WO2013111856A1 - Silver ink composition - Google Patents

Silver ink composition Download PDF

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Publication number
WO2013111856A1
WO2013111856A1 PCT/JP2013/051590 JP2013051590W WO2013111856A1 WO 2013111856 A1 WO2013111856 A1 WO 2013111856A1 JP 2013051590 W JP2013051590 W JP 2013051590W WO 2013111856 A1 WO2013111856 A1 WO 2013111856A1
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WO
WIPO (PCT)
Prior art keywords
group
silver
ink composition
carbon atoms
aliphatic hydrocarbon
Prior art date
Application number
PCT/JP2013/051590
Other languages
French (fr)
Japanese (ja)
Inventor
久美 廣瀬
真里奈 今井
Original Assignee
トッパン・フォームズ株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP2012284712A external-priority patent/JP6116236B2/en
Priority claimed from JP2012284711A external-priority patent/JP6116235B2/en
Application filed by トッパン・フォームズ株式会社 filed Critical トッパン・フォームズ株式会社
Priority to KR1020147019482A priority Critical patent/KR20140106693A/en
Priority to CN201380005696.0A priority patent/CN104053733A/en
Priority to US14/371,913 priority patent/US9371465B2/en
Priority to KR1020167030225A priority patent/KR101763194B1/en
Publication of WO2013111856A1 publication Critical patent/WO2013111856A1/en
Priority to HK15101466.6A priority patent/HK1200861A1/en

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Classifications

    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • 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

Definitions

  • the present invention relates to a silver ink composition suitable for application to an inkjet printing method.
  • This application is filed on January 27, 2012, Japanese Patent Application No. 2012-15581 filed in Japan, January 27, 2012, Japanese Patent Application No. 2012-15582 filed in Japan, December 27, 2012
  • the priority is claimed based on Japanese Patent Application No. 2012-284711 filed in Japan and Japanese Patent Application No. 2012-284712 filed on December 27, 2012, the contents of which are incorporated herein by reference.
  • Metallic silver is widely used as a recording material, a printing plate material, and a highly conductive material because of its excellent conductivity.
  • a silver ink composition containing metallic silver or a component that forms the metallic silver is prepared, and this composition is attached to a substrate by various printing methods. Accordingly, in order to form a metallic silver film, a method of heating (firing) the deposited composition is employed. In order to form a fine metallic silver pattern, an inkjet printing method is widely used as the printing method.
  • a silver ink composition suitable for application to such an ink jet printing method those obtained by dispersing silver nanoparticles in various organic solvents are disclosed (see Patent Documents 1 and 2).
  • the silver ink compositions described in Patent Documents 1 and 2 require an operation of preparing silver nanoparticles as a raw material by reducing silver nitrate using a reducing agent. Has a problem that a complicated process is involved.
  • the present invention has been made in view of the above circumstances, and provides a silver ink composition that can be produced by a simple method, is suitable for application to an inkjet printing method, and can form a practical amount of metallic silver. This is the issue.
  • the present invention relates to a silver carboxylate having a group represented by the formula “—COOAg”, an aliphatic primary amine or secondary amine having 2 to 10 carbon atoms, and an acetylene alcohol represented by the following general formula (2): And a silver ink composition characterized by having a viscosity at 27 ° C. of 40 mPa ⁇ s or less.
  • a hydrocarbon having 6 to 14 carbon atoms is preferably blended, and the dynamic surface tension at 27 ° C. is preferably 56 mN / m or less.
  • R ′ and R ′′ are each independently an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.
  • the silver carboxylate is preferably silver ⁇ -ketocarboxylate represented by the following general formula (1).
  • R represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, a phenyl group, a hydroxyl group, an amino group, or a group represented by the general formula “R 1 -CY 2- ",” CY 3- “,” R 1 -CHY- “,” R 2 O- “,” R 5 R 4 N- “,” (R 3 O) 2 CY- “or” R 6 -C ( ⁇ O) —CY 2 — ”;
  • Y is independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom;
  • R 1 is an aliphatic hydrocarbon group or phenyl group having 1 to 19 carbon atoms;
  • R 2 is an aliphatic group having 1 to 20 carbon atoms
  • R 3 is an aliphatic hydrocarbon group having 1 to 16 carbon atoms;
  • R 4 and R 5 are each independently an aliphatic hydrocarbon group having 1
  • the R is represented by a linear or branched alkyl group, a phenyl group, or the general formula “R 6 —C ( ⁇ O) —CY 2 —”.
  • X is preferably a hydrogen atom, a linear or branched alkyl group, or a benzyl group.
  • the silver ⁇ -ketocarboxylate is silver 2-methylacetoacetate, silver acetoacetate, silver 2-ethylacetoacetate, silver propionylacetate, silver isobutyrylacetate, silver pivaloylacetate, 2-n- One or more selected from the group consisting of silver butyl acetoacetate, silver 2-benzylacetoacetate, silver benzoyl acetate, silver pivaloyl acetoacetate, silver isobutyryl acetoacetate and silver acetone dicarboxylate is preferred.
  • the aliphatic hydrocarbon group bonded to the nitrogen atom of the primary amine or secondary amine is preferably a linear or branched alkyl group.
  • the primary amine or secondary amine is 2-ethylhexylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine. , N-octylamine, N-methylhexylamine, and N-ethylhexylamine are preferable.
  • R ′ and R ′′ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
  • the acetylene alcohols are 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol and 3-methyl-1-pentyne- It is preferably at least one selected from the group consisting of 3-ols.
  • a silver ink composition that can be produced by a simple method, is suitable for application to an ink jet printing method, and can form a practical amount of metallic silver.
  • the silver ink composition of the present invention is a silver carboxylate having a group represented by the formula “—COOAg” (hereinafter sometimes simply referred to as “silver carboxylate”), an aliphatic group having 2 to 10 carbon atoms.
  • amine compound Primary amine or secondary amine
  • acetylene alcohol represented by the following general formula (2)
  • hydrocarbon having 6 to 20 carbon atoms
  • the viscosity at 27 ° C. is 40 mPa ⁇ s or less.
  • R ′ and R ′′ are each independently an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.
  • the silver carboxylate is not particularly limited as long as it has a group represented by the formula “—COOAg”.
  • the number of groups represented by the formula “—COOAg” may be one, or two or more.
  • the position of the group represented by the formula “—COOAg” in the silver carboxylate is not particularly limited.
  • the silver carboxylate is decomposed by heating or the like to form metallic silver.
  • the silver carboxylate may be used alone or in combination of two or more.
  • the combination and ratio can be adjusted arbitrarily.
  • the silver carboxylate is preferably a silver ⁇ -ketocarboxylate represented by the following general formula (1) (hereinafter sometimes abbreviated as “silver ⁇ -ketocarboxylate”).
  • the term “silver carboxylate” includes not only “silver ⁇ -ketocarboxylate” but also a group represented by the formula “—COOAg”. Means silver carboxylate ".
  • R represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, a phenyl group, a hydroxyl group, an amino group, or a group represented by the general formula “R 1 -CY 2- ",” CY 3- “,” R 1 -CHY- “,” R 2 O- “,” R 5 R 4 N- “,” (R 3 O) 2 CY- “or” R 6 -C ( ⁇ O) —CY 2 — ”;
  • Y is independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom;
  • R 1 is an aliphatic hydrocarbon group or phenyl group having 1 to 19 carbon atoms;
  • R 2 is an aliphatic group having 1 to 20 carbon atoms
  • R 3 is an aliphatic hydrocarbon group having 1 to 16 carbon atoms;
  • R 4 and R 5 are each independently an aliphatic hydrocarbon group having 1
  • the silver ⁇ -ketocarboxylate is represented by the general formula (1).
  • R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, a phenyl group, a hydroxyl group, an amino group, or a group represented by the general formula “R 1 -CY 2 -”,” CY 3- “,” R 1 -CHY- “,” R 2 O- ",” R 5 R 4 N- ",” (R 3 O) 2 CY- "or” R 6 -C ( ⁇ O) —CY 2 — ”.
  • the aliphatic hydrocarbon group having 1 to 20 carbon atoms in R may be any of linear, branched and cyclic (aliphatic cyclic group), and may be monocyclic or polycyclic when cyclic. . Further, the aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Preferred examples of the aliphatic hydrocarbon group for R include an alkyl group, an alkenyl group, and an alkynyl group.
  • Examples of the linear or branched alkyl group in R include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -Pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4- Methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group 1-ethyl-1-methylpropyl group,
  • Examples of the cyclic alkyl group in R include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2- Examples thereof include an adamantyl group and a tricyclodecyl group.
  • alkenyl group in R examples include a vinyl group (ethenyl group, —CH ⁇ CH 2 ), an allyl group (2-propenyl group, —CH 2 —CH ⁇ CH 2 ), and a 1-propenyl group (—CH ⁇ CH—CH).
  • one single bond (C—C) between carbon atoms of the alkyl group in R such as ethynyl group (—C ⁇ CH), propargyl group (—CH 2 —C ⁇ CH), etc. ) Is substituted with a triple bond (C ⁇ C).
  • one or more hydrogen atoms may be substituted with a substituent, and preferred examples of the substituent include a fluorine atom, a chlorine atom, and a bromine atom.
  • the number and position of substituents are not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other. That is, all the substituents may be the same, all the substituents may be different, or only some of the substituents may be different.
  • one or more hydrogen atoms may be substituted with a substituent.
  • the substituent include a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms.
  • a monovalent group formed by bonding the aliphatic hydrocarbon group to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group (—OH), a cyano group (—C ⁇ N), a phenoxy group (—O—), C 6 H 5 ) and the like can be exemplified, and the number and position of substituents are not particularly limited.
  • the plural substituents may be the same as or different from each other.
  • Examples of the aliphatic hydrocarbon group that is a substituent include the same aliphatic hydrocarbon groups as those described above for R except that the number of carbon atoms is 1 to 16.
  • Y in R each independently represents a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom.
  • a plurality of Y may be the same or different from each other.
  • R 1 in R is an aliphatic hydrocarbon group having 1 to 19 carbon atoms or a phenyl group (C 6 H 5 —), and the aliphatic hydrocarbon group in R 1 has 1 to 19 carbon atoms. Except for this point, the same aliphatic hydrocarbon groups as those in R can be exemplified.
  • R 2 in R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and examples thereof are the same as the aliphatic hydrocarbon group in R.
  • R 3 in R is an aliphatic hydrocarbon group having 1 to 16 carbon atoms, and examples thereof are the same as the aliphatic hydrocarbon group in R except that the carbon number is 1 to 16.
  • R 4 and R 5 in R are each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms. That is, R 4 and R 5 may be the same as or different from each other, and examples thereof are the same as the aliphatic hydrocarbon group for R except that the number of carbon atoms is 1 to 18.
  • R 6 in R is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a hydroxyl group or a group represented by the formula “AgO—”. The aliphatic hydrocarbon group in R 6 has 1 to Except for being 19, the same aliphatic hydrocarbon groups as those described above for R can be exemplified.
  • R is preferably a linear or branched alkyl group, a phenyl group, or a group represented by the general formula “R 6 —C ( ⁇ O) —CY 2 —”.
  • R 6 is preferably a linear or branched alkyl group, a hydroxyl group, or a group represented by the formula “AgO—”.
  • each X independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a phenyl group in which one or more hydrogen atoms may be substituted with a substituent, or benzyl A group (C 6 H 5 —CH 2 —), a cyano group, an N-phthaloyl-3-aminopropyl group, a 2-ethoxyvinyl group (C 2 H 5 —O—CH ⁇ CH—), or the general formula “R 7 It is a group represented by “O—”, “R 7 S—”, “R 7 —C ( ⁇ O) —” or “R 7 —C ( ⁇ O) —O—”.
  • Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms in X include those similar to the aliphatic hydrocarbon group in R.
  • halogen atom in X examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • substituents include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), nitro Examples include a group (—NO 2 ), and the number and position of substituents are not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other.
  • R 7 in X represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group (C 4 H 3 S—), or a phenyl group or diphenyl in which one or more hydrogen atoms may be substituted with a substituent. group (biphenyl group, C 6 H 5 -C 6 H 4 -) it is.
  • Examples of the aliphatic hydrocarbon group for R 7 include those similar to the aliphatic hydrocarbon group for R except that the aliphatic hydrocarbon group has 1 to 10 carbon atoms.
  • examples of the substituent of the phenyl group and a diphenyl group in R 7, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) can be exemplified the like, the number and position of the substituent is not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other.
  • R 7 is a thienyl group or a diphenyl group
  • the bonding position of these with an adjacent group or atom (oxygen atom, sulfur atom, carbonyl group, carbonyloxy group) in X is not particularly limited.
  • the thienyl group may be either a 2-thienyl group or a 3-thienyl group.
  • two Xs may be bonded as one group through a double bond with a carbon atom sandwiched between two carbonyl groups.
  • a group represented by “ ⁇ CH—C 6 H 4 —NO 2 ” can be exemplified.
  • X is preferably a hydrogen atom, a linear or branched alkyl group, or a benzyl group, and at least one X is preferably a hydrogen atom.
  • the silver ⁇ -ketocarboxylate is silver 2-methylacetoacetate (CH 3 —C ( ⁇ O) —CH (CH 3 ) —C ( ⁇ O) —OAg), silver acetoacetate (CH 3 —C ( ⁇ O)) —CH 2 —C ( ⁇ O) —OAg), silver 2-ethylacetoacetate (CH 3 —C ( ⁇ O) —CH (CH 2 CH 3 ) —C ( ⁇ O) —OAg), silver propionyl acetate (CH 3 CH 2 —C ( ⁇ O) —CH 2 —C ( ⁇ O) —OAg), silver isobutyryl acetate ((CH 3 ) 2 CH—C ( ⁇ O) —CH 2 —C ( ⁇ O) —OAg) , Silver pivaloyl acetate ((CH 3 ) 3 C—C ( ⁇ O) —CH 2 —C ( ⁇ O) —OAg), silver 2-n-butylacetoacetate (CH 3 —
  • the concentration of the remaining raw materials and impurities can be further reduced in the metallic silver formed by the heating (firing) treatment.
  • the silver ⁇ -ketocarboxylate decomposes at a low temperature of preferably 60 to 210 ° C., more preferably 60 to 200 ° C. without using a reducing agent known in the art. Form.
  • silver ⁇ -ketocarboxylate may be used alone or in combination of two or more.
  • the combination and ratio can be adjusted arbitrarily.
  • the silver content in the silver carboxylate is preferably 17% by mass or more, and more preferably 18% by mass or more. By setting it as such a range, the metal silver formed with the method mentioned later becomes favorable in electroconductivity, and becomes more excellent in quality.
  • the upper limit of the silver content is not particularly limited as long as the effect of the present invention is not hindered, but it is preferably 25% by mass in consideration of handleability and the like.
  • the amine compound is an aliphatic primary amine or an aliphatic secondary amine, and is not particularly limited as long as the total number of carbon atoms is 2 to 10, but is preferably bonded to a nitrogen atom.
  • the aliphatic hydrocarbon group is an alkyl group (alkylamine, dialkylamine).
  • the alkyl group may be linear, branched or cyclic.
  • linear or branched alkyl group examples include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group.
  • the cyclic alkyl group may be monocyclic or polycyclic, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, adamantyl group Group, tricyclodecyl group and the like.
  • the amine compound is preferably one in which the alkyl group bonded to the nitrogen atom is linear or branched.
  • the amine preferably has 2 to 9 carbon atoms, more preferably 3 to 8 carbon atoms, specifically, n-propylamine, n-butylamine, n-pentylamine, n- Examples include hexylamine, n-heptylamine, 2-ethylhexylamine, n-octylamine, N-methylhexylamine, N-ethylhexylamine and the like.
  • the amine compounds may be used alone or in combination of two or more. When using 2 or more types together, the combination and ratio may be appropriately selected according to the purpose.
  • the compounding amount of the amine compound is preferably 1 to 6 mol, and more preferably 1.5 to 5 mol, per mol of the carboxylate silver.
  • acetylene alcohols are represented by the general formula (2).
  • R ′ and R ′′ are each independently an alkyl group having 1 to 20 carbon atoms or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.
  • the alkyl group having 1 to 20 carbon atoms in R ′ and R ′′ may be any of linear, branched and cyclic (aliphatic cyclic group). When cyclic, it may be any of monocyclic or polycyclic But you can. Examples of the alkyl group in R ′ and R ′′ include the same alkyl groups as in R.
  • Examples of the substituent in which the hydrogen atom of the phenyl group in R ′ and R ′′ may be substituted include a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, the aliphatic carbon A monovalent group in which a hydrogen group is bonded to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a cyano group, a phenoxy group, etc. can be exemplified, and the hydrogen atom of the phenyl group in R may be substituted Same as the group.
  • the number and position of the substituents are not particularly limited, and when the number of substituents is plural, the plural substituents may be the same as or different from each other.
  • R ′ and R ′′ are preferably an alkyl group having 1 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
  • acetylene alcohols include 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, and 3-methyl-1-pentyn-3-ol.
  • acetylene alcohols may be used alone or in combination of two or more.
  • the combination and ratio can be arbitrarily adjusted.
  • the blending amount of acetylene alcohols is preferably 0.03 to 0.7 mole, and preferably 0.06 to 0.3 mole, per mole of the above-mentioned silver carboxylate. More preferred.
  • the compounding quantity of acetylene alcohol more than a lower limit, the use effect of acetylene alcohol becomes higher, and metallic silver of better quality can be formed by making it the upper limit or less.
  • the hydrocarbon has 6 to 20 carbon atoms, and may be linear, branched or cyclic, and may be any of saturated hydrocarbon and unsaturated hydrocarbon.
  • the hydrocarbon is preferably liquid at 15 to 37 ° C., and more preferably liquid at 15 to 30 ° C.
  • linear or branched saturated hydrocarbon examples include n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-heptane, 2-methyl Hexane, 3-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane, n -Octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,3- Dimethylhexane, 3,4-dimethylhexane, 2,2,3-trimethylpentane, 2,2,4-trimethylpentane (
  • the cyclic saturated hydrocarbon may be monocyclic or polycyclic, but is preferably monocyclic, preferably has 8 or less carbon atoms, and examples thereof include cyclohexane, cycloheptane, and cyclooctane.
  • the unsaturated hydrocarbon one or more single bonds (C—C) between carbon atoms of the saturated hydrocarbon are unsaturated bonds (double bonds (C ⁇ C), triple bonds (C ⁇ C)).
  • the unsaturated hydrocarbon may have either a double bond or a triple bond as an unsaturated bond between carbon atoms, or may have both, and the number of unsaturated bonds. And the position is not particularly limited, but the number of unsaturated bonds is preferably 1 or 2.
  • the unsaturated hydrocarbon may be either cis type or trans type.
  • the unsaturated hydrocarbon is preferably an alkene or alkyne.
  • the hydrocarbons may be used singly or in combination of two or more.
  • the combination and ratio can be arbitrarily adjusted.
  • the compounding amount of the hydrocarbon is preferably 0.05 to 2 mol, more preferably 0.1 to 1.5 mol, per mol of the carboxylate silver. .
  • the viscosity of the silver ink composition can be adjusted to a more suitable low value, and by setting it to the upper limit value or less, metallic silver of better quality can be formed.
  • the silver ink composition may be further blended with other components not corresponding to these within a range not impeding the effects of the present invention.
  • the total blending amount of the silver carboxylate, amine compound, acetylene alcohols and hydrocarbons in the total blending component is preferably 85% by mass or more, and 90% by mass or more. Is more preferably 95% by mass or more, and may be 100% by mass.
  • the viscosity at 27 ° C. of the silver ink composition is 40 mPa ⁇ s or less, preferably 37 mPa ⁇ s or less, and more preferably 33 mPa ⁇ s or less.
  • the silver ink composition has physical properties suitable for the ink jet printing method.
  • the lower limit of the viscosity is not particularly limited, but is preferably 5 mPa ⁇ s in consideration of the handleability of the silver ink composition.
  • the viscosity of the silver ink composition can be measured according to a known method, for example, an ultrasonic viscometer.
  • the viscosity of the silver ink composition can be adjusted by, for example, the type and amount of the blending component, but can be easily adjusted by the type of the hydrocarbon.
  • the viscosity at 27 ° C. of the silver ink composition has been described, but the temperature at the time of use of the silver ink composition is not limited to 27 ° C. and can be arbitrarily selected.
  • the viscosity at 27 ° C. is in the above range, the silver ink composition exhibits an excellent effect under normal use conditions.
  • the silver ink composition has a dynamic surface tension at 27 ° C. of 56 mN / m or less, and preferably 53 mN / m or less. With such a range, the silver ink composition is suitable for the inkjet printing method. It will have the physical properties.
  • the lower limit value of the dynamic surface tension is not particularly limited, but is preferably 28 mN / m in consideration of the handleability of the silver ink composition.
  • the “dynamic surface tension” is calculated using, for example, a so-called “maximum value” that is calculated using the maximum value of the pressure that the bubbles receive from the silver ink composition when bubbles are generated in the silver ink composition. It is calculated
  • the silver ink composition preferably has a static surface tension at 27 ° C. of 30 mN / m or less, and more preferably 28 mN / m or less. By being in such a range, the silver ink composition has physical properties more suitable for the ink jet printing method.
  • the lower limit value of the static surface tension is not particularly limited, but is preferably 14 mN / m in consideration of the handleability of the silver ink composition. In the present invention, for example, the surface tension when the bubble frequency is any of 0.05 to 0.2 Hz by the maximum bubble pressure method may be set to “static surface tension”.
  • the silver ink composition preferably has a surface tension at a bubble frequency of 1 Hz at 27 ° C. in the maximum bubble pressure method of 45 mN / m or less, more preferably 40 mN / m or less. By being in such a range, the silver ink composition has physical properties more suitable for the ink jet printing method.
  • the lower limit value of the surface tension at 1 Hz is not particularly limited, but is preferably 21 mN / m in consideration of the handleability of the silver ink composition.
  • the surface tension (dynamic surface tension, static surface tension, etc.) of the silver ink composition can be adjusted by, for example, the type and amount of the blending component, but can be easily adjusted by the type of the hydrocarbon.
  • the temperature at the time of use of the silver ink composition is not limited to 27 ° C. and can be arbitrarily selected.
  • the surface tension at 27 ° C. is in the above range, the silver ink composition exhibits an excellent effect under normal use conditions.
  • the silver ink composition can be obtained by blending the silver carboxylate, amine compound, acetylene alcohols and hydrocarbons, and, if necessary, the other components. At the time of blending each component, all the components may be added and then mixed, or some components may be mixed while being added sequentially, or all components may be mixed while being added sequentially. Good.
  • the mixing method is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, a method of adding ultrasonic waves, and the like. .
  • the blending component may be dissolved in the silver ink composition, or a part of the components may be dispersed without being dissolved.
  • the temperature at the time of blending is not particularly limited as long as each blended component does not deteriorate, but is preferably ⁇ 5 to 30 ° C.
  • the silver ink composition of the present invention can easily form metallic silver by thermally decomposing silver carboxylate by heating (firing) treatment at a temperature of 60 to 200 ° C., for example. Therefore, a silver metal composition can be formed by applying the silver ink composition to various printing methods such as an ink jet printing method suitable for the viscosity and heat-treating the obtained print pattern.
  • the heating temperature at the time of forming metallic silver may be appropriately adjusted according to the type of silver carboxylate.
  • the silver carboxylate is decomposed at a low temperature of preferably 60 to 210 ° C., more preferably 60 to 200 ° C. to form metallic silver. Therefore, reflecting such a decomposition temperature, the silver ink composition of the present invention has a lower temperature than the conventional metal silver forming material as described above, without using a reducing agent known in the art. Metal silver can be formed.
  • the heating time may be adjusted as appropriate according to the heating temperature.
  • the substrate to be inkjet-printed with the silver ink composition may be a known one, and examples thereof include an ink receiving layer provided on a substrate, but are not limited thereto.
  • the material of the substrate is not particularly limited, and may be selected according to the purpose.
  • paper such as base paper, art paper, coated paper, cast coated paper, resin coated paper, synthetic paper; polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resin, AS resin, ABS resin , Polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyphenylene sulfide, polysulfone, polycarbonate, epoxy resin, melamine resin, phenol resin, urea resin, polyurethane, polyimide, etc.
  • synthetic resin are as follows. Two or more kinds of materials may be laminated.
  • the base material is preferably in the form of a sheet or a film, and preferably has a thickness of 20 to 1000 ⁇ m.
  • the ink receiving layer preferably has a thickness of 1 to 20 ⁇ m. By setting the thickness of the ink receiving layer in such a range, the structure of the ink receiving layer can be more stably maintained, and the quality of the printed matter is further improved.
  • the silver ink composition of the present invention is suitable for application to an ink jet printing method because the viscosity is in the above numerical range. It can be produced by an extremely simple method in which each component is simply blended at a predetermined temperature. Moreover, the obtained silver ink composition can form a practical amount of metallic silver very easily by heat treatment without using the reducing agent or the like.
  • “plurality” means that the number may be at least two or more.
  • Example 1 Manufacture of silver ink composition
  • 2-ethylhexylamine (3.1 g), 3,5-dimethyl-1-hexyn-3-ol (“Surfinol 61” manufactured by Air Products Japan) (0.17 g) and n-octane (0.8 g)
  • a silver ink composition was obtained by adding the mixture into a 13.5 mL vial and stirring, and further adding silver 2-methylacetoacetate (3.0 g) under ice cooling and stirring for 30 minutes.
  • Table 1 shows the amount of each component.
  • Examples 2 to 17, Comparative Examples 1 to 3 A silver ink composition was produced and evaluated in the same manner as in Example 1 except that the types and blending amounts of the components were as shown in Table 1. The results are shown in Table 2. In Table 1, “-” indicates that the component is not blended. Further, metallic silver was produced and evaluated in the same manner as in Example 1 using the obtained silver ink composition. The results are shown in Table 2. In Table 2, “OL” indicates that the value is too large to be measured (overload).
  • the silver ink composition of the present invention has a viscosity of 31 mPa ⁇ s or less, can be easily ejected, and can be confirmed to be suitable for application to the ink jet printing method. Further, a sufficient amount of metallic silver was formed, and its resistance value was as small as 0.4 ⁇ / ⁇ or less, and it was stable even when the heat treatment time changed, and was suitable as a conductive material. On the other hand, the silver ink composition of Comparative Example 1 was not suitable for application to the ink jet printing method because it had a high viscosity and was difficult to discharge because it did not contain hydrocarbons.
  • the silver ink composition of Comparative Example 2 was not suitable for application to the ink jet printing method due to the high viscosity, difficulty in ejection due to the inadequate type of the blended hydrocarbon. Further, the formed metallic silver had a remarkably high resistance value, and the value could not be measured. In addition, the silver ink composition of Comparative Example 3 did not contain hydrocarbons, whereas the amount of silver carboxylate was less than that of Comparative Example 1 and the amount of amine compound was increased. Although the viscosity was low, the formed metallic silver had a high resistance value.
  • Example 18 to 23 A silver ink composition was produced and evaluated in the same manner as in Example 1 except that the types and blending amounts of the components were as shown in Table 3. The results are shown in Table 4. Further, metallic silver was produced and evaluated in the same manner as in Example 1 using the obtained silver ink composition. The results are shown in Table 4.
  • the silver ink composition of the present invention has a viscosity of 25.6 mPa ⁇ s or less, can be easily ejected, and can be confirmed to be suitable for application to the ink jet printing method. It was. Further, a sufficient amount of metallic silver was formed, its resistance value was as small as 5.2 ⁇ / ⁇ or less, and it was stable even when the heat treatment time was changed, and was suitable as a conductive material.
  • the present invention can be used as an ink for ink-jet printing, and is particularly useful for forming a fine metallic silver pattern.

