WO2015045932A1 - Copper thin film forming composition - Google Patents

Copper thin film forming composition Download PDF

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Publication number
WO2015045932A1
WO2015045932A1 PCT/JP2014/074341 JP2014074341W WO2015045932A1 WO 2015045932 A1 WO2015045932 A1 WO 2015045932A1 JP 2014074341 W JP2014074341 W JP 2014074341W WO 2015045932 A1 WO2015045932 A1 WO 2015045932A1
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Prior art keywords
thin film
weight
copper
copper thin
parts
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PCT/JP2014/074341
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French (fr)
Japanese (ja)
Inventor
藤城　光一
今野　高志
義成 山本
敬裕 吉岡
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新日鉄住金化学株式会社
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Priority to JP2015539118A priority Critical patent/JPWO2015045932A1/en
Publication of WO2015045932A1 publication Critical patent/WO2015045932A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/06—Coating on selected surface areas, e.g. using masks

Definitions

  • the present invention relates to a copper thin film forming composition, and more particularly to a copper thin film forming composition that can be suitably used as an ink applied by, for example, an inkjet method.
  • metal material fine arrangement technology and thin film formation technology have been studied.
  • a metal nano ink in which metal nano particles with an average particle size of 100 nm or less are dispersed in a solvent is prepared and applied to a fine pattern shape by an ink jet printing method or a screen printing method.
  • Development of the printed electronics manufacturing technology to be formed is advancing.
  • the metal fine particles are not only optimal for dealing with fine patterns because of their small particle size, but also exhibit characteristics such as a lower melting point when the particle size is smaller. Is expected to be used in various industrial materials.
  • a copper-based particle deposition layer containing a transition metal or the like is formed at a site where the metal copper film is to be formed, and heated in the presence of formic acid gas to deposit copper-based particles. It has been proposed to form a metal copper film selectively only on the portion.
  • Patent Document 2 in the case of copper fine particle ink applied to the ink jet printing method, if the average dispersed particle size of the metal fine particles exceeds 500 nm, clogging of the ink jet head nozzle or the like occurs. A dispersed particle size of 300 nm or less is desirable.
  • the surface energy increases and the metal fine particles easily aggregate due to the progress of micronization, and as the microparticles become finer, an ejection error due to clogging of the aggregated particles in the inkjet nozzle may occur. Concerned.
  • the region where the ejection stability from the ink jet head is ensured requires stable dispersion up to an average dispersed particle size of less than 150 nm.
  • Patent Documents 3 and 4 In addition, in order to solve the problem of ejection stability of ink containing metal fine particles, a copper film forming composition using a complex solution of copper formate not containing metal fine particles has also been proposed (Patent Documents 3 and 4). However, the stability of the complex solution with copper formate and the reduction characteristics at low temperatures cannot be said to have been sufficiently studied, and there remains room for improvement.
  • Japanese Unexamined Patent Publication No. 2008-13466 International publication WO2011 / 0334016 Japanese Unexamined Patent Publication No. 2010-242118 Japanese Unexamined Patent Publication No. 2012-112022
  • An object of the present invention is to provide a copper thin film forming composition that is excellent in stability and can form a copper thin film with good conductivity by heat treatment at a relatively low temperature.
  • the copper thin film forming composition of the present invention has the following components (A) to (D); (A) copper formate, (B) a diamine compound represented by the following general formula (1), and (C) an alkyl group. , A surfactant having 4 to 22 carbon atoms, and (D) an organic solvent containing 30% by weight or more of ethylene glycol.
  • R 1 to R 4 independently represent a hydrogen atom, an optionally substituted alkyl group having 2 to 40 carbon atoms, an alkyl ether group, an alkyl ester group or an OH group, The number is 0, 1, 2 or 4, and X represents a single bond, or —CO—, —O—, —NH—, —NHCO—, or — (CH 2 ) n 1 —O—.
  • composition for forming a copper thin film of the present invention may contain the component (A) in a range of 5 wt% to 75 wt%.
  • the copper thin film forming composition of the present invention may contain the component (B) in a range of 0.05 mol or more and 3 mol or less with respect to 1 mol of the component (A).
  • composition for forming a copper thin film of the present invention may contain the component (C) in a range of 1 wt% to 10 wt%.
  • the copper thin film-forming composition of the present invention may contain the component (D) within a range of 30% by weight to 70% by weight.
  • the composition for forming a copper thin film of the present invention can be easily formed into an ink, has excellent stability, and can form a copper thin film with good conductivity by heat treatment at a relatively low temperature. Therefore, the copper thin film forming composition of the present invention is suitable for applications such as ink jet conductive ink.
  • the copper thin film forming composition according to the present embodiment includes the following components (A) to (D): (A) copper formate, (B) a diamine compound represented by the following general formula (1), (C) a surfactant having an alkyl group and having 4 to 22 carbon atoms, And (D) an organic solvent containing 30% by weight or more of ethylene glycol.
  • R 1 to R 4 independently represent a hydrogen atom, an optionally substituted alkyl group having 2 to 40 carbon atoms, an alkyl ether group, an alkyl ester group or an OH group, The number is 0, 1, 2 or 4, and X represents a single bond, or —CO—, —O—, —NH—, —NHCO—, or — (CH 2 ) n 1 —O—.
  • a component is copper formate.
  • the copper formate defined here is not only Cu (HCOO) 2 but also its hydrate [Cu (HCOO) 2 .4H 2 O] and an organic monoamine capable of substituting coordinated water in the hydrate.
  • the content of copper formate (or a hydrate thereof) in the copper thin film forming composition of the present invention is preferably in the range of, for example, 5% by weight to 75% by weight from the viewpoint of improving the conductivity of the copper thin film. A range of 10 wt% to 65 wt% is more preferable.
  • the content of copper formate (or its hydrate) is less than 5% by weight, the conductivity of the copper thin film may not be sufficiently obtained, and if it exceeds 75% by weight, agglomeration and precipitates are generated. It may be difficult to make a uniform ink.
  • (B) component The diamine compound represented by the general formula (1) of the component (B) (hereinafter sometimes referred to as “diamine compound”) forms a complex with copper formate, and also for thermal decomposition of the formed amine complex. This has the effect of reducing the reduction temperature due to the formic acid produced.
  • R 1 to R 4 represent a hydrogen atom, an optionally substituted alkyl group having 2 to 40 carbon atoms, an alkyl ether group, an alkyl ester group, or an OH group.
  • examples thereof include a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkyl ether group having 2 to 6 carbon atoms, and an OH group, and more preferably, for example, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or R 2 A group in which one of -R 4 is substituted with an OH group can be mentioned.
  • X represents a single bond, or —CO—, —O—, —NH—, —NHCO—, or — (CH 2 ) n 1 —O— (CH 2 ). a divalent group selected from n 2 —O— (CH 2 ) n 3 — (where n 1 , n 2 and n 3 independently represent a number of 0 to 4), or 20 is a divalent hydrocarbon group.
  • Preferred examples of X include those in which n 1 , n 2 and n 3 independently represent a number of 1 to 4, more specifically, In the above, n 1 and n 3 are each 1 or 2, and n 2 is 2 to 4.
  • Preferred examples of the diamine compound represented by the general formula (1) include 1,2-bis (2-aminoethoxy) ethane, 1,4-butanediol bis (3-aminopropyl) ether, ethylenediamine, propylenediamine, Butylethylenediamine, diethylethylenediamine, tetramethylethylenediamine, 2- (2-aminoethylamino) ethanol, bis (2-hydroxyethyl) ethylenediamine, tetrakis (2-hydroxyethyl) ethylenediamine, tetrakis (2-hydroxypropyl) ethylenediamine, and these And alkyl isomers.
  • the content of the diamine compound in the copper thin film forming composition of the present invention is, for example, 0.05 mol or more and 3 mol or less with respect to 1 mol of copper formate, from the viewpoint of improving the conductivity of the copper thin film by the diamine compound. Within the range, the range of 0.1 mol or more and 2 mol or less is more preferable. If the content of the diamine compound is less than 0.05 mol, the conductivity of the copper thin film may not be sufficiently obtained. If the content of the diamine compound exceeds 3 mol, it may remain in the copper thin film and reduce the conductivity. This is not preferable.
  • the copper thin film forming composition according to the present embodiment may contain an amine compound other than the diamine compound represented by the general formula (1).
  • examples of other amine compounds that can be used in combination with the diamine compound represented by the general formula (1) include dimethylethanolamine, methylethanolamine, diethylethanolamine, methyldiethanolamine, ⁇ -aminoethylisopropanolamine, and diethylisopropanolamine. And so on.
  • Component (C) Component (C), a surfactant having an alkyl group and having 4 to 22 carbon atoms, has an action of dispersing a complex of copper formate and an amine. By such a dispersing action, fine nuclei of metallic copper can be generated in a uniformly diffused state during reduction.
  • the component (C) surfactant include nonionic surfactants such as polyoxyethylene alkyl alcohol and acetylene glycol compounds.
  • the component (C) surfactant has a low molecular weight, is decomposed and removed by heat treatment, and hardly remains in the copper thin film.
  • acetylene glycol compounds are particularly preferable.
  • the acetylene glycol compound has a strong dispersing action for dispersing a complex of copper formate and an amine. By such a dispersing action, fine nuclei of metallic copper can be generated in a uniformly diffused state during reduction.
  • the acetylene glycol compound is a low boiling point compound, it is decomposed and removed by heat treatment and hardly remains in the copper thin film. Thus, the acetylene glycol compound exhibits a strong dispersing action until the reduction treatment, and is easily decomposed and removed during the heat treatment.
  • component (C) commercially available products may be used.
  • New Coal 1008 (trade name; manufactured by Nippon Emulsifier Co., Ltd.), New Coal 2308 (trade name; manufactured by Nihon Emulsifier Co., Ltd.), Surfynol (registered) (Trademark) 104A (made by Air Products Japan) etc. can be mentioned.
  • the content of the surfactant of component (C) in the copper thin film forming composition of the present invention is such that the complex of copper formate and a diamine compound is dispersed to form fine and uniform nuclei of metallic copper. From the viewpoint of densifying the obtained copper thin film and improving its electrical conductivity, for example, it is preferably in the range of 1% by weight to 10% by weight, and more preferably in the range of 1% by weight to 5% by weight.
  • the content of the component (C) surfactant is less than 1% by weight, there is a possibility that the dispersion effect is insufficient and the conductivity of the copper thin film may not be sufficiently obtained. We cannot expect improvement of effect.
  • the copper thin film forming composition according to the present embodiment may contain a surfactant other than the surfactant having an alkyl group and having 4 to 22 carbon atoms, which is component (C).
  • a surfactant other than the surfactant having an alkyl group and having 4 to 22 carbon atoms which is component (C).
