanoparticules métalliques, d'oxyde de métal ou de précurseur de métal
EP2608218A1 (fr) 2011-12-21 2013-06-26 Agfa-Gevaert Dispersion comportant des nanoparticules métalliques, oxyde métallique ou précurseur métallique, dispersant polymère et agent clivable thermique
EP2608217A1 (fr) 2011-12-21 2013-06-26 Agfa-Gevaert Dispersion comportant des nanoparticules métalliques, oxyde métallique ou précurseur métallique, dispersant polymère et additif de frittage
EP2671927A1 (fr) 2012-06-05 2013-12-11 Agfa-Gevaert Cassette à chaîne et véhicule motorisé à deux roues doté de celle-ci
EP2781562A1 (fr) 2013-03-20 2014-09-24 Agfa-Gevaert Procédé pour préparer une dispersion de nanoparticules métalliques
EP2821164A1 (fr) 2013-07-04 2015-01-07 Agfa-Gevaert Dispersion de nanoparticules métalliques
WO2015000932A1 (fr) 2013-07-04 2015-01-08 Agfa-Gevaert Procédé de préparation d'une couche ou d'un motif métallique conducteur
WO2015000937A1 (fr) 2013-07-04 2015-01-08 Agfa-Gevaert Dispersion de nanoparticules métalliques
JP2016511773A (ja) * 2013-12-05 2016-04-21 Dic株式会社 金属ナノ粒子保護ポリマー、金属コロイド溶液及びそれらの製造方法
EP3037161A1 (fr) 2014-12-22 2016-06-29 Agfa-Gevaert Dispersion de nanoparticules métalliques
EP3099146A1 (fr) 2015-05-27 2016-11-30 Agfa-Gevaert Dispersion de nanoparticules metalliques
EP3099145A1 (fr) 2015-05-27 2016-11-30 Agfa-Gevaert Dispersion de nanoparticules metalliques
EP3287499A1 (fr) 2016-08-26 2018-02-28 Agfa-Gevaert Dispersion de nanoparticules métalliques
WO2019215068A1 (fr) 2018-05-08 2019-11-14 Agfa-Gevaert Nv Encres conductrices

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JP2006213887A (ja) * 2005-02-07 2006-08-17 Dainippon Ink & Chem Inc 金属固定高分子会合体とその製造方法
JP2007254635A (ja) * 2006-03-24 2007-10-04 Dainippon Ink & Chem Inc 導電性インキ組成物および印刷物
JP2008038180A (ja) * 2006-08-03 2008-02-21 Dainippon Ink & Chem Inc 金属ナノ粒子分散体、およびその製造方法
JP2008056884A (ja) * 2006-08-04 2008-03-13 Hitachi Chem Co Ltd 印刷インキ組成物及び該組成物を用いたカラーフィルターの製造方法

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JP2006213887A (ja) * 2005-02-07 2006-08-17 Dainippon Ink & Chem Inc 金属固定高分子会合体とその製造方法
JP2007254635A (ja) * 2006-03-24 2007-10-04 Dainippon Ink & Chem Inc 導電性インキ組成物および印刷物
JP2008038180A (ja) * 2006-08-03 2008-02-21 Dainippon Ink & Chem Inc 金属ナノ粒子分散体、およびその製造方法
JP2008056884A (ja) * 2006-08-04 2008-03-13 Hitachi Chem Co Ltd 印刷インキ組成物及び該組成物を用いたカラーフィルターの製造方法

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012084813A1 (fr) 2010-12-21 2012-06-28 Agfa-Gevaert Dispersion comprenant des nanoparticules métalliques, d'oxyde de métal ou de précurseur de métal
US9275773B2 (en) 2010-12-21 2016-03-01 Agfa-Gevaert N.V. Dispersion comprising metallic, metal oxide or metal precursor nanoparticles
EP2608218A1 (fr) 2011-12-21 2013-06-26 Agfa-Gevaert Dispersion comportant des nanoparticules métalliques, oxyde métallique ou précurseur métallique, dispersant polymère et agent clivable thermique
EP2608217A1 (fr) 2011-12-21 2013-06-26 Agfa-Gevaert Dispersion comportant des nanoparticules métalliques, oxyde métallique ou précurseur métallique, dispersant polymère et additif de frittage
WO2013092450A1 (fr) 2011-12-21 2013-06-27 Agfa-Gevaert Dispersion comprenant des nanoparticules métalliques, d'oxyde de métal ou de précurseur de métal, dispersant polymère et agent thermiquement clivable
WO2013092576A1 (fr) 2011-12-21 2013-06-27 Agfa-Gevaert Dispersion comprenant des nanoparticules métalliques, d'oxyde de métal ou de précurseurs de métal, dispersant polymère et additif de frittage
EP2671927A1 (fr) 2012-06-05 2013-12-11 Agfa-Gevaert Cassette à chaîne et véhicule motorisé à deux roues doté de celle-ci
WO2013182588A1 (fr) 2012-06-05 2013-12-12 Agfa-Gevaert Dispersion de nanoparticules métalliques
EP2781562A1 (fr) 2013-03-20 2014-09-24 Agfa-Gevaert Procédé pour préparer une dispersion de nanoparticules métalliques
WO2014147079A1 (fr) 2013-03-20 2014-09-25 Agfa-Gevaert Procédé permettant de préparer une dispersion de nanoparticules métalliques
WO2015000891A1 (fr) 2013-07-04 2015-01-08 Agfa-Gevaert Dispersion de nanoparticules métalliques
WO2015000932A1 (fr) 2013-07-04 2015-01-08 Agfa-Gevaert Procédé de préparation d'une couche ou d'un motif métallique conducteur
WO2015000937A1 (fr) 2013-07-04 2015-01-08 Agfa-Gevaert Dispersion de nanoparticules métalliques
EP2821164A1 (fr) 2013-07-04 2015-01-07 Agfa-Gevaert Dispersion de nanoparticules métalliques
JP2016511773A (ja) * 2013-12-05 2016-04-21 Dic株式会社 金属ナノ粒子保護ポリマー、金属コロイド溶液及びそれらの製造方法
EP3037161A1 (fr) 2014-12-22 2016-06-29 Agfa-Gevaert Dispersion de nanoparticules métalliques
US10676630B2 (en) 2014-12-22 2020-06-09 Agfa-Gevaert Metallic nanoparticle dispersion
EP3099146A1 (fr) 2015-05-27 2016-11-30 Agfa-Gevaert Dispersion de nanoparticules metalliques
EP3099145A1 (fr) 2015-05-27 2016-11-30 Agfa-Gevaert Dispersion de nanoparticules metalliques
WO2016189016A1 (fr) 2015-05-27 2016-12-01 Agfa-Gevaert Dispersion de nanoparticules métalliques
EP3287499A1 (fr) 2016-08-26 2018-02-28 Agfa-Gevaert Dispersion de nanoparticules métalliques
WO2018037072A1 (fr) 2016-08-26 2018-03-01 Agfa-Gevaert N.V. Dispersion de nanoparticules métalliques
WO2019215068A1 (fr) 2018-05-08 2019-11-14 Agfa-Gevaert Nv Encres conductrices

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