Abstract

A silver ink composition which is characterized by being obtained by blending a silver carboxylate having a group represented by formula -COOAg, an aliphatic primary amine or secondary amine having 2-10 carbon atoms, an acetylene alcohol represented by general formula (2), and a hydrocarbon having 6-20 carbon atoms. This silver ink composition is also characterized by having a viscosity at 27˚C of 40 mPa·s or less. (In general formula (2), each of R' and R'' independently represents an alkyl group having 1-20 carbon atoms or a phenyl group wherein one or more hydrogen atoms may be substituted by substituents.)

Description

銀インク組成物Silver ink composition
　本発明は、インクジェット印刷法への適用に好適な銀インク組成物に関する。
本願は、２０１２年１月２７日に、日本に出願された特願２０１２－１５５８１号、２０１２年１月２７日に、日本に出願された特願２０１２－１５５８２号、２０１２年１２月２７日に、日本に出願された特願２０１２－２８４７１１号及び２０１２年１２月２７日に、日本に出願された特願２０１２－２８４７１２号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a silver ink composition suitable for application to an inkjet printing method.
This application is filed on January 27, 2012, Japanese Patent Application No. 2012-15581 filed in Japan, January 27, 2012, Japanese Patent Application No. 2012-15582 filed in Japan, December 27, 2012 The priority is claimed based on Japanese Patent Application No. 2012-284711 filed in Japan and Japanese Patent Application No. 2012-284712 filed on December 27, 2012, the contents of which are incorporated herein by reference.
　金属銀は、記録材料や印刷刷版の材料として、また、導電性に優れることから高導電性材料として幅広く使用されている。通常、金属銀をこのような用途に適用する場合には、金属銀又はその形成材料となる成分を含む銀インク組成物を調製し、この組成物を各種印刷法によって被印刷物に付着させ、必要に応じて金属銀の被膜を形成するために、付着した組成物を加熱（焼成）する手法が採用される。微細な金属銀のパターンを形成するためには、前記印刷法としてインクジェット印刷法が汎用される。
　このようなインクジェット印刷法への適用に好適な銀インク組成物としては、銀ナノ粒子を各種有機溶媒中に分散させて得られたものが開示されている（特許文献１及び２参照）。 Metallic silver is widely used as a recording material, a printing plate material, and a highly conductive material because of its excellent conductivity. Usually, when metallic silver is applied to such applications, a silver ink composition containing metallic silver or a component that forms the metallic silver is prepared, and this composition is attached to a substrate by various printing methods. Accordingly, in order to form a metallic silver film, a method of heating (firing) the deposited composition is employed. In order to form a fine metallic silver pattern, an inkjet printing method is widely used as the printing method.
As a silver ink composition suitable for application to such an ink jet printing method, those obtained by dispersing silver nanoparticles in various organic solvents are disclosed (see Patent Documents 1 and 2).
特表２０１０－５０４４０９号公報Special table 2010-504409 特開２０１０－１９６１５０号公報JP 2010-196150 A
　しかし、特許文献１及び２に記載の銀インク組成物では、還元剤を使用して硝酸銀を還元することにより、原料である銀ナノ粒子を調製する操作が必要であり、銀インク組成物の製造には煩雑な工程が伴うという問題点がある。 However, the silver ink compositions described in Patent Documents 1 and 2 require an operation of preparing silver nanoparticles as a raw material by reducing silver nitrate using a reducing agent. Has a problem that a complicated process is involved.
　本発明は、上記事情に鑑みてなされたものであり、簡便な方法で製造でき、インクジェット印刷法への適用に好適であり、実用的な量の金属銀を形成できる銀インク組成物を提供することを課題とする。 The present invention has been made in view of the above circumstances, and provides a silver ink composition that can be produced by a simple method, is suitable for application to an inkjet printing method, and can form a practical amount of metallic silver. This is the issue.
　上記課題を解決するため、
　本発明は、式「－ＣＯＯＡｇ」で表される基を有するカルボン酸銀、炭素数２～１０の脂肪族第一級アミン又は第二級アミン、下記一般式（２）で表されるアセチレンアルコール類、及び炭素数６～２０の炭化水素が配合されてなり、２７℃における粘度が４０ｍＰａ・ｓ以下であることを特徴とする銀インク組成物を提供する。
　本発明の銀インク組成物においては、炭素数６～１４の炭化水素が配合されてなり、２７℃における動的表面張力が５６ｍＮ／ｍ以下であることが好ましい。 To solve the above problem,
The present invention relates to a silver carboxylate having a group represented by the formula “—COOAg”, an aliphatic primary amine or secondary amine having 2 to 10 carbon atoms, and an acetylene alcohol represented by the following general formula (2): And a silver ink composition characterized by having a viscosity at 27 ° C. of 40 mPa · s or less.
In the silver ink composition of the present invention, a hydrocarbon having 6 to 14 carbon atoms is preferably blended, and the dynamic surface tension at 27 ° C. is preferably 56 mN / m or less.
Figure JPOXMLDOC01-appb-C000003
 　　　　　　　　　　　　　　　　　　
（式中、Ｒ’及びＲ’’は、それぞれ独立に炭素数１～２０のアルキル基、又は１個以上の水素原子が置換基で置換されていてもよいフェニル基である。）
Figure JPOXMLDOC01-appb-C000003
(In the formula, R ′ and R ″ are each independently an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.)
　本発明の銀インク組成物においては、前記カルボン酸銀が、下記一般式（１）で表されるβ－ケトカルボン酸銀であることが好ましい。 In the silver ink composition of the present invention, the silver carboxylate is preferably silver β-ketocarboxylate represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000004
 　　　　　　　　　　　　　　　　　　

　（式中、Ｒは１個以上の水素原子が置換基で置換されていてもよい炭素数１～２０の脂肪族炭化水素基若しくはフェニル基、水酸基、アミノ基、又は一般式「Ｒ１－ＣＹ２－」、「ＣＹ３－」、「Ｒ１－ＣＨＹ－」、「Ｒ２Ｏ－」、「Ｒ５Ｒ４Ｎ－」、「（Ｒ３Ｏ）２ＣＹ－」若しくは「Ｒ６－Ｃ（＝Ｏ）－ＣＹ２－」で表される基であり；
　Ｙはそれぞれ独立にフッ素原子、塩素原子、臭素原子又は水素原子であり；Ｒ１は炭素数１～１９の脂肪族炭化水素基又はフェニル基であり；Ｒ２は炭素数１～２０の脂肪族炭化水素基であり；Ｒ３は炭素数１～１６の脂肪族炭化水素基であり；Ｒ４及びＲ５はそれぞれ独立に炭素数１～１８の脂肪族炭化水素基であり；Ｒ６は炭素数１～１９の脂肪族炭化水素基、水酸基又は式「ＡｇＯ－」で表される基であり；
　Ｘはそれぞれ独立に水素原子、炭素数１～２０の脂肪族炭化水素基、ハロゲン原子、１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはベンジル基、シアノ基、Ｎ－フタロイル－３－アミノプロピル基、２－エトキシビニル基、又は一般式「Ｒ７Ｏ－」、「Ｒ７Ｓ－」、「Ｒ７－Ｃ（＝Ｏ）－」若しくは「Ｒ７－Ｃ（＝Ｏ）－Ｏ－」で表される基であり；
　Ｒ７は、炭素数１～１０の脂肪族炭化水素基、チエニル基、又は１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはジフェニル基である。）
Figure JPOXMLDOC01-appb-C000004

(Wherein R represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, a phenyl group, a hydroxyl group, an amino group, or a group represented by the general formula “R 1 -CY 2- "," CY 3- "," R 1 -CHY- "," R 2 O- "," R 5 R 4 N- "," (R 3 O) 2 CY- "or" R 6 -C (═O) —CY 2 — ”;
Y is independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom; R 1 is an aliphatic hydrocarbon group or phenyl group having 1 to 19 carbon atoms; R 2 is an aliphatic group having 1 to 20 carbon atoms R 3 is an aliphatic hydrocarbon group having 1 to 16 carbon atoms; R 4 and R 5 are each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms; R 6 is a carbon group; An aliphatic hydrocarbon group of formula 1 to 19, a hydroxyl group or a group represented by the formula “AgO—”;
X is independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a phenyl group or benzyl group in which one or more hydrogen atoms may be substituted with a substituent, a cyano group, N— A phthaloyl-3-aminopropyl group, a 2-ethoxyvinyl group, or a general formula “R 7 O—”, “R 7 S—”, “R 7 —C (═O) —” or “R 7 —C (= O) —O— ”,
R 7 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group, or a phenyl group or diphenyl group in which one or more hydrogen atoms may be substituted with a substituent. )
　本発明の銀インク組成物においては、前記Ｒが直鎖状若しくは分枝鎖状のアルキル基、フェニル基、又は前記一般式「Ｒ６－Ｃ（＝Ｏ）－ＣＹ２－」で表される基であり、前記Ｘが水素原子、直鎖状若しくは分枝鎖状のアルキル基、又はベンジル基であることが好ましい。
　本発明の銀インク組成物においては、前記β－ケトカルボン酸銀が、２－メチルアセト酢酸銀、アセト酢酸銀、２－エチルアセト酢酸銀、プロピオニル酢酸銀、イソブチリル酢酸銀、ピバロイル酢酸銀、２－ｎ－ブチルアセト酢酸銀、２－ベンジルアセト酢酸銀、ベンゾイル酢酸銀、ピバロイルアセト酢酸銀、イソブチリルアセト酢酸銀及びアセトンジカルボン酸銀からなる群から選択される一種以上であることが好ましい。
　本発明の銀インク組成物においては、前記第一級アミン又は第二級アミンの窒素原子に結合している脂肪族炭化水素基が、直鎖状又は分岐鎖状のアルキル基であることが好ましい。
　本発明の銀インク組成物においては、前記第一級アミン又は第二級アミンが、２－エチルヘキシルアミン、ｎ－プロピルアミン、ｎ－ブチルアミン、ｎ－ペンチルアミン、ｎ－ヘキシルアミン、ｎ－ヘプチルアミン、ｎ－オクチルアミン、Ｎ－メチルヘキシルアミン及びＮ－エチルヘキシルアミンからなる群から選択される一種以上であることが好ましい。
　本発明の銀インク組成物においては、前記Ｒ’及びＲ’’が、炭素数１～１０の直鎖状又は分岐鎖状のアルキル基であることが好ましい。
　本発明の銀インク組成物においては、前記アセチレンアルコール類が、３，５－ジメチル－１－ヘキシン－３－オール、３－メチル－１－ブチン－３－オール及び３－メチル－１－ペンチン－３－オールからなる群から選択される一種以上であることが好ましい。 In the silver ink composition of the present invention, the R is represented by a linear or branched alkyl group, a phenyl group, or the general formula “R 6 —C (═O) —CY 2 —”. And X is preferably a hydrogen atom, a linear or branched alkyl group, or a benzyl group.
In the silver ink composition of the present invention, the silver β-ketocarboxylate is silver 2-methylacetoacetate, silver acetoacetate, silver 2-ethylacetoacetate, silver propionylacetate, silver isobutyrylacetate, silver pivaloylacetate, 2-n- One or more selected from the group consisting of silver butyl acetoacetate, silver 2-benzylacetoacetate, silver benzoyl acetate, silver pivaloyl acetoacetate, silver isobutyryl acetoacetate and silver acetone dicarboxylate is preferred.
In the silver ink composition of the present invention, the aliphatic hydrocarbon group bonded to the nitrogen atom of the primary amine or secondary amine is preferably a linear or branched alkyl group. .
In the silver ink composition of the present invention, the primary amine or secondary amine is 2-ethylhexylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine. , N-octylamine, N-methylhexylamine, and N-ethylhexylamine are preferable.
In the silver ink composition of the present invention, R ′ and R ″ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
In the silver ink composition of the present invention, the acetylene alcohols are 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol and 3-methyl-1-pentyne- It is preferably at least one selected from the group consisting of 3-ols.
　本発明によれば、簡便な方法で製造でき、インクジェット印刷法への適用に好適であり、実用的な量の金属銀を形成できる銀インク組成物が提供される。 According to the present invention, there is provided a silver ink composition that can be produced by a simple method, is suitable for application to an ink jet printing method, and can form a practical amount of metallic silver.
＜銀インク組成物＞
　本発明の銀インク組成物は、式「－ＣＯＯＡｇ」で表される基を有するカルボン酸銀（以下、単に「カルボン酸銀」と略記することがある）、炭素数２～１０の脂肪族第一級アミン又は第二級アミン（以下、「アミン化合物」と略記することがある）、下記一般式（２）で表されるアセチレンアルコール類（以下、「アセチレンアルコール類」と略記することがある）、及び炭素数６～２０の炭化水素（以下、「炭化水素」と略記することがある）が配合されてなり、２７℃における粘度が４０ｍＰａ・ｓ以下であることを特徴とする。 <Silver ink composition>
The silver ink composition of the present invention is a silver carboxylate having a group represented by the formula “—COOAg” (hereinafter sometimes simply referred to as “silver carboxylate”), an aliphatic group having 2 to 10 carbon atoms. Primary amine or secondary amine (hereinafter sometimes abbreviated as “amine compound”), acetylene alcohol represented by the following general formula (2) (hereinafter sometimes abbreviated as “acetylene alcohol”) And a hydrocarbon having 6 to 20 carbon atoms (hereinafter sometimes abbreviated as “hydrocarbon”), and the viscosity at 27 ° C. is 40 mPa · s or less.
Figure JPOXMLDOC01-appb-C000005
 　　　　　　　　　　　　　　　　　　
（式中、Ｒ’及びＲ’’は、それぞれ独立に炭素数１～２０のアルキル基、又は１個以上の水素原子が置換基で置換されていてもよいフェニル基である。）
Figure JPOXMLDOC01-appb-C000005
(In the formula, R ′ and R ″ are each independently an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.)
［カルボン酸銀］
　前記カルボン酸銀は、式「－ＣＯＯＡｇ」で表される基を有していれば特に限定されない。例えば、式「－ＣＯＯＡｇ」で表される基の数は１個のみでもよいし、２個以上でもよい。また、カルボン酸銀中の式「－ＣＯＯＡｇ」で表される基の位置も特に限定されない。
　前記カルボン酸銀は、加熱等によって分解し、金属銀を形成する。 [Silver carboxylate]
The silver carboxylate is not particularly limited as long as it has a group represented by the formula “—COOAg”. For example, the number of groups represented by the formula “—COOAg” may be one, or two or more. Further, the position of the group represented by the formula “—COOAg” in the silver carboxylate is not particularly limited.
The silver carboxylate is decomposed by heating or the like to form metallic silver.
　本発明において、前記カルボン酸銀は、一種を単独で使用してもよいし、二種以上を併用してもよい。二種以上を併用する場合、その組み合わせ及び比率は、任意に調節できる。 In the present invention, the silver carboxylate may be used alone or in combination of two or more. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.
　前記カルボン酸銀は、下記一般式（１）で表されるβ－ケトカルボン酸銀（以下、「β－ケトカルボン酸銀」と略記することがある）であることが好ましい。
　本明細書においては、単なる「カルボン酸銀」との記載は、特に断りの無い限り、「β－ケトカルボン酸銀」だけではなく、これらを包括する、「式「－ＣＯＯＡｇ」で表される基を有するカルボン酸銀」を意味する。 The silver carboxylate is preferably a silver β-ketocarboxylate represented by the following general formula (1) (hereinafter sometimes abbreviated as “silver β-ketocarboxylate”).
In the present specification, unless otherwise specified, the term “silver carboxylate” includes not only “silver β-ketocarboxylate” but also a group represented by the formula “—COOAg”. Means silver carboxylate ".
Figure JPOXMLDOC01-appb-C000006
 　　　　　　　　　　　　　　　　　　

　（式中、Ｒは１個以上の水素原子が置換基で置換されていてもよい炭素数１～２０の脂肪族炭化水素基若しくはフェニル基、水酸基、アミノ基、又は一般式「Ｒ１－ＣＹ２－」、「ＣＹ３－」、「Ｒ１－ＣＨＹ－」、「Ｒ２Ｏ－」、「Ｒ５Ｒ４Ｎ－」、「（Ｒ３Ｏ）２ＣＹ－」若しくは「Ｒ６－Ｃ（＝Ｏ）－ＣＹ２－」で表される基であり；
　Ｙはそれぞれ独立にフッ素原子、塩素原子、臭素原子又は水素原子であり；Ｒ１は炭素数１～１９の脂肪族炭化水素基又はフェニル基であり；Ｒ２は炭素数１～２０の脂肪族炭化水素基であり；Ｒ３は炭素数１～１６の脂肪族炭化水素基であり；Ｒ４及びＲ５はそれぞれ独立に炭素数１～１８の脂肪族炭化水素基であり；Ｒ６は炭素数１～１９の脂肪族炭化水素基、水酸基又は式「ＡｇＯ－」で表される基であり；
　Ｘはそれぞれ独立に水素原子、炭素数１～２０の脂肪族炭化水素基、ハロゲン原子、１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはベンジル基、シアノ基、Ｎ－フタロイル－３－アミノプロピル基、２－エトキシビニル基、又は一般式「Ｒ７Ｏ－」、「Ｒ７Ｓ－」、「Ｒ７－Ｃ（＝Ｏ）－」若しくは「Ｒ７－Ｃ（＝Ｏ）－Ｏ－」で表される基であり；
　Ｒ７は、炭素数１～１０の脂肪族炭化水素基、チエニル基、又は１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはジフェニル基である。）
Figure JPOXMLDOC01-appb-C000006