  • other surfactants that can be used in combination with the surfactant of component (C) include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene noniel phenyl ether, Sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene monolaurate, polyoxyethylene monostearate, oleic acid monoglyceride, stearic acid monoglyceride, polyoxyethylene-polyoxy A propylene block copolymer etc. can be mentioned.
  • (D) component (D)
  • the organic solvent of a component contains 30 weight% or more of ethylene glycol with respect to the whole (D) component.
  • Ethylene glycol is easily miscible with water, has excellent solubility of copper formate, and has a low boiling point (boiling point: 197.3 ° C.). Therefore, it is easily decomposed by heat treatment and does not remain in the copper thin film. The conductivity of the copper thin film can be improved.
  • the amount of ethylene glycol in the organic solvent of component (D) is less than 30% by weight, the decomposition product of the organic solvent remains in the copper thin film and increases the electrical resistance, so that the conductivity of the copper thin film is obtained. Disappear.
  • the content of ethylene glycol in the organic solvent of component (D) is preferably 40% by weight or more, more preferably 50% by weight or more, and preferably 60% by weight or more.
  • a solvent other than ethylene glycol can be used together with ethylene glycol.
  • the solvent other than ethylene glycol include polyhydric alcohols such as propylene glycol, diethylene glycol, propane diol, butane diol, propane triol, polyerylene glycol, and polypropylene glycol, methanol, ethanol, propanol, isopropanol, butanol, hexanol, and terpineol.
  • alcohol solvents such as dihydroterpinyl acetate, methyl acetate, ethyl acetate, propyl acetate, and methyl methacrylate
  • ketone solvents such as acetone, MEK, and MIBK.
  • the content of the organic solvent of the component (D) in the copper thin film forming composition of the present invention is, for example, in the range of 30 wt% or more and 70 wt% or less in order to dissolve the copper formate and maintain the necessary liquid state as the ink.
  • the inside is preferable, and the inside of the range of 55 wt% or more and 65 wt% or less is more preferable.
  • the content of the organic solvent of the component (D) is less than 30% by weight, the reduction becomes unstable and the metallization of copper tends to be insufficient, and when it exceeds 70% by weight, the conductivity tends to decrease. It becomes.
  • the copper thin film forming composition of the present invention includes, as an optional component, for example, a stabilizer, a thickener, an antigelling agent, an antifoaming agent, a leveling agent, a diluent, a dimension stabilizing agent, and the like. It may contain.
  • a stabilizer for example, a stabilizer, a thickener, an antigelling agent, an antifoaming agent, a leveling agent, a diluent, a dimension stabilizing agent, and the like. It may contain.
  • the copper thin film-forming composition of the present invention can be prepared by mixing a predetermined amount of the above essential components and, if necessary, optional components.
  • Application of the copper thin film forming composition of the present invention is performed by applying a conductive ink on a substrate by a coating method such as an ink jet method or a screen printing method to form a coating film. Thereafter, the coating film is heat-treated at a temperature in the range of 200 to 300 ° C., for example, so that conductive layers such as a copper thin film, a copper wiring layer, and a copper electrode layer having excellent conductivity can be formed.
  • the composition for forming a copper thin film of the present invention can be easily formed into an ink, has excellent storage stability, and can form a copper thin film with good conductivity by heat treatment at a relatively low temperature. Therefore, the copper thin film-forming composition of the present invention is used as a conductive ink applied by a coating method such as an ink jet method or a screen printing method, for example, in the process of manufacturing various circuit boards or electronic components, for example, conductive materials such as wiring and electrodes. It can be preferably used for the purpose of forming a layer.
  • Ink evaluation of the copper thin film forming composition was determined visually. When the composition is obtained as a uniform composition as the classification, it is judged as “Yes”, and the composition contains sediment such as aggregates and insoluble components, and is obtained as a non-uniform composition. Was determined to be “impossible”. In addition, it was judged that the composition whose ink conversion evaluation was “impossible” could not be applied and printed.
  • the copper thin film forming composition was applied by fixing the spin coater rotation number ⁇ time to 400 rpm ⁇ 10 seconds so that the copper thin film after the heat treatment was about 1.0 ⁇ m. Thereafter, a volatile solvent was volatilized from the coating film by VCD (manufactured by ULVAC).
  • the above substrate is placed on a hot plate (Fischer Scientific), heated from room temperature to 150 ° C. under a nitrogen stream, held for 15 minutes, and then cooled to 70 ° C. or lower over 15 minutes. A substrate was used. Further, the substrate was heated to an additional temperature of 300 ° C. after the substrate and held for 15 minutes, and the temperature was lowered to 70 ° C. or less over 15 minutes was used as the secondary conductivity evaluation substrate.
  • a hot plate Fischer Scientific
  • Copper formate Copper formate (1) Copper formate (II) tetrahydrate (manufactured by Kishida Chemical Co., Ltd.)
  • Diamine Compound Diamine (1) 1,2-bis (2-aminoethoxy) ethane (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Diamine (2) 1,4-butanediol bis (3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Diamine (3) Bis (2-hydroxyethyl) ethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Surfactant Surfactant (1) Polyoxyethylene (8) Octyl alcohol (Nonionic surfactant, manufactured by Nippon Emulsifier Co., Ltd., trade name: New Coal 1008)
  • Surfactant (2) polyoxyethylene (8) lauryl alcohol (nonionic surfactant, manufactured by Nippon Emulsifier Co., Ltd., trade name: New Coal 2308)
  • Surfactant (3) Acetylene glycol compound (manufactured by Air Products Japan, trade name: Surfynol 104A)
  • D Organic solvent ethylene glycol: manufactured by Kanto Chemical Co., Ltd.
  • Example 1 59.1 parts by weight of ethylene glycol, 22.4 parts by weight of diamine (1), and 17.1 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 1 was obtained. To this, 1.4 parts by weight of the surfactant (1) was added and mixed, and filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition 1. The obtained copper thin film forming composition 1 became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition 1 was visually uniform, and was determined as “possible” as an ink evaluation. The results are shown in Table 1.
  • Example 2 59.2 parts by weight of ethylene glycol, 25.5 parts by weight of diamine (2), and 14.1 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 2 was obtained. To this, 1.2 parts by weight of surfactant (1) was added and mixed, and filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition 2. The obtained copper thin film forming composition 2 became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition 2 was visually uniform, and was determined as “possible” as the ink evaluation. The results are shown in Table 1.
  • Example 3 59.1 parts by weight of ethylene glycol, 22.4 parts by weight of diamine (1), and 17.1 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 3 was obtained. To this, 1.4 parts by weight of surfactant (2) was added and mixed, and filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition 3. The obtained copper thin film forming composition 3 became a blue transparent liquid having fluidity. Moreover, the copper thin film formation composition 3 was uniform visually, and was determined as “possible” as the ink evaluation. The results are shown in Table 1.
  • Example 4 58.7 parts by weight of ethylene glycol, 25.2 parts by weight of diamine (2), and 13.9 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 4 was obtained. To this, 2.2 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition 4. The obtained copper thin film forming composition 4 became a blue transparent liquid having fluidity. Moreover, the copper thin film formation composition 4 was uniform visually, and it was determined as “possible” as ink evaluation. The results are shown in Table 1.
  • Example 5 58.4 parts by weight of ethylene glycol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 5 was obtained. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition 5. The obtained copper thin film forming composition 5 became a blue transparent liquid having fluidity. Moreover, the copper thin film formation composition 5 was uniform visually, and was determined as “possible” as the ink evaluation. The results are shown in Table 1.
  • Example 6 35.1 parts by weight of ethylene glycol, 23.3 parts by weight of methanol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45 to 50 ° C. for 30 minutes. Then, the copper complex ink intermediate 6 was obtained by cooling to room temperature. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition 6. The obtained copper thin film forming composition 6 became a blue transparent liquid having fluidity. Moreover, the copper thin film formation composition 6 was uniform visually, and it was determined as “possible” as ink evaluation. The results are shown in Table 1.
  • Example 7 29.2 parts by weight of ethylene glycol, 29.2 parts by weight of methanol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45-50 ° C. for 30 minutes. Then, the copper complex ink intermediate 7 was obtained by cooling to room temperature. To this, 2.7 parts by weight of surfactant (3) was added and mixed, followed by filtration with a 1 ⁇ m filter to obtain a copper thin film forming composition 7. The obtained copper thin film forming composition 7 became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition 7 was visually uniform, and was determined as “possible” as the ink evaluation. The results are shown in Table 1.
  • Example 8 23.4 parts by weight of ethylene glycol, 35.0 parts by weight of methanol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45 to 50 ° C. for 30 minutes. Then, the copper complex ink intermediate 8 was obtained by cooling to room temperature. To this, 2.7 parts by weight of surfactant (3) was added and mixed, followed by filtration with a 1 ⁇ m filter to obtain a copper thin film forming composition 8. The obtained copper thin film forming composition 8 became a blue transparent liquid having fluidity. Moreover, the copper thin film formation composition 8 was uniform visually, and it was determined as "OK" as an ink evaluation. The results are shown in Table 1.
  • Example 9 35.9 parts by weight of ethylene glycol, 34.0 parts by weight of diamine (1), and 25.9 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 9 was obtained. To this, 4.2 parts by weight of surfactant (3) was added and mixed, followed by filtration with a 1 ⁇ m filter to obtain a copper thin film forming composition 9. The obtained copper thin film forming composition 9 became a blue transparent liquid having fluidity. Moreover, the copper thin film formation composition 9 was uniform visually, and was determined as “possible” as the ink evaluation. The results are shown in Table 1.
  • Example 10 58.4 parts by weight of ethylene glycol, 22.1 parts by weight of diamine (3) and 16.8 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 10 was obtained. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition 10. The obtained copper thin film forming composition 10 became a blue transparent liquid having fluidity. Moreover, the copper thin film formation composition 10 was uniform visually, and was determined as "OK" as ink evaluation. The results are shown in Table 1.
  • Example 11 58.8 parts by weight of ethylene glycol, 26.5 parts by weight of diamine (4), and 12.7 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 11 was obtained. To this, 2.0 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition 11. The obtained copper thin film forming composition 11 became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition 11 was visually uniform, and was determined as “possible” as an ink evaluation. The results are shown in Table 1.
  • Example 12 58.1 parts by weight of ethylene glycol, 19.7 parts by weight of diamine (5), and 19.1 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 12 was obtained.
  • the copper thin film forming composition 12 was obtained by adding and mixing 3.1 weight part surfactant (3) to this, and filtering with a 1 micrometer filter. The obtained copper thin film forming composition 12 became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition 12 was visually uniform, and was determined as “possible” as the ink evaluation. The results are shown in Table 1.
  • Comparative Example 1 56.4 parts by weight of ethylene glycol and 37.6 parts by weight of copper formate (1) were stirred and mixed at 45 to 50 ° C. for 30 minutes, and then cooled to room temperature to obtain a copper complex ink intermediate. To this, 6.0 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition. Although the obtained copper thin film forming composition became a blue liquid, it did not dissolve uniformly, so it was determined as “impossible” by visual ink evaluation. The results are shown in Table 2.
