WO2015045932A1 - Composition pour former une couche mince de cuivre - Google Patents

Composition pour former une couche mince de cuivre 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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English (en)
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/ja
Publication of WO2015045932A1 publication Critical patent/WO2015045932A1/fr

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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.

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Abstract

L'invention porte sur une composition qui permet de former une couche mince de cuivre et qui contient (A) du formiate de cuivre, (B) un composé diamine représenté par la formule générale (1), (C) un tensioactif ayant un groupe alkyle et de 4 à 22 atomes de carbone et (D) un solvant organique contenant 30 % en poids ou plus d'éthylèneglycol. [Formule chimique 1] [Dans la formule, R1 à R4 représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle de 2 à 40 atomes de carbone éventuellement substitué, un groupe éther d'alkyle, un groupe ester alkylique ou un groupe OH, le nombre de groupes OH étant de 0, 1, 2 ou 4 ; X représente une simple liaison ou un groupe divalent choisi parmi -CO-, -O-, -NH-, -NHCO- ou -(CH2)n1-O-(CH2)n2-O-(CH2)n3- (n1, n2 et n3 représentant chacun indépendamment un nombre de 0 à 4) ou un groupe hydrocarboné divalent ayant 1 à 20 atomes de carbone.]
PCT/JP2014/074341 2013-09-30 2014-09-16 Composition pour former une couche mince de cuivre WO2015045932A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017134769A1 (fr) * 2016-02-03 2017-08-10 学校法人工学院大学 Composition de formation d'un film métallique et procédé de formation d'un film métallique
WO2023063207A1 (fr) * 2021-10-14 2023-04-20 Jsr株式会社 Composition pour formation de film à teneur en métal ainsi que procédé de fabrication de celle-ci, film à teneur en métal, et procédé de formation de film à teneur en métal
JP7565533B2 (ja) 2019-08-06 2024-10-11 国立大学法人長岡技術科学大学 基材上に金属膜が形成された複合体の製造方法および複合体

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JP2010242118A (ja) * 2009-04-01 2010-10-28 Adeka Corp 銅薄膜形成用組成物および該組成物を用いた銅薄膜の製造方法
WO2013136937A1 (fr) * 2012-03-16 2013-09-19 株式会社Adeka Composition de formation de film de cuivre et procédé permettant de produire un film de cuivre à l'aide de la composition

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JPH01168866A (ja) * 1987-12-24 1989-07-04 Mitsubishi Gas Chem Co Inc 銅膜形成物品の製造法
JP2012126814A (ja) * 2010-12-15 2012-07-05 Tosoh Corp 導電性インク組成物、及び電気的導通部位の製造方法

Patent Citations (2)

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JP2010242118A (ja) * 2009-04-01 2010-10-28 Adeka Corp 銅薄膜形成用組成物および該組成物を用いた銅薄膜の製造方法
WO2013136937A1 (fr) * 2012-03-16 2013-09-19 株式会社Adeka Composition de formation de film de cuivre et procédé permettant de produire un film de cuivre à l'aide de la composition

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017134769A1 (fr) * 2016-02-03 2017-08-10 学校法人工学院大学 Composition de formation d'un film métallique et procédé de formation d'un film métallique
WO2017135330A1 (fr) * 2016-02-03 2017-08-10 学校法人工学院大学 Composition de formation de film métallique et procédé de formation de film métallique
JPWO2017135330A1 (ja) * 2016-02-03 2018-11-29 学校法人 工学院大学 金属膜形成用組成物および金属膜形成方法
JP2022003170A (ja) * 2016-02-03 2022-01-11 学校法人 工学院大学 金属膜形成用組成物および金属膜形成方法
JP7175532B2 (ja) 2016-02-03 2022-11-21 学校法人 工学院大学 金属膜形成用組成物および金属膜形成方法
JP7565533B2 (ja) 2019-08-06 2024-10-11 国立大学法人長岡技術科学大学 基材上に金属膜が形成された複合体の製造方法および複合体
WO2023063207A1 (fr) * 2021-10-14 2023-04-20 Jsr株式会社 Composition pour formation de film à teneur en métal ainsi que procédé de fabrication de celle-ci, film à teneur en métal, et procédé de formation de film à teneur en métal

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