(Wherein R represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, a phenyl group, a hydroxyl group, an amino group, or a group represented by the general formula “R 1 -CY 2- "," CY 3- "," R 1 -CHY- "," R 2 O- "," R 5 R 4 N- "," (R 3 O) 2 CY- "or" R 6 -C (═O) —CY 2 — ”;
Y is independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom; R 1 is an aliphatic hydrocarbon group or phenyl group having 1 to 19 carbon atoms; R 2 is an aliphatic group having 1 to 20 carbon atoms R 3 is an aliphatic hydrocarbon group having 1 to 16 carbon atoms; R 4 and R 5 are each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms; R 6 is a carbon group; An aliphatic hydrocarbon group of formula 1 to 19, a hydroxyl group or a group represented by the formula “AgO—”;
X is independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a phenyl group or benzyl group in which one or more hydrogen atoms may be substituted with a substituent, a cyano group, N— A phthaloyl-3-aminopropyl group, a 2-ethoxyvinyl group, or a general formula “R 7 O—”, “R 7 S—”, “R 7 —C (═O) —” or “R 7 —C (= O) —O— ”,
R 7 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group, or a phenyl group or diphenyl group in which one or more hydrogen atoms may be substituted with a substituent. )
（β－ケトカルボン酸銀）
　本発明において、前記β－ケトカルボン酸銀は、前記一般式（１）で表される。
　式中、Ｒは１個以上の水素原子が置換基で置換されていてもよい炭素数１～２０の脂肪族炭化水素基若しくはフェニル基、水酸基、アミノ基、又は一般式「Ｒ１－ＣＹ２－」、「ＣＹ３－」、「Ｒ１－ＣＨＹ－」、「Ｒ２Ｏ－」、「Ｒ５Ｒ４Ｎ－」、「（Ｒ３Ｏ）２ＣＹ－」若しくは「Ｒ６－Ｃ（＝Ｏ）－ＣＹ２－」で表される基である。 (Silver β-ketocarboxylate)
In the present invention, the silver β-ketocarboxylate is represented by the general formula (1).
In the formula, R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, a phenyl group, a hydroxyl group, an amino group, or a group represented by the general formula “R 1 -CY 2 -"," CY 3- "," R 1 -CHY- "," R 2 O- "," R 5 R 4 N- "," (R 3 O) 2 CY- "or" R 6 -C ( ═O) —CY 2 — ”.
　Ｒにおける炭素数１～２０の脂肪族炭化水素基は、直鎖状、分岐鎖状及び環状（脂肪族環式基）のいずれでもよく、環状である場合、単環状及び多環状のいずれでもよい。また、前記脂肪族炭化水素基は、飽和脂肪族炭化水素基及び不飽和脂肪族炭化水素基のいずれでもよい。前記脂肪族炭化水素基は、炭素数が１～１０であることが好ましく、１～６であることがより好ましい。Ｒにおける好ましい前記脂肪族炭化水素基としては、アルキル基、アルケニル基、アルキニル基が例示できる。 The aliphatic hydrocarbon group having 1 to 20 carbon atoms in R may be any of linear, branched and cyclic (aliphatic cyclic group), and may be monocyclic or polycyclic when cyclic. . Further, the aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Preferred examples of the aliphatic hydrocarbon group for R include an alkyl group, an alkenyl group, and an alkynyl group.
　Ｒにおける直鎖状又は分枝鎖状の前記アルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ－ペンチル基、１－メチルブチル基、２－メチルブチル基、ｎ－ヘキシル基、１－メチルペンチル基、２－メチルペンチル基、３－メチルペンチル基、４－メチルペンチル基、１，１－ジメチルブチル基、２，２－ジメチルブチル基、３，３－ジメチルブチル基、２，３－ジメチルブチル基、１－エチルブチル基、２－エチルブチル基、３－エチルブチル基、１－エチル－１－メチルプロピル基、ｎ－ヘプチル基、１－メチルヘキシル基、２－メチルヘキシル基、３－メチルヘキシル基、４－メチルヘキシル基、５－メチルヘキシル基、１，１－ジメチルペンチル基、２，２－ジメチルペンチル基、２，３－ジメチルペンチル基、２，４－ジメチルペンチル基、３，３－ジメチルペンチル基、４，４－ジメチルペンチル基、１－エチルペンチル基、２－エチルペンチル基、３－エチルペンチル基、４－エチルペンチル基、２，２，３－トリメチルブチル基、１－プロピルブチル基、ｎ－オクチル基、イソオクチル基、１－メチルヘプチル基、２－メチルヘプチル基、３－メチルヘプチル基、４－メチルヘプチル基、５－メチルヘプチル基、１－エチルヘキシル基、２－エチルヘキシル基、３－エチルヘキシル基、４－エチルヘキシル基、５－エチルヘキシル基、１，１－ジメチルヘキシル基、２，２－ジメチルヘキシル基、３，３－ジメチルヘキシル基、４，４－ジメチルヘキシル基、５，５－ジメチルヘキシル基、１－プロピルペンチル基、２－プロピルペンチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基が例示できる。
　Ｒにおける環状の前記アルキル基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、ノルボルニル基、イソボルニル基、１－アダマンチル基、２－アダマンチル基、トリシクロデシル基が例示できる。 Examples of the linear or branched alkyl group in R include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -Pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4- Methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group 1-ethyl-1-methylpropyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, -Methylhexyl group, 5-methylhexyl group, 1,1-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group 4,4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 4-ethylpentyl group, 2,2,3-trimethylbutyl group, 1-propylbutyl group, n -Octyl, isooctyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl Group, 4-ethylhexyl group, 5-ethylhexyl group, 1,1-dimethylhexyl group, 2,2-dimethylhexyl group, 3, -Dimethylhexyl group, 4,4-dimethylhexyl group, 5,5-dimethylhexyl group, 1-propylpentyl group, 2-propylpentyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group And pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and icosyl group.
Examples of the cyclic alkyl group in R include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2- Examples thereof include an adamantyl group and a tricyclodecyl group.
　Ｒにおける前記アルケニル基としては、ビニル基（エテニル基、－ＣＨ＝ＣＨ２）、アリル基（２－プロペニル基、－ＣＨ２－ＣＨ＝ＣＨ２）、１－プロペニル基（－ＣＨ＝ＣＨ－ＣＨ３）、イソプロペニル基（－Ｃ（ＣＨ３）＝ＣＨ２）、１－ブテニル基（－ＣＨ＝ＣＨ－ＣＨ２－ＣＨ３）、２－ブテニル基（－ＣＨ２－ＣＨ＝ＣＨ－ＣＨ３）、３－ブテニル基（－ＣＨ２－ＣＨ２－ＣＨ＝ＣＨ２）、シクロヘキセニル基、シクロペンテニル基等の、Ｒにおける前記アルキル基の炭素原子間の１個の単結合（Ｃ－Ｃ）が二重結合（Ｃ＝Ｃ）に置換された基が例示できる。
　Ｒにおける前記アルキニル基としては、エチニル基（－Ｃ≡ＣＨ）、プロパルギル基（－ＣＨ２－Ｃ≡ＣＨ）等の、Ｒにおける前記アルキル基の炭素原子間の１個の単結合（Ｃ－Ｃ）が三重結合（Ｃ≡Ｃ）に置換された基が例示できる。 Examples of the alkenyl group in R include a vinyl group (ethenyl group, —CH═CH 2 ), an allyl group (2-propenyl group, —CH 2 —CH═CH 2 ), and a 1-propenyl group (—CH═CH—CH). 3 ), isopropenyl group (—C (CH 3 ) ═CH 2 ), 1-butenyl group (—CH═CH—CH 2 —CH 3 ), 2-butenyl group (—CH 2 —CH═CH—CH 3) ), 3-butenyl group (—CH 2 —CH 2 —CH═CH 2 ), cyclohexenyl group, cyclopentenyl group and the like, one single bond (C—C) between the carbon atoms of the alkyl group in R Is a group in which is substituted with a double bond (C═C).
As the alkynyl group in R, one single bond (C—C) between carbon atoms of the alkyl group in R, such as ethynyl group (—C≡CH), propargyl group (—CH 2 —C≡CH), etc. ) Is substituted with a triple bond (C≡C).
　Ｒにおける炭素数１～２０の脂肪族炭化水素基は、１個以上の水素原子が置換基で置換されていてもよく、好ましい前記置換基としては、フッ素原子、塩素原子、臭素原子が例示できる。また、置換基の数及び位置は特に限定されない。置換基の数が複数である場合、これら複数個の置換基は互いに同一でも異なっていてもよい。すなわち、すべての置換基が同一であってもよいし、すべての置換基が異なっていてもよく、一部の置換基のみが異なっていてもよい。 In the aliphatic hydrocarbon group having 1 to 20 carbon atoms in R, one or more hydrogen atoms may be substituted with a substituent, and preferred examples of the substituent include a fluorine atom, a chlorine atom, and a bromine atom. . Moreover, the number and position of substituents are not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other. That is, all the substituents may be the same, all the substituents may be different, or only some of the substituents may be different.
　Ｒにおけるフェニル基は、１個以上の水素原子が置換基で置換されていてもよく、好ましい前記置換基としては、炭素数が１～１６の飽和又は不飽和の一価の脂肪族炭化水素基、前記脂肪族炭化水素基が酸素原子に結合してなる一価の基、フッ素原子、塩素原子、臭素原子、水酸基（－ＯＨ）、シアノ基（－Ｃ≡Ｎ）、フェノキシ基（－Ｏ－Ｃ６Ｈ５）等が例示でき、置換基の数及び位置は特に限定されない。置換基の数が複数である場合、これら複数個の置換基は互いに同一でも異なっていてもよい。
　置換基である前記脂肪族炭化水素基としては、炭素数が１～１６である点以外は、Ｒにおける前記脂肪族炭化水素基と同様のものが例示できる。 In the phenyl group in R, one or more hydrogen atoms may be substituted with a substituent. Preferred examples of the substituent include a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms. A monovalent group formed by bonding the aliphatic hydrocarbon group to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group (—OH), a cyano group (—C≡N), a phenoxy group (—O—), C 6 H 5 ) and the like can be exemplified, and the number and position of substituents are not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other.
Examples of the aliphatic hydrocarbon group that is a substituent include the same aliphatic hydrocarbon groups as those described above for R except that the number of carbon atoms is 1 to 16.
　ＲにおけるＹは、それぞれ独立にフッ素原子、塩素原子、臭素原子又は水素原子である。一般式「Ｒ１－ＣＹ２－」、「ＣＹ３－」及び「Ｒ６－Ｃ（＝Ｏ）－ＣＹ２－」においては、それぞれ複数個のＹは、互いに同一でも異なっていてもよい。 Y in R each independently represents a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom. In the general formulas “R 1 -CY 2 —”, “CY 3 —” and “R 6 —C (═O) —CY 2 —”, a plurality of Y may be the same or different from each other.
　ＲにおけるＲ１は、炭素数１～１９の脂肪族炭化水素基又はフェニル基（Ｃ６Ｈ５－）であり、Ｒ１における前記脂肪族炭化水素基としては、炭素数が１～１９である点以外は、Ｒにおける前記脂肪族炭化水素基と同様のものが例示できる。
　ＲにおけるＲ２は、炭素数１～２０の脂肪族炭化水素基であり、Ｒにおける前記脂肪族炭化水素基と同様のものが例示できる。
　ＲにおけるＲ３は、炭素数１～１６の脂肪族炭化水素基であり、炭素数が１～１６である点以外は、Ｒにおける前記脂肪族炭化水素基と同様のものが例示できる。
　ＲにおけるＲ４及びＲ５は、それぞれ独立に炭素数１～１８の脂肪族炭化水素基である。すなわち、Ｒ４及びＲ５は、互いに同一でも異なっていてもよく、炭素数が１～１８である点以外は、Ｒにおける前記脂肪族炭化水素基と同様のものが例示できる。
　ＲにおけるＲ６は、炭素数１～１９の脂肪族炭化水素基、水酸基又は式「ＡｇＯ－」で表される基であり、Ｒ６における前記脂肪族炭化水素基としては、炭素数が１～１９である点以外は、Ｒにおける前記脂肪族炭化水素基と同様のものが例示できる。 R 1 in R is an aliphatic hydrocarbon group having 1 to 19 carbon atoms or a phenyl group (C 6 H 5 —), and the aliphatic hydrocarbon group in R 1 has 1 to 19 carbon atoms. Except for this point, the same aliphatic hydrocarbon groups as those in R can be exemplified.
R 2 in R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and examples thereof are the same as the aliphatic hydrocarbon group in R.
R 3 in R is an aliphatic hydrocarbon group having 1 to 16 carbon atoms, and examples thereof are the same as the aliphatic hydrocarbon group in R except that the carbon number is 1 to 16.
R 4 and R 5 in R are each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms. That is, R 4 and R 5 may be the same as or different from each other, and examples thereof are the same as the aliphatic hydrocarbon group for R except that the number of carbon atoms is 1 to 18.
R 6 in R is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a hydroxyl group or a group represented by the formula “AgO—”. The aliphatic hydrocarbon group in R 6 has 1 to Except for being 19, the same aliphatic hydrocarbon groups as those described above for R can be exemplified.
　Ｒは、上記の中でも、直鎖状若しくは分枝鎖状のアルキル基、フェニル基、又は一般式「Ｒ６－Ｃ（＝Ｏ）－ＣＹ２－」で表される基であることが好ましい。Ｒ６は、直鎖状若しくは分枝鎖状のアルキル基、水酸基又は式「ＡｇＯ－」で表される基であることが好ましい。 Among these, R is preferably a linear or branched alkyl group, a phenyl group, or a group represented by the general formula “R 6 —C (═O) —CY 2 —”. R 6 is preferably a linear or branched alkyl group, a hydroxyl group, or a group represented by the formula “AgO—”.
　一般式（１）において、Ｘはそれぞれ独立に水素原子、炭素数１～２０の脂肪族炭化水素基、ハロゲン原子、１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはベンジル基（Ｃ６Ｈ５－ＣＨ２－）、シアノ基、Ｎ－フタロイル－３－アミノプロピル基、２－エトキシビニル基（Ｃ２Ｈ５－Ｏ－ＣＨ＝ＣＨ－）、又は一般式「Ｒ７Ｏ－」、「Ｒ７Ｓ－」、「Ｒ７－Ｃ（＝Ｏ）－」若しくは「Ｒ７－Ｃ（＝Ｏ）－Ｏ－」で表される基である。
　Ｘにおける炭素数１～２０の脂肪族炭化水素基としては、Ｒにおける前記脂肪族炭化水素基と同様のものが例示できる。 In the general formula (1), each X independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a phenyl group in which one or more hydrogen atoms may be substituted with a substituent, or benzyl A group (C 6 H 5 —CH 2 —), a cyano group, an N-phthaloyl-3-aminopropyl group, a 2-ethoxyvinyl group (C 2 H 5 —O—CH═CH—), or the general formula “R 7 It is a group represented by “O—”, “R 7 S—”, “R 7 —C (═O) —” or “R 7 —C (═O) —O—”.
Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms in X include those similar to the aliphatic hydrocarbon group in R.
　Ｘにおけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が例示できる。
　Ｘにおけるフェニル基及びベンジル基は、１個以上の水素原子が置換基で置換されていてもよく、好ましい前記置換基としては、ハロゲン原子（フッ素原子、塩素原子、臭素原子、ヨウ素原子）、ニトロ基（－ＮＯ２）等が例示でき、置換基の数及び位置は特に限定されない。置換基の数が複数である場合、これら複数個の置換基は互いに同一でも異なっていてもよい。 Examples of the halogen atom in X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In the phenyl group and benzyl group in X, one or more hydrogen atoms may be substituted with a substituent. Preferred examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), nitro Examples include a group (—NO 2 ), and the number and position of substituents are not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other.
　ＸにおけるＲ７は、炭素数１～１０の脂肪族炭化水素基、チエニル基（Ｃ４Ｈ３Ｓ－）、又は１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはジフェニル基（ビフェニル基、Ｃ６Ｈ５－Ｃ６Ｈ４－）である。Ｒ７における前記脂肪族炭化水素基としては、炭素数が１～１０である点以外は、Ｒにおける前記脂肪族炭化水素基と同様のものが例示できる。また、Ｒ７におけるフェニル基及びジフェニル基の前記置換基としては、ハロゲン原子（フッ素原子、塩素原子、臭素原子、ヨウ素原子）等が例示でき、置換基の数及び位置は特に限定されない。置換基の数が複数である場合、これら複数個の置換基は互いに同一でも異なっていてもよい。
　Ｒ７がチエニル基又はジフェニル基である場合、これらの、Ｘにおいて隣接する基又は原子（酸素原子、硫黄原子、カルボニル基、カルボニルオキシ基）との結合位置は、特に限定されない。例えば、チエニル基は、２－チエニル基及び３－チエニル基のいずれでもよい。 R 7 in X represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group (C 4 H 3 S—), or a phenyl group or diphenyl in which one or more hydrogen atoms may be substituted with a substituent. group (biphenyl group, C 6 H 5 -C 6 H 4 -) it is. Examples of the aliphatic hydrocarbon group for R 7 include those similar to the aliphatic hydrocarbon group for R except that the aliphatic hydrocarbon group has 1 to 10 carbon atoms. Further, examples of the substituent of the phenyl group and a diphenyl group in R 7, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) can be exemplified the like, the number and position of the substituent is not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other.
When R 7 is a thienyl group or a diphenyl group, the bonding position of these with an adjacent group or atom (oxygen atom, sulfur atom, carbonyl group, carbonyloxy group) in X is not particularly limited. For example, the thienyl group may be either a 2-thienyl group or a 3-thienyl group.
　一般式（１）において、２個のＸは、２個のカルボニル基で挟まれた炭素原子と二重結合を介して１個の基として結合していてもよく、このようなものとしては式「＝ＣＨ－Ｃ６Ｈ４－ＮＯ２」で表される基が例示できる。 In the general formula (1), two Xs may be bonded as one group through a double bond with a carbon atom sandwiched between two carbonyl groups. A group represented by “═CH—C 6 H 4 —NO 2 ” can be exemplified.
　Ｘは、上記の中でも、水素原子、直鎖状若しくは分枝鎖状のアルキル基、又はベンジル基であることが好ましく、少なくとも一方のＸが水素原子であることが好ましい。 X is preferably a hydrogen atom, a linear or branched alkyl group, or a benzyl group, and at least one X is preferably a hydrogen atom.
　前記β－ケトカルボン酸銀は、２－メチルアセト酢酸銀（ＣＨ３－Ｃ（＝Ｏ）－ＣＨ（ＣＨ３）－Ｃ（＝Ｏ）－ＯＡｇ）、アセト酢酸銀（ＣＨ３－Ｃ（＝Ｏ）－ＣＨ２－Ｃ（＝Ｏ）－ＯＡｇ）、２－エチルアセト酢酸銀（ＣＨ３－Ｃ（＝Ｏ）－ＣＨ（ＣＨ２ＣＨ３）－Ｃ（＝Ｏ）－ＯＡｇ）、プロピオニル酢酸銀（ＣＨ３ＣＨ２－Ｃ（＝Ｏ）－ＣＨ２－Ｃ（＝Ｏ）－ＯＡｇ）、イソブチリル酢酸銀（（ＣＨ３）２ＣＨ－Ｃ（＝Ｏ）－ＣＨ２－Ｃ（＝Ｏ）－ＯＡｇ）、ピバロイル酢酸銀（（ＣＨ３）３Ｃ－Ｃ（＝Ｏ）－ＣＨ２－Ｃ（＝Ｏ）－ＯＡｇ）、２－ｎ－ブチルアセト酢酸銀（ＣＨ３－Ｃ（＝Ｏ）－ＣＨ（ＣＨ２ＣＨ２ＣＨ２ＣＨ３）－Ｃ（＝Ｏ）－ＯＡｇ）、２－ベンジルアセト酢酸銀（ＣＨ３－Ｃ（＝Ｏ）－ＣＨ（ＣＨ２Ｃ６Ｈ５）－Ｃ（＝Ｏ）－ＯＡｇ）、ベンゾイル酢酸銀（Ｃ６Ｈ５－Ｃ（＝Ｏ）－ＣＨ２－Ｃ（＝Ｏ）－ＯＡｇ）、ピバロイルアセト酢酸銀（（ＣＨ３）３Ｃ－Ｃ（＝Ｏ）－ＣＨ２－Ｃ（＝Ｏ）－ＣＨ２－Ｃ（＝Ｏ）－ＯＡｇ）、イソブチリルアセト酢酸銀（（ＣＨ３）２ＣＨ－Ｃ（＝Ｏ）－ＣＨ２－Ｃ（＝Ｏ）－ＣＨ２－Ｃ（＝Ｏ）－ＯＡｇ）、又はアセトンジカルボン酸銀（ＡｇＯ－Ｃ（＝Ｏ）－ＣＨ２－Ｃ（＝Ｏ）－ＣＨ２－Ｃ（＝Ｏ）－ＯＡｇ）であることが好ましい。これらβ－ケトカルボン酸銀は、前記一般式（１）で表されるものの中でも、加熱（焼成）処理により形成された金属銀において、残存する原料や不純物の濃度をより低減できる。原料や不純物が少ない程、例えば、形成された金属銀同士の接触が良好となり、導通が容易となり、抵抗率が低下する。 The silver β-ketocarboxylate is silver 2-methylacetoacetate (CH 3 —C (═O) —CH (CH 3 ) —C (═O) —OAg), silver acetoacetate (CH 3 —C (═O)) —CH 2 —C (═O) —OAg), silver 2-ethylacetoacetate (CH 3 —C (═O) —CH (CH 2 CH 3 ) —C (═O) —OAg), silver propionyl acetate (CH 3 CH 2 —C (═O) —CH 2 —C (═O) —OAg), silver isobutyryl acetate ((CH 3 ) 2 CH—C (═O) —CH 2 —C (═O) —OAg) , Silver pivaloyl acetate ((CH 3 ) 3 C—C (═O) —CH 2 —C (═O) —OAg), silver 2-n-butylacetoacetate (CH 3 —C (═O) —CH (CH 2 CH 2 CH 2 CH 3 ) —C (═O) —OAg), silver 2-benzylacetoacetate (CH 3 —C (= O) —CH (CH 2 C 6 H 5 ) —C (═O) —OAg), silver benzoyl acetate (C 6 H 5 —C (═O) —CH 2 —C (═O) —OAg), pivaloylacetate Silver acetate ((CH 3 ) 3 C—C (═O) —CH 2 —C (═O) —CH 2 —C (═O) —OAg), silver isobutyrylacetoacetate ((CH 3 ) 2 CH —C (═O) —CH 2 —C (═O) —CH 2 —C (═O) —OAg), or silver acetone dicarboxylate (AgO—C (═O) —CH 2 —C (═O) —CH 2 —C (═O) —OAg) is preferred. Among these silver β-ketocarboxylates, among those represented by the general formula (1), the concentration of the remaining raw materials and impurities can be further reduced in the metallic silver formed by the heating (firing) treatment. The smaller the raw materials and impurities, for example, the better the contact between the formed metal silvers, the easier the conduction, and the lower the resistivity.
　前記β－ケトカルボン酸銀は、後述するように、当該分野で公知の還元剤等を使用しなくても、好ましくは６０～２１０℃、より好ましくは６０～２００℃という低温で分解し、金属銀を形成する。 As will be described later, the silver β-ketocarboxylate decomposes at a low temperature of preferably 60 to 210 ° C., more preferably 60 to 200 ° C. without using a reducing agent known in the art. Form.