  • Comparative Example 2 After stirring and mixing 58.1 parts by weight of ethylene glycol and 38.8 parts by weight of copper formate (1) at 45 to 50 ° C. for 30 minutes, the mixture was cooled to room temperature to obtain a copper complex ink intermediate. To this, 3.1 parts by weight of surfactant (1) was added and mixed, and filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition. Although the obtained copper thin film forming composition became a blue liquid, it did not dissolve uniformly, so it was determined as “impossible” by visual ink evaluation. The results are shown in Table 2.
  • Comparative Example 3 17.5 parts by weight of ethylene glycol, 40.9 parts by weight of methanol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45-50 ° C. for 30 minutes. Then, the copper complex ink intermediate was obtained by cooling to room temperature. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition. The obtained copper thin film forming composition became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition was visually uniform, and was determined as “possible” as an ink evaluation. The results are shown in Table 2.
  • Comparative Example 4 11.7 parts by weight of ethylene glycol, 46.7 parts by weight of methanol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45 to 50 ° C. for 30 minutes. Then, the copper complex ink intermediate was obtained by cooling to room temperature. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition. The obtained copper thin film forming composition became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition was visually uniform, and was determined as “possible” as an ink evaluation. The results are shown in Table 2.
  • Comparative Example 5 5.9 parts by weight of ethylene glycol, 52.5 parts by weight of methanol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45 to 50 ° C. for 30 minutes. Then, the copper complex ink intermediate was obtained by cooling to room temperature. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition. The obtained copper thin film forming composition became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition was visually uniform, and was determined as “possible” as an ink evaluation. The results are shown in Table 2.
  • Comparative Example 6 By stirring and mixing 58.4 parts by weight of methanol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) at 45-50 ° C. for 30 minutes, the mixture was cooled to room temperature. A copper complex ink intermediate was obtained. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition. The obtained copper thin film forming composition became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition was visually uniform, and was determined as “possible” as an ink evaluation. The results are shown in Table 2.
  • Comparative Example 7 58.4 parts by weight of diethylene glycol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45-50 ° C. for 30 minutes, and then cooled to room temperature. A copper complex ink intermediate was obtained. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition. Although the obtained copper thin film forming composition became a blue liquid, it did not dissolve uniformly, so it was determined as “impossible” by visual ink evaluation. The results are shown in Table 2.
  • Comparative Example 8 58.4 parts by weight of terpineol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45 to 50 ° C. for 30 minutes, and then cooled to room temperature. A copper complex ink intermediate was obtained. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition. Although the obtained copper thin film forming composition became a blue liquid, it did not dissolve uniformly, so it was determined as “impossible” by visual ink evaluation. The results are shown in Table 2.
  • Comparative Example 9 58.4 parts by weight of dihydroterpinyl acetate, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45-50 ° C. for 30 minutes, and then brought to room temperature.
  • the copper complex ink intermediate was obtained by cooling.
  • 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition.
  • the obtained copper thin film forming composition became a blue liquid, it did not dissolve uniformly, so it was determined as “impossible” by visual ink evaluation. The results are shown in Table 2.
  • Comparative Example 10 61.1 parts by weight of ethylene glycol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate was obtained. This was filtered through a 1 ⁇ m filter to obtain a copper thin film forming composition. The obtained copper thin film forming composition became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition was visually uniform, and was determined as “possible” as an ink evaluation. The results are shown in Table 2.
  • the copper thin film forming compositions of Examples 1 to 12 containing a combination of the above components (A) to (D) are easy to ink and have excellent copper thin film conductivity. It was.
  • the compositions of Comparative Examples 1 to 10 which did not have the combination of the above components (A) to (D) were inferior to the examples in either the ink evaluation or the conductivity.

Abstract

This copper thin film forming composition contains (A) copper formate, (B) a diamine compound represented by general formula (1), (C) a surfactant having an alkyl group and 4-22 carbon atoms, and (D) an organic solvent containing 30 wt% or more ethylene glycol. [Chemical formula 1] [In the formula, R1 to R4 independently represent a hydrogen atom, an optionally substituted alkyl group of 2-40 carbon atoms, an alkyl ether group, an alkyl ester group or an OH group, the number of OH groups being 0, 1, 2 or 4; X represents a simple bond, or, a divalent group selected from -CO-, -O-, -NH-, -NHCO- or -(CH2)n1-O-(CH2)n2-O-(CH2)n3- (here, n1, n2 and n3 independently represent a number from 0 to 4), or, a divalent hydrocarbon group having 1-20 carbon atoms.]

Description

銅薄膜形成組成物Copper thin film forming composition
　本発明は、銅薄膜形成組成物に関し、より詳しくは、例えばインクジェット法によって塗布されるインクとして好適に利用できる銅薄膜形成組成物に関する。 The present invention relates to a copper thin film forming composition, and more particularly to a copper thin film forming composition that can be suitably used as an ink applied by, for example, an inkjet method.
　近年、電子機器の小型化や薄型化に伴い、金属材料の微細配置技術や薄膜形成技術が検討されている。例えば、微細且つ緻密な電子機器の製造において、平均粒子径が１００ｎｍ以下である金属ナノ微粒子を溶媒中に分散させた金属ナノインクを調製し、インクジェット印刷法やスクリーン印刷法で微細なパターン形状に塗布形成するプリンテッドエレクトロニクス製造技術の開発が進んでいる。 In recent years, with the miniaturization and thinning of electronic devices, metal material fine arrangement technology and thin film formation technology have been studied. For example, in the manufacture of fine and dense electronic devices, a metal nano ink in which metal nano particles with an average particle size of 100 nm or less are dispersed in a solvent is prepared and applied to a fine pattern shape by an ink jet printing method or a screen printing method. Development of the printed electronics manufacturing technology to be formed is advancing.
　金属微粒子は、バルク金属とは異なり、粒子サイズが小さいためファインパターンへの対応に最適であるだけでなく、粒子サイズが小さくなると融点が下がるなどの特性を示すことから、バルク金属の融点温度未満の低温での処理も期待され、様々な工業材料への利用が有望視されている。 Unlike the bulk metal, the metal fine particles are not only optimal for dealing with fine patterns because of their small particle size, but also exhibit characteristics such as a lower melting point when the particle size is smaller. Is expected to be used in various industrial materials.
　金属ナノインクに使用される金属としては、銀微粒子での検討が多くなされているが、銀は高価であり、コスト面で問題があるため、例えば、特許文献１では、銅微粒子を用いた金属ナノ粒子インクが提案されている。 As a metal used in the metal nano ink, many studies have been made on silver fine particles. However, since silver is expensive and has a problem in terms of cost, for example, in Patent Document 1, metal nano particles using copper fine particles are used. Particle inks have been proposed.
　また、特許文献２では、金属銅膜の形成に際し、金属銅膜を形成したい部位に、遷移金属等を含む銅系粒子堆積層を形成し、ギ酸ガスの存在下で加熱して銅系粒子堆積部のみに選択的に金属銅膜を形成することが提案されている。 Moreover, in patent document 2, when forming a metal copper film, a copper-based particle deposition layer containing a transition metal or the like is formed at a site where the metal copper film is to be formed, and heated in the presence of formic acid gas to deposit copper-based particles. It has been proposed to form a metal copper film selectively only on the portion.
　特許文献２では、インクジェット印刷法に適用する銅微粒子インキの場合、金属微粒子の平均分散粒子径が５００ｎｍを超えるとインクジェットヘッドノズルの目詰まり等が発生するため、安定して印刷するためには平均分散粒子径３００ｎｍ以下が望ましいとされている。しかしながら、実際は微粒子化が進むことで表面エネルギーが増加して金属微粒子が凝集し易くなる、という技術課題があり、微粒子化するほどインクジェットノズル内での凝集粒子の目詰まりによる吐出エラーを引き起こすことが懸念される。工業的な実用性を考えた場合は、インクジェットヘッドからの吐出安定性が担保される領域は、平均分散粒子径が１５０ｎｍを下回る程度までの安定分散が求められている。 In Patent Document 2, in the case of copper fine particle ink applied to the ink jet printing method, if the average dispersed particle size of the metal fine particles exceeds 500 nm, clogging of the ink jet head nozzle or the like occurs. A dispersed particle size of 300 nm or less is desirable. However, in reality, there is a technical problem that the surface energy increases and the metal fine particles easily aggregate due to the progress of micronization, and as the microparticles become finer, an ejection error due to clogging of the aggregated particles in the inkjet nozzle may occur. Concerned. In consideration of industrial practicality, the region where the ejection stability from the ink jet head is ensured requires stable dispersion up to an average dispersed particle size of less than 150 nm.
　また、金属微粒子含有インキの吐出安定性の課題を解決するために、金属微粒子を含まないギ酸銅による錯体溶液での銅膜形成組成物も提案されている（特許文献３、特許文献４）。しかしながら、ギ酸銅による錯体溶液の安定性や、低温での還元特性については、十分な検討が尽くされているとは言えず、改良の余地が残されていた。 In addition, in order to solve the problem of ejection stability of ink containing metal fine particles, a copper film forming composition using a complex solution of copper formate not containing metal fine particles has also been proposed (Patent Documents 3 and 4). However, the stability of the complex solution with copper formate and the reduction characteristics at low temperatures cannot be said to have been sufficiently studied, and there remains room for improvement.
日本国特開２００８－１３４６６号公報Japanese Unexamined Patent Publication No. 2008-13466 国際公開ＷＯ２０１１／０３４０１６号International publication WO2011 / 0334016 日本国特開２０１０－２４２１１８号公報Japanese Unexamined Patent Publication No. 2010-242118 日本国特開２０１２－１１２０２２号公報Japanese Unexamined Patent Publication No. 2012-112022
　本発明の目的は、安定性に優れ、比較的低温での熱処理によって導通性が良好な銅薄膜を形成できる銅薄膜形成組成物を提供することである。 An object of the present invention is to provide a copper thin film forming composition that is excellent in stability and can form a copper thin film with good conductivity by heat treatment at a relatively low temperature.
本発明の銅薄膜形成組成物は、下記成分（Ａ）～（Ｄ）；（Ａ）ギ酸銅、（Ｂ）下記一般式（１）で表されるジアミン化合物、（Ｃ）アルキル基を有し、炭素数４～２２である界面活性剤、及び（Ｄ）３０重量％以上のエチレングリコールを含有する有機溶媒を含有する。 The copper thin film forming composition of the present invention has the following components (A) to (D); (A) copper formate, (B) a diamine compound represented by the following general formula (1), and (C) an alkyl group. , A surfactant having 4 to 22 carbon atoms, and (D) an organic solvent containing 30% by weight or more of ethylene glycol.
