JP2010103143A - Method of manufacturing metal film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a metal film using a compound of low polarity and low viscosity, and to provide a method of manufacturing a metal film at low temperature. <P>SOLUTION: In a method of manufacturing a metal film, a composition containing at least one selected from metallic particles formed on the surface of a substrate, metallic particles having an oxide film or metal oxide particles is heat-treated under presence of a compound represented by formula 1. In the formula 1, R<SP>1</SP>is hydrogen or an alkyl group of 1-6C, R<SP>2</SP>is an alkyl group of 1-6C which may have a substituent containing a nitrogen atom and an oxygen atom, -NR<SP>6</SP>R<SP>7</SP>, -OR<SP>8</SP>, -CR<SP>10</SP>=CArR<SP>9</SP>or Ar, and R<SP>3</SP>and R<SP>4</SP>are alkyl groups of 1-6C or hydrocarbylene groups of 2-12C independently from each other. Here, R<SP>6</SP>and R<SP>7</SP>are alkyl groups of 1-6C which may contain an oxygen atom independently from each other, R<SP>8</SP>is an alkyl group of 1-6C, R<SP>9</SP>and R<SP>10</SP>are hydrogen, phenyl groups or alkyl groups of 1-6C independently from each other, and Ar is a phenyl group, a pyridyl group or a thienyl group after reducing the pressure to the second pressure. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a metal film. More specifically, a metal obtained by heat-treating a composition containing at least one of metal particles formed on the substrate surface, metal particles having an oxide film, and metal oxide particles in the presence of a specific compound. The present invention relates to a film manufacturing method.

  As a technique for forming wiring on a circuit board or the like, a method of patterning a metal foil, a metal vapor deposition film, or a metal plating film by using photolithography and etching is generally used. Since this method is a subtractive method of discarding unnecessary portions of metal with a large number of steps, there is a problem that the utilization efficiency of the metal is poor and a large amount of waste liquid is generated.

  As a method for improving the metal utilization efficiency, several additive methods have been proposed in which a metal film is formed only at a necessary place without using etching to form a wiring. As an example, there is a method in which a plating resist is printed on a substrate, electroless plating is performed, and a metal film is formed only on a portion without the resist. A method is also known in which a catalyst is printed on a substrate, electroless plating is performed, and a metal film is formed only on a portion where the catalyst is present. However, these methods also have a drawback that it is necessary to treat the plating waste liquid.

  On the other hand, a wiring pattern forming technique using a printing method, which is also an additive method, has attracted widespread attention. The use of metal nanoparticles is particularly attracting attention as a wiring pattern forming technique by a printing method. This is a method in which a paste or ink-like composition containing metal nanoparticles is printed on a substrate and subjected to a firing treatment to sinter the metal nanoparticles to form a wiring. Since metal nanoparticles have a lower sintering temperature than bulk metal or micron order metal particles, they can be processed at a temperature considerably lower than the melting point of the metal itself. In addition, it is a great advantage that the wiring pattern can be miniaturized by using ultrafine particles of nanoparticles. As a result, it is expected that the wiring board can be miniaturized, and the associated weight can be reduced, and a transparent conductive film can be created by a printing method.

  The formation of wiring patterns by printing metal nanoparticle paste is a highly promising method, but some of the metals used in wiring patterns are made into nano-sized particles, as represented by copper. Some are very susceptible to oxidation. In such a metal, the oxide generated on the metal particles hinders the sintering, and in order to sinter the metal particles, firing in a reducing atmosphere is necessary. As a firing method in a reducing atmosphere, a method of firing in a hydrogen-mixed nitrogen stream (Patent Document 1), a firing method using atomic hydrogen (Patent Document 2), and a method of firing in the presence of alcohols such as ethylene glycol ( Patent Document 3) has been proposed. The method using hydrogen or atomic hydrogen has not been widely used due to problems such as the need for advanced atmosphere control and special equipment. In addition, the method using alcohols can be said to be a relatively versatile method because it can be made to act by mixing alcohols with steam or in a paste, but only alcohols can be used. And there are not many options. Since alcohols are generally highly polar and compatible materials are limited, the components that can be blended in the paste are limited. In the conductive paste, an epoxy resin is often blended as a polymer component, but ethylene glycol which is a kind of polyols (having a plurality of hydroxyl groups in the molecule) suitably used in Patent Document 3 is not compatible with this. Therefore, blending is difficult. In addition, there are many methods for synthesizing metal nanoparticles, and the surface is coated with a low-polarity compound, but even when the above-mentioned components with poor compatibility are not included, ethylene glycol is coated with a low-polarity compound. Since the affinity with the surface of the formed metal nanoparticle itself is low, there is a concern that it is difficult to act on the particle surface, and furthermore, it cannot act. In addition, polyols generally have high viscosity, and if they are mixed with solids such as metal particles, the viscosity becomes even higher. However, there are printing methods that can use only low-viscosity pastes, such as wiring patterning in the inkjet method. As such, the use of high viscosity liquids such as ethylene glycol significantly reduces the choice of printing method and paste design. From such a background, it is considered necessary to develop a new baking method using a low-polarity, low-viscosity compound.