　本発明において、β－ケトカルボン酸銀は、一種を単独で使用してもよいし、二種以上を併用してもよい。二種以上を併用する場合、その組み合わせ及び比率は、任意に調節できる。 In the present invention, silver β-ketocarboxylate may be used alone or in combination of two or more. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.
　銀インク組成物において、カルボン酸銀中の銀の含有量は、１７質量％以上であることが好ましく、１８質量％以上であることがより好ましい。このような範囲とすることで、後述する方法で形成された金属銀は、導電性が良好となり、品質により優れたものとなる。前記銀の含有量の上限値は、本発明の効果を妨げない限り特に限定されないが、取り扱い性等を考慮すると２５質量％であることが好ましい。 In the silver ink composition, the silver content in the silver carboxylate is preferably 17% by mass or more, and more preferably 18% by mass or more. By setting it as such a range, the metal silver formed with the method mentioned later becomes favorable in electroconductivity, and becomes more excellent in quality. The upper limit of the silver content is not particularly limited as long as the effect of the present invention is not hindered, but it is preferably 25% by mass in consideration of handleability and the like.
［アミン化合物］
　本発明において、前記アミン化合物は、脂肪族第一級アミン又は脂肪族第二級アミンで、炭素原子の総数が２～１０であれば特に限定されないが、好ましいものとして、窒素原子に結合している脂肪族炭化水素基がアルキル基であるもの（アルキルアミン、ジアルキルアミン）が例示できる。前記アルキル基は、直鎖状、分岐鎖状及び環状のいずれでもよい。
　前記直鎖状又は分岐鎖状のアルキル基としては、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｎ－ヘキシル基、２－メチルペンチル基、３－メチルペンチル基、４－メチルペンチル基、１，１－ジメチルブチル基、２，２－ジメチルブチル基、３，３－ジメチルブチル基、１，２－ジメチルブチル基、１，３－ジメチルブチル基、２，３－ジメチルブチル基、ｎ－ヘプチル基、ｎ－オクチル基、２－エチルヘキシル基、ノニル基、デシル基等が例示できる。
　前記環状のアルキル基は、単環状及び多環状のいずれでもよく、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘブチル基、シクロオクチル基、シクロノニル基、シクロデシル基、ノルボルニル基、イソボルニル基、アダマンチル基、トリシクロデシル基等が例示できる。 [Amine compound]
In the present invention, the amine compound is an aliphatic primary amine or an aliphatic secondary amine, and is not particularly limited as long as the total number of carbon atoms is 2 to 10, but is preferably bonded to a nitrogen atom. Examples are those in which the aliphatic hydrocarbon group is an alkyl group (alkylamine, dialkylamine). The alkyl group may be linear, branched or cyclic.
Examples of the linear or branched alkyl group include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group. , Neopentyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, nonyl group, decyl group and the like.
The cyclic alkyl group may be monocyclic or polycyclic, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, adamantyl group Group, tricyclodecyl group and the like.
　なかでも、前記アミン化合物としては、窒素原子に結合しているアルキル基が、直鎖状又は分岐鎖状であるものが好ましい。前記アミンは、炭素数が２～９であるものが好ましく、炭素数が３～８であるものがより好ましく、具体的には、ｎ－プロピルアミン、ｎ－ブチルアミン、ｎ－ペンチルアミン、ｎ－ヘキシルアミン、ｎ－ヘプチルアミン、２－エチルヘキシルアミン、ｎ－オクチルアミン、Ｎ－メチルヘキシルアミン、Ｎ－エチルヘキシルアミン等が例示できる。 Among them, the amine compound is preferably one in which the alkyl group bonded to the nitrogen atom is linear or branched. The amine preferably has 2 to 9 carbon atoms, more preferably 3 to 8 carbon atoms, specifically, n-propylamine, n-butylamine, n-pentylamine, n- Examples include hexylamine, n-heptylamine, 2-ethylhexylamine, n-octylamine, N-methylhexylamine, N-ethylhexylamine and the like.
　前記アミン化合物は、一種を単独で使用してもよいし、二種以上を併用してもよい。二種以上を併用する場合、その組み合わせ及び比率は、目的に応じて適宜選択すればよい。 The amine compounds may be used alone or in combination of two or more. When using 2 or more types together, the combination and ratio may be appropriately selected according to the purpose.
　銀インク組成物において、前記アミン化合物の配合量は、前記カルボン酸銀の配合量１モルあたり１～６モルであることが好ましく、１．５～５モルであることがより好ましい。アミン化合物の配合量を下限値以上とすることで、アミン化合物の使用効果がより高くなり、上限値以下とすることで、より良好な品質の金属銀を形成できる。 In the silver ink composition, the compounding amount of the amine compound is preferably 1 to 6 mol, and more preferably 1.5 to 5 mol, per mol of the carboxylate silver. By making the compounding quantity of an amine compound more than a lower limit, the use effect of an amine compound becomes higher, and metallic silver of better quality can be formed by making it the upper limit or less.
［アセチレンアルコール類］
　本発明において、アセチレンアルコール類は、前記一般式（２）で表される。
　一般式（２）において、Ｒ’及びＲ’’は、それぞれ独立に炭素数１～２０のアルキル基、又は１個以上の水素原子が置換基で置換されていてもよいフェニル基である。
　Ｒ’及びＲ’’における炭素数１～２０のアルキル基は、直鎖状、分岐鎖状及び環状（脂肪族環式基）のいずれでもよく、環状である場合、単環状及び多環状のいずれでもよい。Ｒ’及びＲ’’における前記アルキル基としては、Ｒにおける前記アルキル基と同様のものが例示できる。 [Acetylene alcohols]
In the present invention, acetylene alcohols are represented by the general formula (2).
In the general formula (2), R ′ and R ″ are each independently an alkyl group having 1 to 20 carbon atoms or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.
The alkyl group having 1 to 20 carbon atoms in R ′ and R ″ may be any of linear, branched and cyclic (aliphatic cyclic group). When cyclic, it may be any of monocyclic or polycyclic But you can. Examples of the alkyl group in R ′ and R ″ include the same alkyl groups as in R.
　Ｒ’及びＲ’’におけるフェニル基の水素原子が置換されていてもよい前記置換基としては、炭素数が１～１６の飽和又は不飽和の一価の脂肪族炭化水素基、前記脂肪族炭化水素基が酸素原子に結合した一価の基、フッ素原子、塩素原子、臭素原子、水酸基、シアノ基、フェノキシ基等が例示でき、Ｒにおけるフェニル基の水素原子が置換されていてもよい前記置換基と同様である。置換基の数及び位置は特に限定されず、置換基の数が複数である場合、これら複数の置換基は互いに同一でも異なっていてもよい。 Examples of the substituent in which the hydrogen atom of the phenyl group in R ′ and R ″ may be substituted include a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, the aliphatic carbon A monovalent group in which a hydrogen group is bonded to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a cyano group, a phenoxy group, etc. can be exemplified, and the hydrogen atom of the phenyl group in R may be substituted Same as the group. The number and position of the substituents are not particularly limited, and when the number of substituents is plural, the plural substituents may be the same as or different from each other.
　Ｒ’及びＲ’’は、炭素数１～２０のアルキル基であることが好ましく、炭素数１～１０の直鎖状又は分岐鎖状のアルキル基であることがより好ましい。 R ′ and R ″ are preferably an alkyl group having 1 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
　好ましい前記アセチレンアルコール類としては、３，５－ジメチル－１－ヘキシン－３－オール、３－メチル－１－ブチン－３－オール、３－メチル－１－ペンチン－３－オールが例示できる。 Preferable examples of the acetylene alcohols include 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, and 3-methyl-1-pentyn-3-ol.
　本発明において、アセチレンアルコール類は、一種を単独で使用してもよいし、二種以上を併用してもよい。二種以上を併用する場合で、その組み合わせ及び比率は、任意に調節できる。 In the present invention, acetylene alcohols may be used alone or in combination of two or more. When two or more kinds are used in combination, the combination and ratio can be arbitrarily adjusted.
　銀インク組成物において、アセチレンアルコール類の配合量は、前記カルボン酸銀の配合量１モルあたり０．０３～０．７モルであることが好ましく、０．０６～０．３モルであることがより好ましい。アセチレンアルコール類の配合量を下限値以上とすることで、アセチレンアルコール類の使用効果がより高くなり、上限値以下とすることで、より良好な品質の金属銀を形成できる。 In the silver ink composition, the blending amount of acetylene alcohols is preferably 0.03 to 0.7 mole, and preferably 0.06 to 0.3 mole, per mole of the above-mentioned silver carboxylate. More preferred. By making the compounding quantity of acetylene alcohol more than a lower limit, the use effect of acetylene alcohol becomes higher, and metallic silver of better quality can be formed by making it the upper limit or less.
（炭化水素）
　本発明において、前記炭化水素は、炭素数が６～２０であり、直鎖状、分岐鎖状及び環状のいずれでもよく、飽和炭化水素及び不飽和炭化水素のいずれでもよい。前記炭化水素は、１５～３７℃で液状であるものが好ましく、１５～３０℃で液状であるものがより好ましい。 (hydrocarbon)
In the present invention, the hydrocarbon has 6 to 20 carbon atoms, and may be linear, branched or cyclic, and may be any of saturated hydrocarbon and unsaturated hydrocarbon. The hydrocarbon is preferably liquid at 15 to 37 ° C., and more preferably liquid at 15 to 30 ° C.
　直鎖状又は分岐鎖状の前記飽和炭化水素としては、ｎ－ヘキサン、２－メチルペンタン、３－メチルペンタン、２，２－ジメチルブタン、２，３－ジメチルブタン、ｎ－ヘプタン、２－メチルヘキサン、３－メチルヘキサン、２，２－ジメチルペンタン、２，３－ジメチルペンタン、２，４－ジメチルペンタン、３，３－ジメチルペンタン、３－エチルペンタン、２，２，３－トリメチルブタン、ｎ－オクタン、２－メチルヘプタン、３－メチルヘプタン、４－メチルヘプタン、２，２－ジメチルヘキサン、２，３－ジメチルヘキサン、２，４－ジメチルヘキサン、２，５－ジメチルヘキサン、３，３－ジメチルヘキサン、３，４－ジメチルヘキサン、２，２，３－トリメチルペンタン、２，２，４－トリメチルペンタン（イソオクタン）、２，３，３－トリメチルペンタン、２，３，４－トリメチルペンタン、３－エチル－２－メチルペンタン、３－エチル－３－メチルペンタン、２，２，３，３－テトラメチルブタン、ｎ－ノナン、２－メチルオクタン、３－メチルオクタン、４－メチルオクタン、２，２－ジメチルヘプタン、２，３－ジメチルヘプタン、２，４－ジメチルヘプタン、２，５－ジメチルヘプタン、２，６－ジメチルヘプタン、３，３ジメチルヘプタン、３，４－ジメチルヘプタン、３，５－ジメチルヘプタン、４，４－ジメチルヘプタン、２，２，４，４，－テトラメチルペンタン、デカン、ウンデカン、ドデカン、トリデカン、テトラデカン、ペンタデカン、ヘキサデカン、ヘプタデカン、オクタデカン、ノナカン、エイコサンが例示できる。 Examples of the linear or branched saturated hydrocarbon include n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-heptane, 2-methyl Hexane, 3-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane, n -Octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,3- Dimethylhexane, 3,4-dimethylhexane, 2,2,3-trimethylpentane, 2,2,4-trimethylpentane (isooctane) 2,3,3-trimethylpentane, 2,3,4-trimethylpentane, 3-ethyl-2-methylpentane, 3-ethyl-3-methylpentane, 2,2,3,3-tetramethylbutane, n- Nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2,2-dimethylheptane, 2,3-dimethylheptane, 2,4-dimethylheptane, 2,5-dimethylheptane, 2,6-dimethyl Heptane, 3,3 dimethylheptane, 3,4-dimethylheptane, 3,5-dimethylheptane, 4,4-dimethylheptane, 2,2,4,4, -tetramethylpentane, decane, undecane, dodecane, tridecane, Examples include tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonacan, and eicosane.
　環状の前記飽和炭化水素は、単環状及び多環状のいずれでもよいが、単環状であることが好ましく、炭素数が８以下であることが好ましく、シクロヘキサン、シクロヘプタン、シクロオクタンが例示できる。 The cyclic saturated hydrocarbon may be monocyclic or polycyclic, but is preferably monocyclic, preferably has 8 or less carbon atoms, and examples thereof include cyclohexane, cycloheptane, and cyclooctane.
　前記不飽和炭化水素としては、前記飽和炭化水素の炭素原子間の１個以上の単結合（Ｃ－Ｃ）が、不飽和結合（二重結合（Ｃ＝Ｃ）、三重結合（Ｃ≡Ｃ））に置換されたものが例示できる。
　前記不飽和炭化水素は、炭素原子間の不飽和結合として、二重結合及び三重結合のいずれか一方のみを有していてもよいし、両方を有していてもよく、不飽和結合の数及び位置は特に限定されないが、不飽和結合の数は１又は２であることが好ましい。また、前記不飽和結合として二重結合を有する場合、前記不飽和炭化水素は、ｃｉｓ型及びｔｒａｎｓ型のいずれでもよい。
　前記不飽和炭化水素は、アルケン又はアルキンであることが好ましい。 As the unsaturated hydrocarbon, one or more single bonds (C—C) between carbon atoms of the saturated hydrocarbon are unsaturated bonds (double bonds (C═C), triple bonds (C≡C)). ) Can be exemplified.
The unsaturated hydrocarbon may have either a double bond or a triple bond as an unsaturated bond between carbon atoms, or may have both, and the number of unsaturated bonds. And the position is not particularly limited, but the number of unsaturated bonds is preferably 1 or 2. When the unsaturated bond has a double bond, the unsaturated hydrocarbon may be either cis type or trans type.
The unsaturated hydrocarbon is preferably an alkene or alkyne.
　本発明において、前記炭化水素は、一種を単独で使用してもよいし、二種以上を併用してもよい。二種以上を併用する場合で、その組み合わせ及び比率は、任意に調節できる。 In the present invention, the hydrocarbons may be used singly or in combination of two or more. When two or more kinds are used in combination, the combination and ratio can be arbitrarily adjusted.
　銀インク組成物において、前記炭化水素の配合量は、前記カルボン酸銀の配合量１モルあたり０．０５～２モルであることが好ましく、０．１～１．５モルであることがより好ましい。炭化水素の配合量を下限値以上とすることで、銀インク組成物の粘度をより適した低い値に調節でき、上限値以下とすることで、より良好な品質の金属銀を形成できる。 In the silver ink composition, the compounding amount of the hydrocarbon is preferably 0.05 to 2 mol, more preferably 0.1 to 1.5 mol, per mol of the carboxylate silver. . By setting the blending amount of the hydrocarbon to the lower limit value or more, the viscosity of the silver ink composition can be adjusted to a more suitable low value, and by setting it to the upper limit value or less, metallic silver of better quality can be formed.
［その他の成分］
　銀インク組成物は、前記カルボン酸銀、アミン化合物、アセチレンアルコール類及び炭化水素以外に、本発明の効果を妨げない範囲内において、これらに該当しないその他の成分がさらに配合されてなるものでもよい。
　銀インク組成物は、配合成分の総量に占める、前記カルボン酸銀、アミン化合物、アセチレンアルコール類及び炭化水素の総配合量が、８５質量％以上であることが好ましく、９０質量％以上であることがより好ましく、９５質量％以上であることが特に好ましく、１００質量％であってもよい。 [Other ingredients]
In addition to the silver carboxylate, amine compound, acetylene alcohols and hydrocarbons, the silver ink composition may be further blended with other components not corresponding to these within a range not impeding the effects of the present invention. .
In the silver ink composition, the total blending amount of the silver carboxylate, amine compound, acetylene alcohols and hydrocarbons in the total blending component is preferably 85% by mass or more, and 90% by mass or more. Is more preferably 95% by mass or more, and may be 100% by mass.
［銀インク組成物の粘度］
　銀インク組成物は、２７℃における粘度が４０ｍＰａ・ｓ以下であり、３７ｍＰａ・ｓ以下であることが好ましく、３３ｍＰａ・ｓ以下であることがより好ましい。上限値以下であることで、銀インク組成物は、インクジェット印刷法において適した物性を有するものとなる。
　また、前記粘度の下限値は特に限定されないが、銀インク組成物の取り扱い性等を考慮すると、５ｍＰａ・ｓであることが好ましい。 [Viscosity of silver ink composition]
The viscosity at 27 ° C. of the silver ink composition is 40 mPa · s or less, preferably 37 mPa · s or less, and more preferably 33 mPa · s or less. By being below the upper limit, the silver ink composition has physical properties suitable for the ink jet printing method.
The lower limit of the viscosity is not particularly limited, but is preferably 5 mPa · s in consideration of the handleability of the silver ink composition.
　銀インク組成物の粘度は、公知の方法にしたがって測定でき、例えば、超音波式粘度計により測定できる。 The viscosity of the silver ink composition can be measured according to a known method, for example, an ultrasonic viscometer.
　銀インク組成物の粘度は、例えば、配合成分の種類及び量で調節できるが、特に前記炭化水素の種類で容易に調節できる。 The viscosity of the silver ink composition can be adjusted by, for example, the type and amount of the blending component, but can be easily adjusted by the type of the hydrocarbon.
　ここでは銀インク組成物の２７℃における粘度について説明したが、銀インク組成物の使用時の温度は、２７℃に限定されるものではなく、任意に選択できる。２７℃における粘度が上記のような範囲であることで、通常の使用条件で、前記銀インク組成物は、優れた効果を奏する。 Here, the viscosity at 27 ° C. of the silver ink composition has been described, but the temperature at the time of use of the silver ink composition is not limited to 27 ° C. and can be arbitrarily selected. When the viscosity at 27 ° C. is in the above range, the silver ink composition exhibits an excellent effect under normal use conditions.
［銀インク組成物の表面張力］
　銀インク組成物は、２７℃における動的表面張力が５６ｍＮ／ｍ以下であり、５３ｍＮ／ｍ以下であることが好ましく、このような範囲であることで、銀インク組成物はインクジェット印刷法に適した物性を有するものとなる。
　前記動的表面張力の下限値は特に限定されないが、銀インク組成物の取り扱い性等を考慮すると、２８ｍＮ／ｍであることが好ましい。
　本発明において、「動的表面張力」は、例えば、銀インク組成物中に気泡を発生させた場合の、該気泡が銀インク組成物から受ける圧力の最大値を用いて算出する、所謂「最大泡圧法」で求められる。最大泡圧法では、例えば、気泡周波数が９～１１Ｈｚのいずれかの場合において、動的表面張力を求めればよい。 [Surface tension of silver ink composition]
The silver ink composition has a dynamic surface tension at 27 ° C. of 56 mN / m or less, and preferably 53 mN / m or less. With such a range, the silver ink composition is suitable for the inkjet printing method. It will have the physical properties.
The lower limit value of the dynamic surface tension is not particularly limited, but is preferably 28 mN / m in consideration of the handleability of the silver ink composition.
In the present invention, the “dynamic surface tension” is calculated using, for example, a so-called “maximum value” that is calculated using the maximum value of the pressure that the bubbles receive from the silver ink composition when bubbles are generated in the silver ink composition. It is calculated | required by the "bubble pressure method. In the maximum bubble pressure method, for example, the dynamic surface tension may be obtained when the bubble frequency is any of 9 to 11 Hz.
　また、銀インク組成物は、２７℃における静的表面張力が、３０ｍＮ／ｍ以下であることが好ましく、２８ｍＮ／ｍ以下であることがより好ましい。このような範囲であることで、銀インク組成物は、インクジェット印刷法により適した物性を有するものとなる。
　前記静的表面張力の下限値は特に限定されないが、銀インク組成物の取り扱い性等を考慮すると、１４ｍＮ／ｍであることが好ましい。
　本発明においては、例えば、前記最大泡圧法で、気泡周波数が０．０５～０．２Ｈｚのいずれかの場合の表面張力を「静的表面張力」とすればよい。 Further, the silver ink composition preferably has a static surface tension at 27 ° C. of 30 mN / m or less, and more preferably 28 mN / m or less. By being in such a range, the silver ink composition has physical properties more suitable for the ink jet printing method.
The lower limit value of the static surface tension is not particularly limited, but is preferably 14 mN / m in consideration of the handleability of the silver ink composition.
In the present invention, for example, the surface tension when the bubble frequency is any of 0.05 to 0.2 Hz by the maximum bubble pressure method may be set to “static surface tension”.
　また、銀インク組成物は、前記最大泡圧法での２７℃における、気泡周波数が１Ｈｚでの表面張力が、４５ｍＮ／ｍ以下であることが好ましく、４０ｍＮ／ｍ以下であることがより好ましい。このような範囲であることで、銀インク組成物は、インクジェット印刷法により適した物性を有するものとなる。