Figure JPOXMLDOC01-appb-C000002
 ［式中、Ｒ１～Ｒ４は独立して、水素原子、置換されていてもよい炭素数２～４０のアルキル基、アルキルエーテル基、アルキルエステル基又はＯＨ基を示すが、前記ＯＨ基の数は０、１、２又は４であり、Ｘは単結合を示すか、あるいは、－ＣＯ－、－Ｏ－、－ＮＨ－、－ＮＨＣＯ－、もしくは、－（ＣＨ２）ｎ１－Ｏ－（ＣＨ２）ｎ２－Ｏ－（ＣＨ２）ｎ３－（ここで、ｎ１，ｎ２，ｎ３は独立して０～４の数を示す）から選ばれる２価の基、又は、炭素数１～２０の２価の炭化水素基を示す。］
Figure JPOXMLDOC01-appb-C000002
 [Wherein R 1 to R 4 independently represent a hydrogen atom, an optionally substituted alkyl group having 2 to 40 carbon atoms, an alkyl ether group, an alkyl ester group or an OH group, The number is 0, 1, 2 or 4, and X represents a single bond, or —CO—, —O—, —NH—, —NHCO—, or — (CH 2 ) n 1 —O—. A divalent group selected from (CH 2 ) n 2 —O— (CH 2 ) n 3 — (wherein n 1 , n 2 and n 3 independently represent a number of 0 to 4), or A divalent hydrocarbon group having 1 to 20 carbon atoms is shown. ]
　本発明の銅薄膜形成組成物は、前記（Ａ）成分を５重量％以上７５重量％以下の範囲内で含有するものであってもよい。 The composition for forming a copper thin film of the present invention may contain the component (A) in a range of 5 wt% to 75 wt%.
　本発明の銅薄膜形成組成物は、前記（Ａ）成分１モルに対し、前記（Ｂ）成分を０．０５モル以上３モル以下の範囲内で含有するものであってもよい。 The copper thin film forming composition of the present invention may contain the component (B) in a range of 0.05 mol or more and 3 mol or less with respect to 1 mol of the component (A).
　本発明の銅薄膜形成組成物は、前記（Ｃ）成分を１重量％以上１０重量％以下の範囲内で含有するものであってもよい。 The composition for forming a copper thin film of the present invention may contain the component (C) in a range of 1 wt% to 10 wt%.
　本発明の銅薄膜形成組成物は、前記（Ｄ）成分を、３０重量％以上７０重量％以下の範囲内で含有するものであってもよい。 The copper thin film-forming composition of the present invention may contain the component (D) within a range of 30% by weight to 70% by weight.
　本発明の銅薄膜形成組成物は、インキ化が容易で、安定性に優れ、比較的低温での熱処理によって導通性が良好な銅薄膜を形成できる。従って、本発明の銅薄膜形成組成物は、例えばインクジェット用導電性インクなどの用途に適している。 The composition for forming a copper thin film of the present invention can be easily formed into an ink, has excellent stability, and can form a copper thin film with good conductivity by heat treatment at a relatively low temperature. Therefore, the copper thin film forming composition of the present invention is suitable for applications such as ink jet conductive ink.
　本実施の形態に係る銅薄膜形成組成物は、下記成分（Ａ）～（Ｄ）；
（Ａ）ギ酸銅、
（Ｂ）下記一般式（１）で表されるジアミン化合物、
（Ｃ）アルキル基を有し、炭素数４～２２である界面活性剤、
及び
（Ｄ）３０重量％以上のエチレングリコールを含有する有機溶媒
を含有する。 The copper thin film forming composition according to the present embodiment includes the following components (A) to (D):
(A) copper formate,
(B) a diamine compound represented by the following general formula (1),
(C) a surfactant having an alkyl group and having 4 to 22 carbon atoms,
And (D) an organic solvent containing 30% by weight or more of ethylene glycol.
Figure JPOXMLDOC01-appb-C000003
 ［式中、Ｒ１～Ｒ４は独立して、水素原子、置換されていてもよい炭素数２～４０のアルキル基、アルキルエーテル基、アルキルエステル基又はＯＨ基を示すが、前記ＯＨ基の数は０、１、２又は４であり、Ｘは単結合を示すか、あるいは、－ＣＯ－、－Ｏ－、－ＮＨ－、－ＮＨＣＯ－、もしくは、－（ＣＨ２）ｎ１－Ｏ－（ＣＨ２）ｎ２－Ｏ－（ＣＨ２）ｎ３－（ここで、ｎ１，ｎ２，ｎ３は独立して０～４の数を示す）から選ばれる２価の基、又は、炭素数１～２０の２価の炭化水素基を示す。］
Figure JPOXMLDOC01-appb-C000003
 [Wherein R 1 to R 4 independently represent a hydrogen atom, an optionally substituted alkyl group having 2 to 40 carbon atoms, an alkyl ether group, an alkyl ester group or an OH group, The number is 0, 1, 2 or 4, and X represents a single bond, or —CO—, —O—, —NH—, —NHCO—, or — (CH 2 ) n 1 —O—. A divalent group selected from (CH 2 ) n 2 —O— (CH 2 ) n 3 — (wherein n 1 , n 2 and n 3 independently represent a number of 0 to 4), or A divalent hydrocarbon group having 1 to 20 carbon atoms is shown. ]
（Ａ）成分：
　（Ａ）成分は、ギ酸銅である。ここで定義するギ酸銅とは、Ｃｕ(ＨＣＯＯ)２のみならず、その水和物［Ｃｕ(ＨＣＯＯ)２・４Ｈ２Ｏ］や、当該水和物における配位水を置換可能とする有機モノアミンが配位したギ酸銅錯体を意味する。本発明の銅薄膜形成組成物中のギ酸銅（又はその水和物）の含有量は、銅薄膜の導通性を良好にする観点から、例えば５重量％以上７５重量％以下の範囲内が好ましく、１０重量％以上６５重量％以下の範囲内がより好ましい。ギ酸銅（又はその水和物）の含有量が５重量％を下回ると、銅薄膜の導通性が十分に得られない可能性があり、７５重量％を超えると凝集や沈殿物が生成して均一なインキ化が困難となる場合がある。 (A) component:
(A) A component is copper formate. The copper formate defined here is not only Cu (HCOO) 2 but also its hydrate [Cu (HCOO) 2 .4H 2 O] and an organic monoamine capable of substituting coordinated water in the hydrate. Means a copper formate complex coordinated with The content of copper formate (or a hydrate thereof) in the copper thin film forming composition of the present invention is preferably in the range of, for example, 5% by weight to 75% by weight from the viewpoint of improving the conductivity of the copper thin film. A range of 10 wt% to 65 wt% is more preferable. If the content of copper formate (or its hydrate) is less than 5% by weight, the conductivity of the copper thin film may not be sufficiently obtained, and if it exceeds 75% by weight, agglomeration and precipitates are generated. It may be difficult to make a uniform ink.
（Ｂ）成分：
　（Ｂ）成分の一般式（１）で表されるジアミン化合物（以下、「ジアミン化合物」と記すことがある）は、ギ酸銅との錯体を形成するとともに、形成されたアミン錯体の熱分解に伴って生成するギ酸による還元の温度を下げる効果がある。 (B) component:
The diamine compound represented by the general formula (1) of the component (B) (hereinafter sometimes referred to as “diamine compound”) forms a complex with copper formate, and also for thermal decomposition of the formed amine complex. This has the effect of reducing the reduction temperature due to the formic acid produced.
　一般式（１）中、Ｒ１～Ｒ４は、水素原子、置換されていてもよい炭素数２～４０のアルキル基、アルキルエーテル基、アルキルエステル基又はＯＨ基を示すが、好ましくは、例えば水素原子、炭素数１～８のアルキル基、炭素数が２～６のアルキルエーテル基又はＯＨ基を挙げることができ、より好ましくは、例えば水素原子、炭素数１～６のアルキル基又はＲ２～Ｒ４のうち１つがＯＨ基で置換されているものを挙げることができる。 In the general formula (1), R 1 to R 4 represent a hydrogen atom, an optionally substituted alkyl group having 2 to 40 carbon atoms, an alkyl ether group, an alkyl ester group, or an OH group. Preferably, for example, Examples thereof include a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkyl ether group having 2 to 6 carbon atoms, and an OH group, and more preferably, for example, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or R 2 A group in which one of -R 4 is substituted with an OH group can be mentioned.
　一般式（１）中、Ｘは、単結合を示すか、あるいは、－ＣＯ－、－Ｏ－、－ＮＨ－、－ＮＨＣＯ－、もしくは、－（ＣＨ２）ｎ１－Ｏ－（ＣＨ２）ｎ２－Ｏ－（ＣＨ２）ｎ３－（ここで、ｎ１，ｎ２，ｎ３は独立して０～４の数を示す）から選ばれる２価の基、又は、炭素数１～２０の２価の炭化水素基を示すが、好ましいＸとしては、例えば、上記ｎ１，ｎ２，ｎ３が独立して１～４の数を示すものを挙げることができ、より具体的には、上記ｎ１，ｎ３がそれぞれ１又は２であり、ｎ２が２ないし４であるものを挙げることができる。 In the general formula (1), X represents a single bond, or —CO—, —O—, —NH—, —NHCO—, or — (CH 2 ) n 1 —O— (CH 2 ). a divalent group selected from n 2 —O— (CH 2 ) n 3 — (where n 1 , n 2 and n 3 independently represent a number of 0 to 4), or 20 is a divalent hydrocarbon group. Preferred examples of X include those in which n 1 , n 2 and n 3 independently represent a number of 1 to 4, more specifically, In the above, n 1 and n 3 are each 1 or 2, and n 2 is 2 to 4.
　一般式（１）で表されるジアミン化合物の好ましい例としては、１,２‐ビス（２‐アミノエトキシ）エタン、１,４-ブタンジオールビス（３‐アミノプロピル）エーテル、エチレンジアミン、プロピレンジアミン、ブチルエチレンジアミン、ジエチルエチレンジアミン、テトラメチルエチレンジアミン、２－（２－アミノエチルアミノ）エタノール、ビス（２－ヒドロキシエチル）エチレンジアミン、テトラキス（２－ヒドロキシエチル）エチレンジアミン、テトラキス（２－ヒドロキシプロピル）エチレンジアミン、またこれらのアルキル異性体等を挙げることができる。 Preferred examples of the diamine compound represented by the general formula (1) include 1,2-bis (2-aminoethoxy) ethane, 1,4-butanediol bis (3-aminopropyl) ether, ethylenediamine, propylenediamine, Butylethylenediamine, diethylethylenediamine, tetramethylethylenediamine, 2- (2-aminoethylamino) ethanol, bis (2-hydroxyethyl) ethylenediamine, tetrakis (2-hydroxyethyl) ethylenediamine, tetrakis (2-hydroxypropyl) ethylenediamine, and these And alkyl isomers.