In addition, the technology for sintering metal particles is highly demanded for lowering the sintering temperature. This is because a low-temperature general-purpose resin such as polyethylene terephthalate (PET) can be used as a substrate by lowering the sintering temperature. Further, when the firing temperature is lowered, there is an advantage that an inexpensive material can be used for a member used in the manufacturing apparatus, and the energy cost is lowered. Furthermore, in applications where the firing process is performed with electronic components mounted, such as a multilayer board, there is a need for a low-temperature wiring pattern formation technique because there is no risk of the electronic components being damaged by high temperatures. However, to date, no method has been known that falls below the sintering temperature of 200 ° C. in the methods disclosed in Patent Documents 4 and 5.
International Publication No. 2003/051562 Pamphlet Japanese Patent No. 3870273 Japanese Patent No. 3939735 JP 2008-146999 A JP 2008-146991 A

  The problem to be solved by the present invention is to provide a method for producing a metal film using a low-polarity, low-viscosity compound, and to provide a method for producing a metal film at a low temperature.

  As a result of repeated investigations to solve the above problems, the present inventors have obtained a composition containing at least one of metal particles formed on the substrate surface, metal particles having an oxide film, and metal oxide particles. The inventors have found that a method for producing a metal film by performing heat treatment in the presence of a compound represented by the following formula 1 is effective, and have completed the present invention.

Wherein R ¹ is hydrogen or an alkyl group having 1 to 6 carbon atoms, R ² is a nitrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent containing an oxygen atom, —NR ⁶ R ⁷ , —OR ⁸ , —CR ¹⁰ = CArR ⁹ or Ar, and R ³ and R ⁴ are each independently an alkyl group having 1 to 6 carbon atoms, or R ³ and R ⁴ together form a ring. A hydrocarbylene group having 2 to 12 carbon atoms which may be substituted with a hydroxyl group (wherein R ⁶ and R ⁷ are independently of each other a carbon atom having 1 to 6 carbon atoms which may contain an oxygen atom) An alkyl group (R ⁶ and R ⁷ may form a ring), R ⁸ is an alkyl group having 1 to 6 carbon atoms, and R ⁹ and R ¹⁰ are each independently hydrogen, phenyl group or carbon An alkyl group having 1 to 6 carbon atoms, and Ar is an alkyl group having 1 to 6 carbon atoms. A phenyl group optionally substituted by a cyclic substituent formed by an alkyloxy group, a hydroxyl group, a hydroxymethyl group, a formyl group, an amino group, a monoalkylamino group or a dialkylamino group, or a combination of these substituents, Pyridyl group or thienyl group.)

  In the conventional method using an alcohol reducing agent, a polymer component that has been limited in use due to low compatibility with alcohols can be used as a component of the composition. Moreover, it becomes possible to produce a low-viscosity paste as compared with the case of using alcohols. In addition, by appropriately selecting the compound represented by Formula 1, it becomes possible to produce a metal film at a lower temperature than in the prior art.

  The method for producing a metal film of the present invention is represented by Formula 1, wherein a composition containing at least one selected from metal particles formed on a substrate surface, metal particles having an oxide film, and metal oxide particles is represented by Formula 1. The heat treatment is carried out in the presence of a compound.

  As the metal, cobalt or a metal having a smaller ionization tendency, such as gold, silver, copper, nickel, tin, palladium, platinum, or the like can be used. Among these metals, silver, copper, nickel or tin useful when a metal film is used is preferable.

  The oxide film in the metal particle having the oxide film refers to a metal oxide phase existing on the particle surface, which may cover the whole particle or may partially cover it.

  The metal particles, metal particles having an oxide film, or metal oxide particles may be covered with an organic substance such as a dispersant. The dispersant here is a role of controlling the particle size when synthesizing metal particles or the like, or assisting the dispersion of particles when preparing a paste or ink containing metal particles or the like. Refers to the compound responsible for. It is not limited whether the dispersant is a low molecule or a high molecule, but since it is generally easy to sinter, the dispersant is preferably a low molecule.