　前記１Ｈｚでの表面張力の下限値は特に限定されないが、銀インク組成物の取り扱い性等を考慮すると、２１ｍＮ／ｍであることが好ましい。 The silver ink composition preferably has a surface tension at a bubble frequency of 1 Hz at 27 ° C. in the maximum bubble pressure method of 45 mN / m or less, more preferably 40 mN / m or less. By being in such a range, the silver ink composition has physical properties more suitable for the ink jet printing method.
The lower limit value of the surface tension at 1 Hz is not particularly limited, but is preferably 21 mN / m in consideration of the handleability of the silver ink composition.
　銀インク組成物の表面張力（動的表面張力、静的表面張力等）は、例えば、配合成分の種類及び量で調節できるが、特に前記炭化水素の種類で容易に調節できる。 The surface tension (dynamic surface tension, static surface tension, etc.) of the silver ink composition can be adjusted by, for example, the type and amount of the blending component, but can be easily adjusted by the type of the hydrocarbon.
　なお、ここでは銀インク組成物の２７℃における表面張力について説明したが、銀インク組成物の使用時の温度は、２７℃に限定されるものではなく、任意に選択できる。２７℃における表面張力が上記のような範囲であることで、通常の使用条件で、前記銀インク組成物は、優れた効果を奏する。 Although the surface tension at 27 ° C. of the silver ink composition has been described here, the temperature at the time of use of the silver ink composition is not limited to 27 ° C. and can be arbitrarily selected. When the surface tension at 27 ° C. is in the above range, the silver ink composition exhibits an excellent effect under normal use conditions.
［銀インク組成物の製造］
　銀インク組成物は、前記カルボン酸銀、アミン化合物、アセチレンアルコール類及び炭化水素、並びに必要に応じて前記その他の成分を配合することで得られる。
　各成分の配合時には、すべての成分を添加してからこれらを混合してもよいし、一部の成分を順次添加しながら混合してもよく、すべての成分を順次添加しながら混合してもよい。
　混合方法は特に限定されず、撹拌子又は撹拌翼等を回転させて混合する方法、ミキサーを使用して混合する方法、超音波を加えて混合する方法等、公知の方法から適宜選択すればよい。 [Production of silver ink composition]
The silver ink composition can be obtained by blending the silver carboxylate, amine compound, acetylene alcohols and hydrocarbons, and, if necessary, the other components.
At the time of blending each component, all the components may be added and then mixed, or some components may be mixed while being added sequentially, or all components may be mixed while being added sequentially. Good.
The mixing method is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, a method of adding ultrasonic waves, and the like. .
　配合成分は、銀インク組成物中ですべて溶解していてもよいし、一部の成分が溶解せずに分散した状態であってもよい。 The blending component may be dissolved in the silver ink composition, or a part of the components may be dispersed without being dissolved.
　配合時の温度は、各配合成分が劣化しない限り特に限定されないが、－５～３０℃であることが好ましい。 The temperature at the time of blending is not particularly limited as long as each blended component does not deteriorate, but is preferably −5 to 30 ° C.
［金属銀］
　本発明の銀インク組成物は、例えば、６０～２００℃等の温度で加熱（焼成）処理することにより、カルボン酸銀を熱分解させ、容易に金属銀を形成できる。したがって、銀インク組成物を、その粘度に適したインクジェット印刷法等の各種印刷法に適用し、得られた印刷パターンを加熱処理することで、金属銀のパターンを形成できる。 [Metallic silver]
The silver ink composition of the present invention can easily form metallic silver by thermally decomposing silver carboxylate by heating (firing) treatment at a temperature of 60 to 200 ° C., for example. Therefore, a silver metal composition can be formed by applying the silver ink composition to various printing methods such as an ink jet printing method suitable for the viscosity and heat-treating the obtained print pattern.
　金属銀形成時の加熱温度は、カルボン酸銀の種類に応じて、適宜調節すればよい。カルボン酸銀は、例えば、好ましくは６０～２１０℃、より好ましくは６０～２００℃という低温で分解し、金属銀を形成する。したがって、このような分解温度を反映して、本発明の銀インク組成物は、当該分野で公知の還元剤等を使用しなくても、上記のような従来の金属銀形成材料よりも低温で金属銀を形成できる。加熱時間は、加熱温度に応じて適宜調節すればよい。 The heating temperature at the time of forming metallic silver may be appropriately adjusted according to the type of silver carboxylate. The silver carboxylate is decomposed at a low temperature of preferably 60 to 210 ° C., more preferably 60 to 200 ° C. to form metallic silver. Therefore, reflecting such a decomposition temperature, the silver ink composition of the present invention has a lower temperature than the conventional metal silver forming material as described above, without using a reducing agent known in the art. Metal silver can be formed. The heating time may be adjusted as appropriate according to the heating temperature.
　前記銀インク組成物でインクジェット印刷を行う被印刷物は、公知のものでよく、基材上にインク受理層が設けられたものが例示できるが、これに限定されない。 The substrate to be inkjet-printed with the silver ink composition may be a known one, and examples thereof include an ink receiving layer provided on a substrate, but are not limited thereto.
　前記基材の材質は特に限定されず、目的に応じて選択すればよい。具体的には、原紙、アート紙、コート紙、キャストコート紙、レジンコート紙、合成紙等の紙類；ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、ポリ酢酸ビニル、アクリル樹脂、ＡＳ樹脂、ＡＢＳ樹脂、ポリアミド、ポリアセタール、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリトリメチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリフェニレンスルファイド、ポリスルホン、ポリカーボネート、エポキシ樹脂、メラミン樹脂、フェノール樹脂、尿素樹脂、ポリウレタン、ポリイミド等の合成樹脂等が例示できる。また、二種以上の材質のものが積層されたものでもよい。 The material of the substrate is not particularly limited, and may be selected according to the purpose. Specifically, paper such as base paper, art paper, coated paper, cast coated paper, resin coated paper, synthetic paper; polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resin, AS resin, ABS resin , Polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyphenylene sulfide, polysulfone, polycarbonate, epoxy resin, melamine resin, phenol resin, urea resin, polyurethane, polyimide, etc. Examples of the synthetic resin are as follows. Two or more kinds of materials may be laminated.
　前記基材は、形状がシート状又はフィルム状であることが好ましく、厚さが２０～１０００μｍであることが好ましい。基材の厚さを下限値以上とすることで、インク受理層の構造をより安定して保持でき、上限値以下とすることで、被印刷物としての取り扱い性がより良好となる。 The base material is preferably in the form of a sheet or a film, and preferably has a thickness of 20 to 1000 μm. By setting the thickness of the base material to the lower limit value or more, the structure of the ink receiving layer can be more stably maintained, and by setting the thickness to the upper limit value or less, the handleability as a printed material becomes better.
　インク受理層は、厚さが１～２０μｍであることが好ましい。インク受理層の厚さをこのような範囲とすることで、インク受理層の構造をより安定して保持できると共に、印刷物の品質がより向上する。 The ink receiving layer preferably has a thickness of 1 to 20 μm. By setting the thickness of the ink receiving layer in such a range, the structure of the ink receiving layer can be more stably maintained, and the quality of the printed matter is further improved.
　本発明の銀インク組成物は、粘度が上記数値範囲であることで、インクジェット印刷法への適用に好適なものである。各成分を所定の温度で配合するだけという、極めて簡便な方法で製造可能である。しかも、得られた銀インク組成物は、前記還元剤等を使用しなくても、そのまま加熱処理することで、極めて容易に実用的な量の金属銀を形成できる。
なお、本発明において「複数」とは、少なくとも２つ以上の任意の数であってよいことを意味する。 The silver ink composition of the present invention is suitable for application to an ink jet printing method because the viscosity is in the above numerical range. It can be produced by an extremely simple method in which each component is simply blended at a predetermined temperature. Moreover, the obtained silver ink composition can form a practical amount of metallic silver very easily by heat treatment without using the reducing agent or the like.
In the present invention, “plurality” means that the number may be at least two or more.
　以下、具体的実施例により、本発明についてより詳細に説明する。ただし、本発明は、以下に示す実施例に、何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.
＜銀インク組成物の製造及び評価＞
［実施例１］
（銀インク組成物の製造）
　２－エチルヘキシルアミン（３．１ｇ）、３，５－ジメチル－１－ヘキシン－３－オール（エアープロダクツジャパン社製「サーフィノール６１」）（０．１７ｇ）及びｎ－オクタン（０．８ｇ）を、１３．５ｍＬバイアル瓶内に添加して撹拌し、さらにここへ、氷冷下２－メチルアセト酢酸銀（３．０ｇ）を添加して、３０分間撹拌することで、銀インク組成物を得た。各成分の配合量を表１に示す。 <Production and Evaluation of Silver Ink Composition>
[Example 1]
(Manufacture of silver ink composition)
2-ethylhexylamine (3.1 g), 3,5-dimethyl-1-hexyn-3-ol (“Surfinol 61” manufactured by Air Products Japan) (0.17 g) and n-octane (0.8 g) A silver ink composition was obtained by adding the mixture into a 13.5 mL vial and stirring, and further adding silver 2-methylacetoacetate (3.0 g) under ice cooling and stirring for 30 minutes. . Table 1 shows the amount of each component.
（銀インク組成物の評価）
・粘度
　得られた銀インク組成物（７ｇ）中に、超音波式粘度計（ＣＢＣ社製「ＶＩＳＣＯＭＡＴＥ　ＶＭ－１０Ａ」）のセンサー（振動体）を浸漬し、温度２７℃の環境下で、銀インク組成物の粘度を測定した。結果を表２に示す。
・表面張力
　得られた銀インク組成物（７ｇ）中に、表面張力計（英弘精機社製「ポータブル表面張力計シータｔ６０」）のセンサーを浸漬し、温度２７℃の環境下で、気泡周波数を０Ｈｚから１０Ｈｚまで変化させ、最大泡圧法により、銀インク組成物の０．１Ｈｚの場合の表面張力（静的表面張力）、１Ｈｚの場合の表面張力、及び１０Ｈｚの場合の表面張力（動的表面張力）をそれぞれ測定した。結果を表２に示す。 (Evaluation of silver ink composition)
・ Viscosity In the obtained silver ink composition (7 g), a sensor (vibrating body) of an ultrasonic viscometer (“VISCOMATE VM-10A” manufactured by CBC) was immersed, and silver was used in an environment at a temperature of 27 ° C. The viscosity of the ink composition was measured. The results are shown in Table 2.
・ Surface tension In the obtained silver ink composition (7 g), a sensor of a surface tension meter (“Portable Surface Tension Meter Theta t60” manufactured by Eihiro Seiki Co., Ltd.) is immersed, and the bubble frequency is measured in an environment at a temperature of 27 ° C. The surface tension of the silver ink composition at 0.1 Hz (static surface tension), the surface tension at 1 Hz, and the surface tension at 10 Hz (dynamic surface) by changing from 0 Hz to 10 Hz and using the maximum bubble pressure method. Tension) was measured. The results are shown in Table 2.
＜金属銀の製造及び評価＞
（金属銀の製造）
　ポリエチレンテレフタレート（ＰＥＴ）製の基材（東レ社製「ルミラーＳ１０」、厚さ１００μｍ）上に、上記で得られた銀インク組成物を吐出させ、塗布した。このときの銀インク組成物の基材上への塗布量は、１５±１ｇ／ｍ２となるように調節した。
　次いで、この銀インク組成物に対して、８０℃で３０分間の熱風吹き付けによる加熱処理、さらに１５０℃で３０分間又は６０分間の熱風吹き付けによる加熱処理を順次行い、二通りで金属銀を形成させた。 <Manufacture and evaluation of metallic silver>
(Manufacture of metallic silver)
The silver ink composition obtained above was discharged and applied onto a polyethylene terephthalate (PET) base material (“Lumirror S10” manufactured by Toray Industries, Inc., thickness 100 μm). The coating amount of the silver ink composition on the substrate at this time was adjusted to 15 ± 1 g / m 2 .
Next, this silver ink composition is sequentially subjected to heat treatment by hot air blowing at 80 ° C. for 30 minutes, and further by heat treatment by hot air blowing at 150 ° C. for 30 minutes or 60 minutes to form metallic silver in two ways. It was.
（金属銀の評価）
　得られた金属銀において、電気抵抗測定装置「ロレスタＭＣＰ－Ｔ６１０（三菱化学アナリティック社製）」を使用して、ＪＩＳ　Ｋ　７１９４（ＡＳＴＭ　Ｄ　９９１）に準じて、表面抵抗値（Ω／□）を測定した。結果を表２に示す。 (Evaluation of metallic silver)
In the obtained metallic silver, the surface resistance value (Ω / □) was measured in accordance with JIS K 7194 (ASTM D 991) using an electrical resistance measuring device “Loresta MCP-T610 (manufactured by Mitsubishi Chemical Analytic Co., Ltd.)”. Was measured. The results are shown in Table 2.
＜銀インク組成物の製造及び評価、並びに金属銀の製造及び評価＞
［実施例２～１７、比較例１～３］
　各成分の種類と配合量を表１に示す通りとしたこと以外は、実施例１と同様に銀インク組成物を製造及び評価した。結果を表２に示す。表１中、「－」は、その成分が未配合であることを示す。
　さらに、得られた銀インク組成物を使用して、実施例１と同様に金属銀を製造及び評価した。結果を表２に示す。表２中、「ＯＬ」は値が大き過ぎて測定できなかった（オーバーロード）ことを示す。 <Manufacture and evaluation of silver ink composition, and manufacture and evaluation of metallic silver>
[Examples 2 to 17, Comparative Examples 1 to 3]
A silver ink composition was produced and evaluated in the same manner as in Example 1 except that the types and blending amounts of the components were as shown in Table 1. The results are shown in Table 2. In Table 1, “-” indicates that the component is not blended.
Further, metallic silver was produced and evaluated in the same manner as in Example 1 using the obtained silver ink composition. The results are shown in Table 2. In Table 2, “OL” indicates that the value is too large to be measured (overload).
　表１に示す各略号は、以下のものを意味する。
（ａ）カルボン酸銀
　（ａ）－１：２－メチルアセト酢酸銀
（ｂ）アミン化合物
　（ｂ）－１：２－エチルヘキシルアミン
（ｃ）アセチレンアルコール類
　（ｃ）－１：３，５－ジメチル－１－ヘキシン－３－オール
　（ｃ）－２：３－メチル－１－ペンチン－３－オール（日信化学工業社製「オルフィンＰ」）
　（ｃ）－３：３－メチル－１－ブチン－３－オール（日信化学工業社製「オルフィンＢ」） Each abbreviation shown in Table 1 means the following.
(A) Silver carboxylate (a) -1: Silver 2-methylacetoacetate (b) Amine compound (b) -1: 2-ethylhexylamine (c) Acetylene alcohols (c) -1: 3,5-dimethyl- 1-hexyn-3-ol (c) -2: 3-methyl-1-pentyn-3-ol (“Orphine P” manufactured by Nissin Chemical Industry Co., Ltd.)
(C) -3: 3-Methyl-1-butyn-3-ol (“Orphine B” manufactured by Nissin Chemical Industry Co., Ltd.)
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　上記結果から明らかなように、本発明の銀インク組成物は、粘度が３１ｍＰａ・ｓ以下であり、容易に吐出可能で、インクジェット印刷法への適用に適したものであることを確認できた。また、金属銀は十分な量が形成され、その抵抗値は０．４Ω／□以下と小さく、加熱処理の時間が変化しても安定しており、導電性材料として好適なものであった。
　これに対して、比較例１の銀インク組成物は、炭化水素を配合しなかったことにより、粘度が高く、吐出に困難を伴い、インクジェット印刷法への適用に適さないものであった。
　また、比較例２の銀インク組成物は、配合した炭化水素の種類が適さなかったことにより、粘度が高く、吐出に困難を伴い、インクジェット印刷法への適用に適さないものであった。さらに、形成された金属銀は抵抗値が著しく高く、その値を測定できなかった。
　また、比較例３の銀インク組成物は、炭化水素を配合しなかったのに対し、比較例１よりもカルボン酸銀の配合量を少なくし、アミン化合物の配合量を多くしたものであり、粘度が低かったものの、形成された金属銀は抵抗値が高かった。 As is clear from the above results, the silver ink composition of the present invention has a viscosity of 31 mPa · s or less, can be easily ejected, and can be confirmed to be suitable for application to the ink jet printing method. Further, a sufficient amount of metallic silver was formed, and its resistance value was as small as 0.4Ω / □ or less, and it was stable even when the heat treatment time changed, and was suitable as a conductive material.
On the other hand, the silver ink composition of Comparative Example 1 was not suitable for application to the ink jet printing method because it had a high viscosity and was difficult to discharge because it did not contain hydrocarbons.
Further, the silver ink composition of Comparative Example 2 was not suitable for application to the ink jet printing method due to the high viscosity, difficulty in ejection due to the inadequate type of the blended hydrocarbon. Further, the formed metallic silver had a remarkably high resistance value, and the value could not be measured.
In addition, the silver ink composition of Comparative Example 3 did not contain hydrocarbons, whereas the amount of silver carboxylate was less than that of Comparative Example 1 and the amount of amine compound was increased. Although the viscosity was low, the formed metallic silver had a high resistance value.
＜銀インク組成物の製造及び評価、並びに金属銀の製造及び評価＞
［実施例１８～２３］
　各成分の種類と配合量を表３に示す通りとしたこと以外は、実施例１と同様に銀インク組成物を製造及び評価した。結果を表４に示す。
　さらに、得られた銀インク組成物を使用して、実施例１と同様に金属銀を製造及び評価した。結果を表４に示す。 <Manufacture and evaluation of silver ink composition, and manufacture and evaluation of metallic silver>
[Examples 18 to 23]
A silver ink composition was produced and evaluated in the same manner as in Example 1 except that the types and blending amounts of the components were as shown in Table 3. The results are shown in Table 4.
Further, metallic silver was produced and evaluated in the same manner as in Example 1 using the obtained silver ink composition. The results are shown in Table 4.
　表３に示す各略号は、以下のものを意味する。
（ａ）カルボン酸銀
　（ａ）－２：アセト酢酸銀
　（ａ）－３：ピバロイル酢酸銀
　（ａ）－４：イソブチリル酢酸銀
　（ａ）－５：アセトンジカルボン酸銀 Each abbreviation shown in Table 3 means the following.
(A) Silver carboxylate (a) -2: Silver acetoacetate (a) -3: Silver pivaloyl acetate (a) -4: Silver isobutyryl acetate (a) -5: Silver acetone dicarboxylate
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　上記結果から明らかなように、本発明の銀インク組成物は、粘度が２５．６ｍＰａ・ｓ以下であり、容易に吐出可能で、インクジェット印刷法への適用に適したものであることを確認できた。また、金属銀は十分な量が形成され、その抵抗値は５．２Ω／□以下と小さく、加熱処理の時間が変化しても安定しており、導電性材料として好適なものであった。 As is clear from the above results, the silver ink composition of the present invention has a viscosity of 25.6 mPa · s or less, can be easily ejected, and can be confirmed to be suitable for application to the ink jet printing method. It was. Further, a sufficient amount of metallic silver was formed, its resistance value was as small as 5.2 Ω / □ or less, and it was stable even when the heat treatment time was changed, and was suitable as a conductive material.
　本発明は、インクジェット印刷用のインクとして利用可能であり、微細な金属銀のパターン形成に特に有用である。 The present invention can be used as an ink for ink-jet printing, and is particularly useful for forming a fine metallic silver pattern.