　本発明の銅薄膜形成組成物中のジアミン化合物の含有量は、ジアミン化合物によって銅薄膜の導通性を良好にする観点から、ギ酸銅１モルに対して、例えば０．０５モル以上３モル以下の範囲内が好ましく、０．１モル以上２モル以下の範囲内がより好ましい。ジアミン化合物の含有量が０．０５モルを下回ると、銅薄膜の導通性が十分に得られない可能性があり、３モルを超えると、銅薄膜に残存して導通性を低下させる可能性があるため好ましくはない。 The content of the diamine compound in the copper thin film forming composition of the present invention is, for example, 0.05 mol or more and 3 mol or less with respect to 1 mol of copper formate, from the viewpoint of improving the conductivity of the copper thin film by the diamine compound. Within the range, the range of 0.1 mol or more and 2 mol or less is more preferable. If the content of the diamine compound is less than 0.05 mol, the conductivity of the copper thin film may not be sufficiently obtained. If the content of the diamine compound exceeds 3 mol, it may remain in the copper thin film and reduce the conductivity. This is not preferable.
　なお、本実施の形態に係る銅薄膜形成組成物には、一般式（１）で表されるジアミン化合物以外のアミン化合物を含有してもよい。一般式（１）で表されるジアミン化合物と組み合わせて使用可能な他のアミン化合物としては、例えばジメチルエタノールアミン、メチルエタノールアミン、ジエチルエタノールアミン、メチルジエタノールアミン、β―アミノエチルイソプロパノールアミン、ジエチルイソプロパノールアミンなどを挙げることができる。 In addition, the copper thin film forming composition according to the present embodiment may contain an amine compound other than the diamine compound represented by the general formula (1). Examples of other amine compounds that can be used in combination with the diamine compound represented by the general formula (1) include dimethylethanolamine, methylethanolamine, diethylethanolamine, methyldiethanolamine, β-aminoethylisopropanolamine, and diethylisopropanolamine. And so on.
（Ｃ）成分：
　（Ｃ）成分である、アルキル基を有し、炭素数４～２２である界面活性剤は、ギ酸銅とアミンとの錯体を分散させる作用を有している。このような分散作用によって、還元時には、金属銅の微小な核を均一に拡散した状態で生成させることができる。（Ｃ）成分の界面活性剤の好ましい例としては、ポリオキシエチレンアルキルアルコール、アセチレングリコール化合物などのノニオン系界面活性剤を挙げることができる。（Ｃ）成分の界面活性剤は、低分子量であり、熱処理によって分解・除去され、銅薄膜中に残存しにくい。 Component (C):
Component (C), a surfactant having an alkyl group and having 4 to 22 carbon atoms, has an action of dispersing a complex of copper formate and an amine. By such a dispersing action, fine nuclei of metallic copper can be generated in a uniformly diffused state during reduction. Preferable examples of the component (C) surfactant include nonionic surfactants such as polyoxyethylene alkyl alcohol and acetylene glycol compounds. The component (C) surfactant has a low molecular weight, is decomposed and removed by heat treatment, and hardly remains in the copper thin film.
　上記ノニオン系界面活性剤の中でも、特に、アセチレングリコール化合物が好ましい。アセチレングリコール化合物は、ギ酸銅とアミンとの錯体を分散させる強い分散作用を有している。このような分散作用によって、還元時には、金属銅の微小な核を均一に拡散した状態で生成させることができる。また、アセチレングリコール化合物は、低沸点化合物であるため、熱処理によって分解・除去され、銅薄膜中に残存しにくい。このように、アセチレングリコール化合物は、還元処理までは強い分散作用を奏し、熱処理時には容易に分解して除去される。 Among the above nonionic surfactants, acetylene glycol compounds are particularly preferable. The acetylene glycol compound has a strong dispersing action for dispersing a complex of copper formate and an amine. By such a dispersing action, fine nuclei of metallic copper can be generated in a uniformly diffused state during reduction. In addition, since the acetylene glycol compound is a low boiling point compound, it is decomposed and removed by heat treatment and hardly remains in the copper thin film. Thus, the acetylene glycol compound exhibits a strong dispersing action until the reduction treatment, and is easily decomposed and removed during the heat treatment.
　（Ｃ）成分としては、市販品を利用することも可能であり、例えば、ニューコール１００８（商品名；日本乳化剤社製）、ニューコール２３０８（商品名；日本乳化剤社製）、サーフィノール（登録商標）１０４Ａ（エアープロダクツジャパン社製）などを挙げることができる。 As the component (C), commercially available products may be used. For example, New Coal 1008 (trade name; manufactured by Nippon Emulsifier Co., Ltd.), New Coal 2308 (trade name; manufactured by Nihon Emulsifier Co., Ltd.), Surfynol (registered) (Trademark) 104A (made by Air Products Japan) etc. can be mentioned.
　本発明の銅薄膜形成組成物中の（Ｃ）成分の界面活性剤の含有量は、ギ酸銅とジアミン化合物との錯体を分散させ、金属銅の微細で均一な核を生成させることによって、最終的に得られる銅薄膜を緻密にし、その導通性を良好にする観点から、例えば１重量％以上１０重量％以下の範囲内が好ましく、１重量％以上５重量％以下の範囲内がより好ましい。（Ｃ）成分の界面活性剤の含有量が１重量％を下回ると、分散効果が不十分となって銅薄膜の導通性が十分に得られない可能性があり、１０重量％を超えても効果の向上が期待できない。 The content of the surfactant of component (C) in the copper thin film forming composition of the present invention is such that the complex of copper formate and a diamine compound is dispersed to form fine and uniform nuclei of metallic copper. From the viewpoint of densifying the obtained copper thin film and improving its electrical conductivity, for example, it is preferably in the range of 1% by weight to 10% by weight, and more preferably in the range of 1% by weight to 5% by weight. When the content of the component (C) surfactant is less than 1% by weight, there is a possibility that the dispersion effect is insufficient and the conductivity of the copper thin film may not be sufficiently obtained. We cannot expect improvement of effect.
　なお、本実施の形態に係る銅薄膜形成組成物には、（Ｃ）成分である、アルキル基を有し、炭素数４～２２である界面活性剤以外の界面活性剤を含有してもよい。（Ｃ）成分の界面活性剤と組み合わせて使用可能な他の界面活性剤としては、例えばポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニエルフェニルエーテル、ソルビタンモノラウレート、ソルビタンモノステアレート、ソルビタントリオレエート、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンモノラウレート、ポリオキシエチレンモノステアレート、オレイン酸モノグリセライド、ステアリン酸モノグリセライド、ポリオキシエチレン－ポリオキシプロピレンブロックコポリマーなどを挙げることができる。 The copper thin film forming composition according to the present embodiment may contain a surfactant other than the surfactant having an alkyl group and having 4 to 22 carbon atoms, which is component (C). . Examples of other surfactants that can be used in combination with the surfactant of component (C) include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene noniel phenyl ether, Sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene monolaurate, polyoxyethylene monostearate, oleic acid monoglyceride, stearic acid monoglyceride, polyoxyethylene-polyoxy A propylene block copolymer etc. can be mentioned.
（Ｄ）成分：
　（Ｄ）成分の有機溶媒は、（Ｄ）成分の全体に対し、エチレングリコールを３０重量％以上含有する。エチレングリコールは、水と混和しやすく、ギ酸銅の溶解性に優れており、かつ、低沸点（沸点１９７．３℃）であるため、熱処理によって容易に分解して銅薄膜中に残存せず、銅薄膜の導通性を良好にすることができる。しかし、（Ｄ）成分の有機溶媒中のエチレングリコールの量が３０重量％未満では、有機溶媒の分解物が銅薄膜中に残存して電気抵抗を上昇させるため、銅薄膜の導通性が得られなくなる。このような観点から、（Ｄ）成分の有機溶媒中のエチレングリコールの含有量は４０重量％以上が好ましく、５０重量％以上がより好ましく、６０重量％以上が望ましい。 (D) component:
(D) The organic solvent of a component contains 30 weight% or more of ethylene glycol with respect to the whole (D) component. Ethylene glycol is easily miscible with water, has excellent solubility of copper formate, and has a low boiling point (boiling point: 197.3 ° C.). Therefore, it is easily decomposed by heat treatment and does not remain in the copper thin film. The conductivity of the copper thin film can be improved. However, if the amount of ethylene glycol in the organic solvent of component (D) is less than 30% by weight, the decomposition product of the organic solvent remains in the copper thin film and increases the electrical resistance, so that the conductivity of the copper thin film is obtained. Disappear. From such a viewpoint, the content of ethylene glycol in the organic solvent of component (D) is preferably 40% by weight or more, more preferably 50% by weight or more, and preferably 60% by weight or more.
　（Ｄ）成分の有機溶媒としては、エチレングリコールとともに、エチレングリコール以外の溶媒も使用することができる。エチレングリコール以外の溶媒としては、例えば、プロピレングリコール、ジエチレングリコール、プロパンジール、ブタンジオール、プロパントリオール、ポリエリレングリコール、ポリプロピレングリコールなどの多価アルコール、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、ヘキサノール、ターピネオール等のアルコール系溶媒、ジヒドロターピニルアセテート、メチルアセテート、エチルアセテート、プロピルアセテート、メチルメタクリレートなどのエステル系溶媒、アセトン、ＭＥＫ、ＭＩＢＫなどのケトン系溶媒を挙げることができる。 (D) As an organic solvent of component (D), a solvent other than ethylene glycol can be used together with ethylene glycol. Examples of the solvent other than ethylene glycol include polyhydric alcohols such as propylene glycol, diethylene glycol, propane diol, butane diol, propane triol, polyerylene glycol, and polypropylene glycol, methanol, ethanol, propanol, isopropanol, butanol, hexanol, and terpineol. And alcohol solvents such as dihydroterpinyl acetate, methyl acetate, ethyl acetate, propyl acetate, and methyl methacrylate, and ketone solvents such as acetone, MEK, and MIBK.
　本発明の銅薄膜形成組成物中の（Ｄ）成分の有機溶媒の含有量は、ギ酸銅を溶解してインクとして必要な液状態を維持するため、例えば３０重量％以上７０重量％以下の範囲内が好ましく、５５重量％以上６５重量％以下の範囲内がより好ましい。（Ｄ）成分の有機溶媒の含有量が３０重量％未満であると、還元が不安定となり、銅の金属化が不十分になる傾向となり、７０重量％を超えると、導電性が低下する傾向となる。 The content of the organic solvent of the component (D) in the copper thin film forming composition of the present invention is, for example, in the range of 30 wt% or more and 70 wt% or less in order to dissolve the copper formate and maintain the necessary liquid state as the ink. The inside is preferable, and the inside of the range of 55 wt% or more and 65 wt% or less is more preferable. When the content of the organic solvent of the component (D) is less than 30% by weight, the reduction becomes unstable and the metallization of copper tends to be insufficient, and when it exceeds 70% by weight, the conductivity tends to decrease. It becomes.