  As the metal particles, metal particles having an oxide film or metal oxide particles, nanoparticles such as silver, copper, nickel and tin (average particle size: 25 to 200 nm) are commercially available from Sigma-Aldrich Japan Co., Ltd. as reagents. These can be used. Further, metal particles can be synthesized in accordance with the following papers and the like, and these can also be used (example of literature: “Chemical Materials”, Vol. 20, p. 5399 (2008), “Chemical ・"Materials", 12, 1354 (2000), "Chemical Materials", 17, 856 (2005), "Advanced Functional Materials", 18, 679 (2008) "Chemical Communications", page 778 (2004)).

  The method for producing a metal film of the present invention is characterized by using a compound represented by Formula 1. Although the detailed mechanism of action of the compound represented by Formula 1 in the present invention is unclear, it is possible to prevent oxidation, reduce metal oxide, and sinter metal particles against metal particles, metal particles having an oxide film, or metal oxide particles. It is thought that it acts such as promotion of.

The compound represented by Formula 1 is substituted with a hydroxyl group in which R ³ and R ⁴ are each independently an alkyl group having 1 to 6 carbon atoms and R ³ and R ⁴ together form a ring. It can be roughly divided into two types in the case of a hydrocarbylene group having 2 to 12 carbon atoms.

When R ³ and R ⁴ are each independently an alkyl group having 1 to 6 carbon atoms, preferred specific examples include a methyl group, an ethyl group, and a propyl group.

When R ³ and R ⁴ are a hydrocarbylene group having 2 to 12 carbon atoms which may be substituted with a hydroxyl group which forms a ring together, the compound represented by the formula 1 is represented by the following general formula 2 Indicated by the formula. In the case of the compound represented by Formula 2, the stability of the compound is high and the effect of promoting the sintering of metal particles, metal particles having an oxide film or metal oxide particles is large, so that the metal of the present invention It is preferably used in a film production method.

(Wherein, R ¹ and R ² are the same as defined above, and R ⁵ represents a hydrocarbylene group having 2 to 12 carbon atoms which may be substituted with a hydroxyl group).

Also, choose the R ⁵ as partial structures shown in Formula 3 to R ⁵ form is 5 to 6-membered ring, for structural stability of the 5- to 6-membered ring, easier handling, when synthesizing Is also preferably used because the target compound can be obtained with good yield.

Specific examples of such R ⁵ include ethylene group, propylene group, propane-1,3-diyl group, 2,3-butylene group, 1,2-butylene group, butane-1,3-diyl group, 2 , 2-dimethylpropane-1,3-diyl group.

^{R 1} in Formula 1 is hydrogen or an alkyl group having 1 to 6 carbon atoms. Preferable specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group and an ethyl group. In the present invention, R ¹ is preferably hydrogen or a methyl group.

R ² is a nitrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent containing an oxygen atom, —NR ⁶ R ⁷ , —OR ⁸ , —CR ¹⁰ = CArR ⁹ or Ar ( Here, R ^{6 to} R ¹⁰ and Ar are the same as defined above.

When R ² is a C 1-6 alkyl group optionally having a substituent containing a nitrogen atom or an oxygen atom, preferably a methyl group, an ethyl group, a propyl group, an isobutyl group, an aminomethyl group, N-methylamino group, more preferably aminomethyl group and N-methylamino group.

When R ² is —NR ⁶ R ^7, it is preferably a dimethylamino group or a diethylamino group, more preferably a dimethylamino group.

When R ² is ^-CR 10 = CArR ^9, preferably styryl group.

When R ² is Ar, it is preferably a phenyl group, a pyridyl group, or a thienyl group, and more preferably a phenyl group. In addition, when R ³ and R ⁴ are each independently an alkyl group having 1 to 6 carbon atoms, R ² is a compound selected from any one of —NR ⁶ R ⁷ , —CR ¹⁰ = CArR ⁹ and Ar. In some cases, a highly conductive metal film is obtained, which is preferable. When the compound represented by Formula 1 is the compound represented by Formula 2, R ² is —NR ⁶ R ⁷ , —OR ⁸ , —CR ¹⁰ = CArR ^9. A compound selected from Ar and Ar is preferable because a highly conductive metal film can be obtained. Further, when the compound represented by Formula 1 is a compound represented by Formula 2 and R ² is a compound of —NR ⁶ R ⁷ or —OR ⁸ , a metal film having particularly high conductivity is obtained, which is more preferable. .