Claims (9)

  1. 　式－ＣＯＯＡｇで表される基を有するカルボン酸銀、炭素数２～１０の脂肪族第一級アミン又は第二級アミン、下記一般式（２）で表されるアセチレンアルコール類、及び炭素数６～２０の炭化水素が配合されてなり、２７℃における粘度が４０ｍＰａ・ｓ以下である銀インク組成物。
    Figure JPOXMLDOC01-appb-C000001
     　　　　　　　　　　　　　　　　　　
    （式中、Ｒ’及びＲ’’は、それぞれ独立に炭素数１～２０のアルキル基、又は１個以上の水素原子が置換基で置換されていてもよいフェニル基である。）     Silver carboxylate having a group represented by the formula —COOAg, aliphatic primary amine or secondary amine having 2 to 10 carbon atoms, acetylene alcohol represented by the following general formula (2), and carbon number 6 A silver ink composition comprising ˜20 hydrocarbons and a viscosity at 27 ° C. of 40 mPa · s or less.
    Figure JPOXMLDOC01-appb-C000001
    (In the formula, R ′ and R ″ are each independently an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.)
  2. 　炭素数６～１４の炭化水素が配合されてなり、２７℃における動的表面張力が５６ｍＮ／ｍ以下である請求項１に記載の銀インク組成物。 The silver ink composition according to claim 1, comprising a hydrocarbon having 6 to 14 carbon atoms and a dynamic surface tension at 27 ° C of 56 mN / m or less.
  3. 　前記カルボン酸銀が、下記一般式（１）で表されるβ－ケトカルボン酸銀である請求項１又は２に記載の銀インク組成物。
    Figure JPOXMLDOC01-appb-C000002
     　　　　　　　　　　　　　　　　　　