　本発明の銅薄膜形成組成物には、必須成分以外に、任意の成分として、例えば、安定剤、増粘剤、ゲル化防止剤、消泡剤、レベリング剤、希釈剤、寸法安定化剤等を含有してもよい。 In addition to the essential components, the copper thin film forming composition of the present invention includes, as an optional component, for example, a stabilizer, a thickener, an antigelling agent, an antifoaming agent, a leveling agent, a diluent, a dimension stabilizing agent, and the like. It may contain.
　本発明の銅薄膜形成組成物は、所定量の上記必須成分及び必要に応じて任意成分を混合することによって調製できる。 The copper thin film-forming composition of the present invention can be prepared by mixing a predetermined amount of the above essential components and, if necessary, optional components.
　本発明の銅薄膜形成組成物の適用は、導電性インクとして、例えばインクジェット法、スクリーン印刷法などの塗布法により基材上に塗布し、塗布膜を形成することによって行われる。その後、塗布膜を、例えば２００～３００℃の範囲内の温度で熱処理することによって、導通性に優れた銅薄膜、銅配線層、銅電極層などの導電層を形成できる。 Application of the copper thin film forming composition of the present invention is performed by applying a conductive ink on a substrate by a coating method such as an ink jet method or a screen printing method to form a coating film. Thereafter, the coating film is heat-treated at a temperature in the range of 200 to 300 ° C., for example, so that conductive layers such as a copper thin film, a copper wiring layer, and a copper electrode layer having excellent conductivity can be formed.
　本発明の銅薄膜形成組成物は、インク化が容易であり、保存安定性に優れ、比較的低温での熱処理によって導通性が良好な銅薄膜を形成できる。従って、本発明の銅薄膜形成組成物は、例えばインクジェット法、スクリーン印刷法などの塗布方法によって適用される導電性インクとして、各種回路基板や電子部品の製造過程で、例えば配線、電極等の導電層の形成目的で好ましく使用できる。 The composition for forming a copper thin film of the present invention can be easily formed into an ink, has excellent storage stability, and can form a copper thin film with good conductivity by heat treatment at a relatively low temperature. Therefore, the copper thin film-forming composition of the present invention is used as a conductive ink applied by a coating method such as an ink jet method or a screen printing method, for example, in the process of manufacturing various circuit boards or electronic components, for example, conductive materials such as wiring and electrodes. It can be preferably used for the purpose of forming a layer.
　以下に実施例を示し、本発明の特徴をより具体的に説明する。ただし、本発明は実施例に制約されるものではなく、特にことわりのない限り各種の塗工方法、評価方法により特性を得るものである。 Hereinafter, the features of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples, and the characteristics are obtained by various coating methods and evaluation methods unless otherwise specified.
［インキ化評価］
　銅薄膜形成組成物のインキ化評価は目視によって判定した。その区分けとして組成物が均一な組成物として得られた場合は、「可」と判定し、組成物が凝集物や不溶解成分等の沈降物を含み、不均一な組成物として得られた場合は、「不可」と判定した。なお、インキ化評価が「不可」の組成物は、塗布および印刷ができないと判断した。 [Ink evaluation]
Ink evaluation of the copper thin film forming composition was determined visually. When the composition is obtained as a uniform composition as the classification, it is judged as “Yes”, and the composition contains sediment such as aggregates and insoluble components, and is obtained as a non-uniform composition. Was determined to be “impossible”. In addition, it was judged that the composition whose ink conversion evaluation was “impossible” could not be applied and printed.
［基板への塗布］
　加熱処理後の銅薄膜が１．０μｍ程度となるようにスピンコーターの回転数×時間を４００ｒｐｍ×１０秒に固定して銅薄膜形成組成物を塗工した。その後、ＶＣＤ（アルバック社製）にて揮発性溶媒を塗布膜中から揮発させた。 [Coating to substrate]
The copper thin film forming composition was applied by fixing the spin coater rotation number × time to 400 rpm × 10 seconds so that the copper thin film after the heat treatment was about 1.0 μm. Thereafter, a volatile solvent was volatilized from the coating film by VCD (manufactured by ULVAC).
［加熱（銅薄膜形成方法）］
　前述の基板をホットプレート（ＦｉｓｃｈｅｒＳｃｉｅｎｔｉｆｉｃ社製）上に乗せ、窒素気流下で常温から１５０℃に昇温して１５分間保持した後、１５分間かけて７０℃以下に降温したものは一次導通性評価基板とした。また、前記基板に次いで３００℃に追加昇温して１５分間保持、１５分間かけて７０℃以下したものは二次導通性評価基板とした。 [Heating (Cu thin film forming method)]
The above substrate is placed on a hot plate (Fischer Scientific), heated from room temperature to 150 ° C. under a nitrogen stream, held for 15 minutes, and then cooled to 70 ° C. or lower over 15 minutes. A substrate was used. Further, the substrate was heated to an additional temperature of 300 ° C. after the substrate and held for 15 minutes, and the temperature was lowered to 70 ° C. or less over 15 minutes was used as the secondary conductivity evaluation substrate.
［導通性評価］
　前述の基板の導通性評価は、ロレスタＧＰ　ＭＣＰ－Ｔ６１０（三菱化学アナリテック社製）、ＡＳＰプローブを用いて四探針法による体積抵抗率で評価した。評価方法はＪＩＳＫ７１９４に準拠して行った。 [Conductivity evaluation]
The above-mentioned conductivity evaluation of the substrate was evaluated by volume resistivity by a four-probe method using a Loresta GP MCP-T610 (manufactured by Mitsubishi Chemical Analytech) and an ASP probe. The evaluation method was performed according to JISK7194.
　実施例及び比較例の銅薄膜形成組成物を作製するために使用した原料とその略号は以下のとおりである。
（Ａ）ギ酸銅
ギ酸銅（１）：ギ酸銅（II）四水和物（キシダ化学社製） The raw materials and their abbreviations used to produce the copper thin film forming compositions of the examples and comparative examples are as follows.
(A) Copper formate Copper formate (1): Copper formate (II) tetrahydrate (manufactured by Kishida Chemical Co., Ltd.)
（Ｂ）ジアミン化合物
ジアミン（１）：１,２‐ビス（２‐アミノエトキシ）エタン（東京化成工業社製）
ジアミン（２）：１,４-ブタンジオールビス（３‐アミノプロピル）エーテル（東京化成工業社製）
ジアミン（３）：ビス（２－ヒドロキシエチル）エチレンジアミン（東京化成工業社製）
ジアミン（４）：テトラキス（２－ヒドロキシプロピル）エチレンジアミン（東京化成工業社製）
ジアミン（５）：ブチルエチレンジアミン（東京化成工業社製） (B) Diamine Compound Diamine (1): 1,2-bis (2-aminoethoxy) ethane (manufactured by Tokyo Chemical Industry Co., Ltd.)
Diamine (2): 1,4-butanediol bis (3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
Diamine (3): Bis (2-hydroxyethyl) ethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
Diamine (4): Tetrakis (2-hydroxypropyl) ethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
Diamine (5): Butylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
（Ｃ）界面活性剤
界面活性剤（１）：ポリオキシエチレン（８）オクチルアルコール（ノニオン性界面活性剤、日本乳化剤社製、商品名；ニューコール１００８）
界面活性剤（２）：ポリオキシエチレン（８）ラウリルアルコール（ノニオン性界面活性剤、日本乳化剤社製、商品名；ニューコール２３０８）
界面活性剤（３）：アセチレングリコール化合物（エアープロダクツジャパン社製、商品名；サーフィノール１０４Ａ）
（Ｄ）有機溶媒
エチレングリコール：関東化学社製、特級 (C) Surfactant Surfactant (1): Polyoxyethylene (8) Octyl alcohol (Nonionic surfactant, manufactured by Nippon Emulsifier Co., Ltd., trade name: New Coal 1008)
Surfactant (2): polyoxyethylene (8) lauryl alcohol (nonionic surfactant, manufactured by Nippon Emulsifier Co., Ltd., trade name: New Coal 2308)
Surfactant (3): Acetylene glycol compound (manufactured by Air Products Japan, trade name: Surfynol 104A)
(D) Organic solvent ethylene glycol: manufactured by Kanto Chemical Co., Ltd.
［実施例１］
　５９．１重量部のエチレングリコール、２２．４重量部のジアミン（１）、及び１７．１重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体１を得た。これに、１．４重量部の界面活性剤（１）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物１を得た。得られた銅薄膜形成組成物１は流動性を有する青色透明の液体となった。また、銅薄膜形成組成物１は目視にて均一であり、インキ化評価として、「可」と判定した。結果を表１に示す。 [Example 1]
59.1 parts by weight of ethylene glycol, 22.4 parts by weight of diamine (1), and 17.1 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 1 was obtained. To this, 1.4 parts by weight of the surfactant (1) was added and mixed, and filtered through a 1 μm filter to obtain a copper thin film forming composition 1. The obtained copper thin film forming composition 1 became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition 1 was visually uniform, and was determined as “possible” as an ink evaluation. The results are shown in Table 1.
［実施例２］
　５９．２重量部のエチレングリコール、２５．５重量部のジアミン（２）、及び１４．１重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体２を得た。これに、１．２重量部の界面活性剤（１）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物２を得た。得られた銅薄膜形成組成物２は流動性を有する青色透明の液体となった。また、銅薄膜形成組成物２は目視にて均一であり、インキ化評価として、「可」と判定した。結果を表１に示す。 [Example 2]
59.2 parts by weight of ethylene glycol, 25.5 parts by weight of diamine (2), and 14.1 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 2 was obtained. To this, 1.2 parts by weight of surfactant (1) was added and mixed, and filtered through a 1 μm filter to obtain a copper thin film forming composition 2. The obtained copper thin film forming composition 2 became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition 2 was visually uniform, and was determined as “possible” as the ink evaluation. The results are shown in Table 1.
［実施例３］
　５９．１重量部のエチレングリコール、２２．４重量部のジアミン（１）、及び１７．１重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体３を得た。これに、１．４重量部の界面活性剤（２）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物３を得た。得られた銅薄膜形成組成物３は流動性を有する青色透明の液体となった。また、銅薄膜形成組成物３は目視にて均一であり、インキ化評価として、「可」と判定した。結果を表１に示す。 [Example 3]
59.1 parts by weight of ethylene glycol, 22.4 parts by weight of diamine (1), and 17.1 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 3 was obtained. To this, 1.4 parts by weight of surfactant (2) was added and mixed, and filtered through a 1 μm filter to obtain a copper thin film forming composition 3. The obtained copper thin film forming composition 3 became a blue transparent liquid having fluidity. Moreover, the copper thin film formation composition 3 was uniform visually, and was determined as “possible” as the ink evaluation. The results are shown in Table 1.