    　（式中、Ｒは１個以上の水素原子が置換基で置換されていてもよい炭素数１～２０の脂肪族炭化水素基若しくはフェニル基、水酸基、アミノ基、又は一般式Ｒ１－ＣＹ２－、ＣＹ３－、Ｒ１－ＣＨＹ－、Ｒ２Ｏ－、Ｒ５Ｒ４Ｎ－、（Ｒ３Ｏ）２ＣＹ－若しくはＲ６－Ｃ（＝Ｏ）－ＣＹ２－で表される基であり；
    　Ｙはそれぞれ独立にフッ素原子、塩素原子、臭素原子又は水素原子であり；Ｒ１は炭素数１～１９の脂肪族炭化水素基又はフェニル基であり；Ｒ２は炭素数１～２０の脂肪族炭化水素基であり；Ｒ３は炭素数１～１６の脂肪族炭化水素基であり；Ｒ４及びＲ５はそれぞれ独立に炭素数１～１８の脂肪族炭化水素基であり；Ｒ６は炭素数１～１９の脂肪族炭化水素基、水酸基又は式ＡｇＯ－で表される基であり；
    　Ｘはそれぞれ独立に水素原子、炭素数１～２０の脂肪族炭化水素基、ハロゲン原子、１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはベンジル基、シアノ基、Ｎ－フタロイル－３－アミノプロピル基、２－エトキシビニル基、又は一般式Ｒ７Ｏ－、Ｒ７Ｓ－、Ｒ７－Ｃ（＝Ｏ）－若しくはＲ７－Ｃ（＝Ｏ）－Ｏ－で表される基であり；
    　Ｒ７は、炭素数１～１０の脂肪族炭化水素基、チエニル基、又は１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはジフェニル基である。）     The silver ink composition according to claim 1 or 2, wherein the silver carboxylate is a β-ketocarboxylate silver represented by the following general formula (1).
    Figure JPOXMLDOC01-appb-C000002