［実施例４］
　５８．７重量部のエチレングリコール、２５．２重量部のジアミン（２）、及び１３．９重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体４を得た。これに、２．２重量部の界面活性剤（３）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物４を得た。得られた銅薄膜形成組成物４は流動性を有する青色透明の液体となった。また、銅薄膜形成組成物４は目視にて均一であり、インキ化評価として、「可」と判定した。結果を表１に示す。 [Example 4]
58.7 parts by weight of ethylene glycol, 25.2 parts by weight of diamine (2), and 13.9 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 4 was obtained. To this, 2.2 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 μm filter to obtain a copper thin film forming composition 4. The obtained copper thin film forming composition 4 became a blue transparent liquid having fluidity. Moreover, the copper thin film formation composition 4 was uniform visually, and it was determined as “possible” as ink evaluation. The results are shown in Table 1.
［実施例５］
　５８．４重量部のエチレングリコール、２２．１重量部のジアミン（１）、及び１６．８重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体５を得た。これに、２．７重量部の界面活性剤（３）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物５を得た。得られた銅薄膜形成組成物５は流動性を有する青色透明の液体となった。また、銅薄膜形成組成物５は目視にて均一であり、インキ化評価として、「可」と判定した。結果を表１に示す。 [Example 5]
58.4 parts by weight of ethylene glycol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 5 was obtained. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 μm filter to obtain a copper thin film forming composition 5. The obtained copper thin film forming composition 5 became a blue transparent liquid having fluidity. Moreover, the copper thin film formation composition 5 was uniform visually, and was determined as “possible” as the ink evaluation. The results are shown in Table 1.
［実施例６］
　３５．１重量部のエチレングリコール、２３．３重量部のメタノール、２２．１重量部のジアミン（１）、及び１６．８重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体６を得た。これに、２．７重量部の界面活性剤（３）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物６を得た。得られた銅薄膜形成組成物６は流動性を有する青色透明の液体となった。また、銅薄膜形成組成物６は目視にて均一であり、インキ化評価として、「可」と判定した。結果を表１に示す。 [Example 6]
35.1 parts by weight of ethylene glycol, 23.3 parts by weight of methanol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45 to 50 ° C. for 30 minutes. Then, the copper complex ink intermediate 6 was obtained by cooling to room temperature. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 μm filter to obtain a copper thin film forming composition 6. The obtained copper thin film forming composition 6 became a blue transparent liquid having fluidity. Moreover, the copper thin film formation composition 6 was uniform visually, and it was determined as “possible” as ink evaluation. The results are shown in Table 1.
［実施例７］
　２９．２重量部のエチレングリコール、２９．２重量部のメタノール、２２．１重量部のジアミン（１）、及び１６．８重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体７を得た。これに、２．７重量部の界面活性剤（３）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物７を得た。得られた銅薄膜形成組成物７は流動性を有する青色透明の液体となった。また、銅薄膜形成組成物７は目視にて均一であり、インキ化評価として、「可」と判定した。結果を表１に示す。 [Example 7]
29.2 parts by weight of ethylene glycol, 29.2 parts by weight of methanol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45-50 ° C. for 30 minutes. Then, the copper complex ink intermediate 7 was obtained by cooling to room temperature. To this, 2.7 parts by weight of surfactant (3) was added and mixed, followed by filtration with a 1 μm filter to obtain a copper thin film forming composition 7. The obtained copper thin film forming composition 7 became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition 7 was visually uniform, and was determined as “possible” as the ink evaluation. The results are shown in Table 1.
［実施例８］
　２３．４重量部のエチレングリコール、３５．０重量部のメタノール、２２．１重量部のジアミン（１）、及び１６．８重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体８を得た。これに、２．７重量部の界面活性剤（３）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物８を得た。得られた銅薄膜形成組成物８は流動性を有する青色透明の液体となった。また、銅薄膜形成組成物８は目視にて均一であり、インキ化評価として、「可」と判定した。結果を表１に示す。 [Example 8]
23.4 parts by weight of ethylene glycol, 35.0 parts by weight of methanol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45 to 50 ° C. for 30 minutes. Then, the copper complex ink intermediate 8 was obtained by cooling to room temperature. To this, 2.7 parts by weight of surfactant (3) was added and mixed, followed by filtration with a 1 μm filter to obtain a copper thin film forming composition 8. The obtained copper thin film forming composition 8 became a blue transparent liquid having fluidity. Moreover, the copper thin film formation composition 8 was uniform visually, and it was determined as "OK" as an ink evaluation. The results are shown in Table 1.
［実施例９］
　３５．９重量部のエチレングリコール、３４．０重量部のジアミン（１）、及び２５．９重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体９を得た。これに、４．２重量部の界面活性剤（３）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物９を得た。得られた銅薄膜形成組成物９は流動性を有する青色透明の液体となった。また、銅薄膜形成組成物９は目視にて均一であり、インキ化評価として、「可」と判定した。結果を表１に示す。 [Example 9]
35.9 parts by weight of ethylene glycol, 34.0 parts by weight of diamine (1), and 25.9 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 9 was obtained. To this, 4.2 parts by weight of surfactant (3) was added and mixed, followed by filtration with a 1 μm filter to obtain a copper thin film forming composition 9. The obtained copper thin film forming composition 9 became a blue transparent liquid having fluidity. Moreover, the copper thin film formation composition 9 was uniform visually, and was determined as “possible” as the ink evaluation. The results are shown in Table 1.
［実施例１０］
　５８．４重量部のエチレングリコール、２２．１重量部のジアミン（３）、及び１６．８重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体１０を得た。これに、２．７重量部の界面活性剤（３）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物１０を得た。得られた銅薄膜形成組成物１０は流動性を有する青色透明の液体となった。また、銅薄膜形成組成物１０は目視にて均一であり、インキ化評価として、「可」と判定した。結果を表１に示す。 [Example 10]
58.4 parts by weight of ethylene glycol, 22.1 parts by weight of diamine (3) and 16.8 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 10 was obtained. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 μm filter to obtain a copper thin film forming composition 10. The obtained copper thin film forming composition 10 became a blue transparent liquid having fluidity. Moreover, the copper thin film formation composition 10 was uniform visually, and was determined as "OK" as ink evaluation. The results are shown in Table 1.
［実施例１１］
　５８．８重量部のエチレングリコール、２６．５重量部のジアミン（４）、及び１２．７重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体１１を得た。これに、２．０重量部の界面活性剤（３）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物１１を得た。得られた銅薄膜形成組成物１１は流動性を有する青色透明の液体となった。また、銅薄膜形成組成物１１は目視にて均一であり、インキ化評価として、「可」と判定した。結果を表１に示す。 [Example 11]
58.8 parts by weight of ethylene glycol, 26.5 parts by weight of diamine (4), and 12.7 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 11 was obtained. To this, 2.0 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 μm filter to obtain a copper thin film forming composition 11. The obtained copper thin film forming composition 11 became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition 11 was visually uniform, and was determined as “possible” as an ink evaluation. The results are shown in Table 1.
［実施例１２］
　５８．１重量部のエチレングリコール、１９．７重量部のジアミン（５）、及び１９．１重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体１２を得た。これに、３．１重量部の界面活性剤（３）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物１２を得た。得られた銅薄膜形成組成物１２は流動性を有する青色透明の液体となった。また、銅薄膜形成組成物１２は目視にて均一であり、インキ化評価として、「可」と判定した。結果を表１に示す。 [Example 12]
58.1 parts by weight of ethylene glycol, 19.7 parts by weight of diamine (5), and 19.1 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate 12 was obtained. The copper thin film forming composition 12 was obtained by adding and mixing 3.1 weight part surfactant (3) to this, and filtering with a 1 micrometer filter. The obtained copper thin film forming composition 12 became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition 12 was visually uniform, and was determined as “possible” as the ink evaluation. The results are shown in Table 1.
比較例１
　５６．４重量部のエチレングリコール、及び３７．６重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体を得た。これに、６．０重量部の界面活性剤（３）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物を得た。得られた銅薄膜形成組成物は青色の液体となったが、均一に溶解しなかったため、目視によるインキ化評価で「不可」と判定した。結果を表２に示す。 Comparative Example 1
56.4 parts by weight of ethylene glycol and 37.6 parts by weight of copper formate (1) were stirred and mixed at 45 to 50 ° C. for 30 minutes, and then cooled to room temperature to obtain a copper complex ink intermediate. To this, 6.0 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 μm filter to obtain a copper thin film forming composition. Although the obtained copper thin film forming composition became a blue liquid, it did not dissolve uniformly, so it was determined as “impossible” by visual ink evaluation. The results are shown in Table 2.
比較例２
　５８．１重量部のエチレングリコール、及び３８．８重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体を得た。これに、３．１重量部の界面活性剤（１）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物を得た。得られた銅薄膜形成組成物は青色の液体となったが、均一に溶解しなかったため、目視によるインキ化評価で「不可」と判定した。結果を表２に示す。 Comparative Example 2
After stirring and mixing 58.1 parts by weight of ethylene glycol and 38.8 parts by weight of copper formate (1) at 45 to 50 ° C. for 30 minutes, the mixture was cooled to room temperature to obtain a copper complex ink intermediate. To this, 3.1 parts by weight of surfactant (1) was added and mixed, and filtered through a 1 μm filter to obtain a copper thin film forming composition. Although the obtained copper thin film forming composition became a blue liquid, it did not dissolve uniformly, so it was determined as “impossible” by visual ink evaluation. The results are shown in Table 2.
比較例３
　１７．５重量部のエチレングリコール、４０．９重量部のメタノール、２２．１重量部のジアミン（１）、及び１６．８重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体を得た。これに、２．７重量部の界面活性剤（３）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物を得た。得られた銅薄膜形成組成物は流動性を有する青色透明の液体となった。また、銅薄膜形成組成物は目視にて均一であり、インキ化評価として、「可」と判定した。結果を表２に示す。 Comparative Example 3
17.5 parts by weight of ethylene glycol, 40.9 parts by weight of methanol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45-50 ° C. for 30 minutes. Then, the copper complex ink intermediate was obtained by cooling to room temperature. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 μm filter to obtain a copper thin film forming composition. The obtained copper thin film forming composition became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition was visually uniform, and was determined as “possible” as an ink evaluation. The results are shown in Table 2.
比較例４
　１１．７重量部のエチレングリコール、４６．７重量部のメタノール、２２．１重量部のジアミン（１）、及び１６．８重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体を得た。これに、２．７重量部の界面活性剤（３）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物を得た。得られた銅薄膜形成組成物は流動性を有する青色透明の液体となった。また、銅薄膜形成組成物は目視にて均一であり、インキ化評価として、「可」と判定した。結果を表２に示す。 Comparative Example 4
11.7 parts by weight of ethylene glycol, 46.7 parts by weight of methanol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45 to 50 ° C. for 30 minutes. Then, the copper complex ink intermediate was obtained by cooling to room temperature. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 μm filter to obtain a copper thin film forming composition. The obtained copper thin film forming composition became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition was visually uniform, and was determined as “possible” as an ink evaluation. The results are shown in Table 2.