    (Wherein R represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, a phenyl group, a hydroxyl group, an amino group, or a group represented by the general formula R 1 -CY 2 —, CY 3 —, R 1 —CHY—, R 2 O—, R 5 R 4 N—, (R 3 O) 2 CY— or R 6 —C (═O) —CY 2 — Is;
    Y is independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom; R 1 is an aliphatic hydrocarbon group or phenyl group having 1 to 19 carbon atoms; R 2 is an aliphatic group having 1 to 20 carbon atoms R 3 is an aliphatic hydrocarbon group having 1 to 16 carbon atoms; R 4 and R 5 are each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms; R 6 is a carbon group; An aliphatic hydrocarbon group having a number of 1 to 19, a hydroxyl group or a group represented by the formula AgO—;
    X is independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a phenyl group or benzyl group in which one or more hydrogen atoms may be substituted with a substituent, a cyano group, N— A phthaloyl-3-aminopropyl group, a 2-ethoxyvinyl group, or a group represented by the general formula R 7 O—, R 7 S—, R 7 —C (═O) — or R 7 —C (═O) —O— A group to be
    R 7 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group, or a phenyl group or diphenyl group in which one or more hydrogen atoms may be substituted with a substituent. )
  4. 　前記Ｒが直鎖状若しくは分枝鎖状のアルキル基、フェニル基、又は前記一般式Ｒ６－Ｃ（＝Ｏ）－ＣＹ２－で表される基であり、前記Ｘが水素原子、直鎖状若しくは分枝鎖状のアルキル基、又はベンジル基である請求項３に記載の銀インク組成物。 R is a linear or branched alkyl group, a phenyl group, or a group represented by the general formula R 6 —C (═O) —CY 2 —, wherein X is a hydrogen atom, a linear chain The silver ink composition according to claim 3, which is a linear or branched alkyl group or a benzyl group.
  5. 　前記β－ケトカルボン酸銀が、２－メチルアセト酢酸銀、アセト酢酸銀、２－エチルアセト酢酸銀、プロピオニル酢酸銀、イソブチリル酢酸銀、ピバロイル酢酸銀、２－ｎ－ブチルアセト酢酸銀、２－ベンジルアセト酢酸銀、ベンゾイル酢酸銀、ピバロイルアセト酢酸銀、イソブチリルアセト酢酸銀及びアセトンジカルボン酸銀からなる群から選択される一種以上である請求項３又は４に記載の銀インク組成物。 The silver β-ketocarboxylate is silver 2-methylacetoacetate, silver acetoacetate, silver 2-ethylacetoacetate, silver propionylacetate, silver isobutyrylacetate, silver pivaloylacetate, silver 2-n-butylacetoacetate, silver 2-benzylacetoacetate The silver ink composition according to claim 3 or 4, which is one or more selected from the group consisting of silver benzoyl acetate, silver pivaloyl acetoacetate, silver isobutyryl acetoacetate and silver acetone dicarboxylate.
  6. 　前記第一級アミン又は第二級アミンの窒素原子に結合している脂肪族炭化水素基が、直鎖状又は分岐鎖状のアルキル基である請求項１～５のいずれか一項に記載の銀インク組成物。 The aliphatic hydrocarbon group bonded to the nitrogen atom of the primary amine or the secondary amine is a linear or branched alkyl group according to any one of claims 1 to 5. Silver ink composition.
  7. 　前記第一級アミン又は第二級アミンが、２－エチルヘキシルアミン、ｎ－プロピルアミン、ｎ－ブチルアミン、ｎ－ペンチルアミン、ｎ－ヘキシルアミン、ｎ－ヘプチルアミン、ｎ－オクチルアミン、Ｎ－メチルヘキシルアミン及びＮ－エチルヘキシルアミンからなる群から選択される一種以上である請求項１～６のいずれか一項に記載の銀インク組成物。 The primary amine or secondary amine is 2-ethylhexylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, N-methylhexyl. The silver ink composition according to any one of claims 1 to 6, wherein the silver ink composition is at least one selected from the group consisting of an amine and N-ethylhexylamine.
  8. 　前記Ｒ’及びＲ’’が、炭素数１～１０の直鎖状又は分岐鎖状のアルキル基である請求項１～７のいずれか一項に記載の銀インク組成物。 The silver ink composition according to any one of claims 1 to 7, wherein R 'and R' 'are linear or branched alkyl groups having 1 to 10 carbon atoms.
  9. 　前記アセチレンアルコール類が、３，５－ジメチル－１－ヘキシン－３－オール、３－メチル－１－ブチン－３－オール及び３－メチル－１－ペンチン－３－オールからなる群から選択される一種以上である請求項１～８のいずれか一項に記載の銀インク組成物。 The acetylene alcohol is selected from the group consisting of 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol and 3-methyl-1-pentyn-3-ol. The silver ink composition according to any one of claims 1 to 8, wherein the silver ink composition is one or more.
PCT/JP2013/051590 2012-01-27 2013-01-25 Silver ink composition WO2013111856A1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150224578A1 (en) * 2012-08-07 2015-08-13 Daicel Corporation Method for producing silver nanoparticles, silver nanoparticles, and silver coating material composition
JP2017115090A (en) * 2015-12-25 2017-06-29 トッパン・フォームズ株式会社 Silver ink composition
US10301497B2 (en) 2014-04-17 2019-05-28 Electroninks Incorporated Conductive ink compositions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009114232A (en) * 2007-11-01 2009-05-28 Osaka Industrial Promotion Organization INK CONTAINING SILVER beta-KETOCARBOXYLATE
JP2009197133A (en) * 2008-02-21 2009-09-03 Osaka Industrial Promotion Organization INK CONTAINING SILVER beta-KETOCARBOXYLATE
JP2011063813A (en) * 2010-11-30 2011-03-31 Toppan Forms Co Ltd Ink and method for forming wiring
JP2011241242A (en) * 2010-05-14 2011-12-01 Seiko Epson Corp Aqueous ink composition and recorded article using the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009114232A (en) * 2007-11-01 2009-05-28 Osaka Industrial Promotion Organization INK CONTAINING SILVER beta-KETOCARBOXYLATE
JP2009197133A (en) * 2008-02-21 2009-09-03 Osaka Industrial Promotion Organization INK CONTAINING SILVER beta-KETOCARBOXYLATE
JP2011241242A (en) * 2010-05-14 2011-12-01 Seiko Epson Corp Aqueous ink composition and recorded article using the same
JP2011063813A (en) * 2010-11-30 2011-03-31 Toppan Forms Co Ltd Ink and method for forming wiring

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150224578A1 (en) * 2012-08-07 2015-08-13 Daicel Corporation Method for producing silver nanoparticles, silver nanoparticles, and silver coating material composition
US9656322B2 (en) * 2012-08-07 2017-05-23 Daicel Corporation Method for producing silver nanoparticles, silver nanoparticles, and silver coating material composition
US10301497B2 (en) 2014-04-17 2019-05-28 Electroninks Incorporated Conductive ink compositions
US11180673B2 (en) 2014-04-17 2021-11-23 Electroninks Incorporated Conductive ink compositions
JP2017115090A (en) * 2015-12-25 2017-06-29 トッパン・フォームズ株式会社 Silver ink composition

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