比較例５
　５．９重量部のエチレングリコール、５２．５重量部のメタノール、２２．１重量部のジアミン（１）、及び１６．８重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体を得た。これに、２．７重量部の界面活性剤（３）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物を得た。得られた銅薄膜形成組成物は流動性を有する青色透明の液体となった。また、銅薄膜形成組成物は目視にて均一であり、インキ化評価として、「可」と判定した。結果を表２に示す。 Comparative Example 5
5.9 parts by weight of ethylene glycol, 52.5 parts by weight of methanol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45 to 50 ° C. for 30 minutes. Then, the copper complex ink intermediate was obtained by cooling to room temperature. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 μm filter to obtain a copper thin film forming composition. The obtained copper thin film forming composition became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition was visually uniform, and was determined as “possible” as an ink evaluation. The results are shown in Table 2.
比較例６
　５８．４重量部のメタノール、２２．１重量部のジアミン（１）、及び１６．８重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体を得た。これに、２．７重量部の界面活性剤（３）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物を得た。得られた銅薄膜形成組成物は流動性を有する青色透明の液体となった。また、銅薄膜形成組成物は目視にて均一であり、インキ化評価として、「可」と判定した。結果を表２に示す。 Comparative Example 6
By stirring and mixing 58.4 parts by weight of methanol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) at 45-50 ° C. for 30 minutes, the mixture was cooled to room temperature. A copper complex ink intermediate was obtained. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 μm filter to obtain a copper thin film forming composition. The obtained copper thin film forming composition became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition was visually uniform, and was determined as “possible” as an ink evaluation. The results are shown in Table 2.
比較例７
　５８．４重量部のジエチレングリコール、２２．１重量部のジアミン（１）、及び１６．８重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体を得た。これに、２．７重量部の界面活性剤（３）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物を得た。得られた銅薄膜形成組成物は青色の液体となったが、均一に溶解しなかったため、目視によるインキ化評価で「不可」と判定した。結果を表２に示す。 Comparative Example 7
58.4 parts by weight of diethylene glycol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45-50 ° C. for 30 minutes, and then cooled to room temperature. A copper complex ink intermediate was obtained. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 μm filter to obtain a copper thin film forming composition. Although the obtained copper thin film forming composition became a blue liquid, it did not dissolve uniformly, so it was determined as “impossible” by visual ink evaluation. The results are shown in Table 2.
比較例８
　５８．４重量部のターピネオール、２２．１重量部のジアミン（１）、及び１６．８重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体を得た。これに、２．７重量部の界面活性剤（３）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物を得た。得られた銅薄膜形成組成物は青色の液体となったが、均一に溶解しなかったため、目視によるインキ化評価で「不可」と判定した。結果を表２に示す。 Comparative Example 8
58.4 parts by weight of terpineol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45 to 50 ° C. for 30 minutes, and then cooled to room temperature. A copper complex ink intermediate was obtained. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 μm filter to obtain a copper thin film forming composition. Although the obtained copper thin film forming composition became a blue liquid, it did not dissolve uniformly, so it was determined as “impossible” by visual ink evaluation. The results are shown in Table 2.
比較例９
　５８．４重量部のジヒドロターピニルアセテート、２２．１重量部のジアミン（１）、及び１６．８重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体を得た。これに、２．７重量部の界面活性剤（３）を添加混合し、１μｍフィルターでろ過することで銅薄膜形成組成物を得た。得られた銅薄膜形成組成物は青色の液体となったが、均一に溶解しなかったため、目視によるインキ化評価で「不可」と判定した。結果を表２に示す。 Comparative Example 9
58.4 parts by weight of dihydroterpinyl acetate, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) were stirred and mixed at 45-50 ° C. for 30 minutes, and then brought to room temperature. The copper complex ink intermediate was obtained by cooling. To this, 2.7 parts by weight of surfactant (3) was added and mixed, and filtered through a 1 μm filter to obtain a copper thin film forming composition. Although the obtained copper thin film forming composition became a blue liquid, it did not dissolve uniformly, so it was determined as “impossible” by visual ink evaluation. The results are shown in Table 2.
比較例１０
　６１．１重量部のエチレングリコール、２２．１重量部のジアミン（１）、及び１６．８重量部のギ酸銅（１）を４５～５０℃で３０分間攪拌混合した後、室温に冷却することで銅錯体インク中間体を得た。これを１μｍフィルターでろ過することで銅薄膜形成組成物を得た。得られた銅薄膜形成組成物は流動性を有する青色透明の液体となった。また、銅薄膜形成組成物は目視にて均一であり、インキ化評価として、「可」と判定した。結果を表２に示す。 Comparative Example 10
61.1 parts by weight of ethylene glycol, 22.1 parts by weight of diamine (1), and 16.8 parts by weight of copper formate (1) are stirred and mixed at 45-50 ° C. for 30 minutes and then cooled to room temperature. A copper complex ink intermediate was obtained. This was filtered through a 1 μm filter to obtain a copper thin film forming composition. The obtained copper thin film forming composition became a blue transparent liquid having fluidity. Moreover, the copper thin film forming composition was visually uniform, and was determined as “possible” as an ink evaluation. The results are shown in Table 2.
　以上の結果をまとめて、表１及び２に示す。なお、表１及び２中、「塗布条件」は、１０秒当たりのスピンコーターの回転数を示し、「一次導通性」は、一次導通性評価基板の導通性評価の結果を示し、「二次導通性」は、二次導通性評価基板の導通性評価の結果を示す。 The above results are summarized in Tables 1 and 2. In Tables 1 and 2, “application condition” indicates the number of rotations of the spin coater per 10 seconds, “primary conductivity” indicates the result of the conductivity evaluation of the primary conductivity evaluation substrate, and “secondary conductivity” “Conductivity” indicates the result of the conductivity evaluation of the secondary conductivity evaluation board.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表１及び表２より、上記成分（Ａ）～（Ｄ）を組み合わせて含有する実施例１～１２の銅薄膜形成組成物では、インキ化が容易であり、かつ銅薄膜の導通性も優れていた。一方、上記成分（Ａ）～（Ｄ）の組み合わせを備えていない比較例１～１０の組成物では、インキ化評価又は導通性のいずれかの特性において実施例に比べ劣っていた。 From Tables 1 and 2, the copper thin film forming compositions of Examples 1 to 12 containing a combination of the above components (A) to (D) are easy to ink and have excellent copper thin film conductivity. It was. On the other hand, the compositions of Comparative Examples 1 to 10 which did not have the combination of the above components (A) to (D) were inferior to the examples in either the ink evaluation or the conductivity.
　以上、本発明の実施の形態を例示の目的で詳細に説明したが、本発明は上記実施の形態に制約されることはない。 As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention is not restrict | limited to the said embodiment.
　本国際出願は、２０１３年９月３０日に出願された日本国特許出願２０１３－２０２９１０号に基づく優先権を主張するものであり、当該出願の全内容をここに援用する。
  This international application claims priority based on Japanese Patent Application No. 2013-202910 filed on September 30, 2013, the entire contents of which are incorporated herein by reference.

Claims (5)

  1. 　下記成分（Ａ）～（Ｄ）；
    （Ａ）ギ酸銅、
    （Ｂ）下記一般式（１）で表されるジアミン化合物、
    Figure JPOXMLDOC01-appb-C000001
     ［式中、Ｒ１～Ｒ４は独立して、水素原子、置換されていてもよい炭素数２～４０のアルキル基、アルキルエーテル基、アルキルエステル基又はＯＨ基を示すが、前記ＯＨ基の数は０、１、２又は４であり、Ｘは単結合を示すか、あるいは、－ＣＯ－、－Ｏ－、－ＮＨ－、－ＮＨＣＯ－、もしくは、－（ＣＨ２）ｎ１－Ｏ－（ＣＨ２）ｎ２－Ｏ－（ＣＨ２）ｎ３－（ここで、ｎ１，ｎ２，ｎ３は独立して０～４の数を示す）から選ばれる２価の基、又は、炭素数１～２０の２価の炭化水素基を示す。］
    （Ｃ）アルキル基を有し、炭素数４～２２である界面活性剤、
    及び
    （Ｄ）３０重量％以上のエチレングリコールを含有する有機溶媒
    を含有する銅薄膜形成組成物。     The following components (A) to (D);
    (A) copper formate,
    (B) a diamine compound represented by the following general formula (1),
    Figure JPOXMLDOC01-appb-C000001
     [Wherein R 1 to R 4 independently represent a hydrogen atom, an optionally substituted alkyl group having 2 to 40 carbon atoms, an alkyl ether group, an alkyl ester group or an OH group, The number is 0, 1, 2 or 4, and X represents a single bond, or —CO—, —O—, —NH—, —NHCO—, or — (CH 2 ) n 1 —O—. A divalent group selected from (CH 2 ) n 2 —O— (CH 2 ) n 3 — (wherein n 1 , n 2 and n 3 independently represent a number of 0 to 4), or A divalent hydrocarbon group having 1 to 20 carbon atoms is shown. ]
    (C) a surfactant having an alkyl group and having 4 to 22 carbon atoms,
    And (D) a copper thin film forming composition containing an organic solvent containing 30% by weight or more of ethylene glycol.
  2. 　前記（Ａ）成分を５重量％以上７５重量％以下の範囲内で含有する請求項１に記載の銅薄膜形成組成物。 The composition for forming a copper thin film according to claim 1, comprising the component (A) in a range of 5 wt% to 75 wt%.
  3. 　前記（Ａ）成分１モルに対し、前記（Ｂ）成分を０．０５モル以上３モル以下の範囲内で含有する請求項１に記載の銅薄膜形成組成物。 The composition for forming a copper thin film according to claim 1, wherein the component (B) is contained in a range of 0.05 mol to 3 mol with respect to 1 mol of the component (A).
  4. 　前記（Ｃ）成分を１重量％以上１０重量％以下の範囲内で含有する請求項１に記載の銅薄膜形成組成物。 The composition for forming a copper thin film according to claim 1, comprising the component (C) in a range of 1 wt% to 10 wt%.
  5. 　前記（Ｄ）成分を、３０重量％以上７０重量％以下の範囲内で含有する請求項１に記載の銅薄膜形成組成物。 The composition for forming a copper thin film according to claim 1, comprising the component (D) in a range of 30 wt% to 70 wt%.
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WO2017135330A1 (en) * 2016-02-03 2017-08-10 学校法人工学院大学 Metal film forming composition and metal film forming method
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WO2023063207A1 (en) * 2021-10-14 2023-04-20 Jsr株式会社 Metal-containing film formation composition, metal-containing film, metal-containing film formation method, and production method of metal-containing film formation composition

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