  Specific examples of the compound represented by Formula 1 include, but are not limited to, compounds of Formula 4 to Formula 43. These compounds can be used alone or in combination of two or more.

Of these compounds, Formulas 4 to 28 are examples of compounds represented by Formula 2. Of these, Formulas 15 to 22 are examples of compounds in which R ² is —NR ⁶ R ^7. Compounds of Formula 23 are examples of compounds in which R ² is —OR ^8. Formulas 24 and 25 are R ^2. Are examples of compounds where —CR ¹⁰ = CArR ⁹ and Formulas ^10, 12, 26-28 are examples of compounds where R ² is Ar. Formulas 29 to 43 are examples of compounds in which R ³ and R ⁴ are alkyl groups having 1 to 6 carbon atoms. Of these, Formulas 29 to 38 are examples of compounds in which R ² is —NR ⁶ R ⁷ , Formula 39 is an example of a compound in which R ² is —CR ¹⁰ = CArR ⁹ , and Formulas 40 to 43 are R Examples of compounds in which ² is Ar.

  The compound represented by Formula 1 is commercially available from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan Co., Ltd., Alpha Acer Co., etc. As for compounds not commercially available, “Journal of Heterocyclic Chemistry”, 17, p. 1345 (1980), “Journal of American Chemical Society”, p. 111, p. 1381 (1989). “Chemical Berichte”, 101, 41 (1968), “Journal of Korean Chemical Society”, 39, 218 (1995), “Chemistry a European Journal” 13, 5566 (2007), "Journal of Medicinal Chemistry", 35, 1996 (1992), "Burtan de la Societe Simique de France", 12, 4985 ( 1968), "Archibok", Vol. 12, p. 58 (2001) “Journal of Organic Chemistry”, 60, 2931 (1995), “Journal of Organic Chemistry”, 43, 3417 (1978), “Tetrahedron Letters”, 46, According to the literature such as page 2341 (2005), it can be synthesized.

  The metal particles, metal particles having an oxide film or metal oxide particles in the present invention preferably have an average particle diameter of 1 to 200 nm. If it is the said particle size, sintering at the temperature considerably lower than melting | fusing point of a metal is possible. The particle size here refers to the particle size of primary particles and can be measured by morphological observation with an electron microscope. The calculation of the average particle size is based on the number average, and it is obtained by selecting any 100 particles from the range of particles that can be observed with an electron microscope and averaging the particle size by the number of particles. It is done. A primary particle is a minimum three-dimensional unit structure composed of two or more atoms that can be recognized by an electron microscope. There are no particular restrictions on the shape of the primary particles, and various forms such as spheres, polyhedrons, flat plates, and needles are possible, and their particle sizes depend on the diameter of the same volume sphere, that is, the equivalent volume sphere equivalent diameter. Define. Since the temperature required for sintering becomes lower as the average particle size is smaller, the more preferable range of the average particle size is 1 to 100 nm, and more preferably 1 to 50 nm.

  The composition containing at least one or more selected from metal particles, metal particles having an oxide film, and metal oxide particles in the present invention may contain components other than particles. When components other than particles are contained, the content is preferably 70% by weight or less in the composition.

  As a component other than the particles contained in the composition, a polymer or a polymer precursor is preferably contained. The polymer or polymer precursor is added for the purpose of improving the dispersion of the metal particles, controlling the viscosity characteristics, and improving the adhesion between the conductive film and the substrate. In particular, a polymer used for improving the adhesion between the conductive film and the substrate is called a binder polymer and is blended in many conductive pastes. Preferred examples of the polymer include acrylic polymers (that is, polymers or copolymers of acrylic monomers such as (meth) acrylic acid ester, (meth) acrylic acid, (meth) acrylamide, (meth) acrylonitrile), polyvinyl pyrrolidone. , Polyvinyl acetal, polyester, polyamide, polyimide, polyurethane and the like. These polymers may be non-crosslinked polymers or fine particles of crosslinked polymers. A polymer precursor is a precursor that generates a polymer upon heating, and is an uncured epoxy resin (a mixture of an epoxy compound and a curing agent), an uncured phenol resin (a mixture of a resole and a curing agent), or an uncured resin. Examples include cyanate resins (a mixture of a cyanate compound and a curing agent).

  The composition may contain a volatile solvent, that is, an organic solvent or water. Specific examples of preferred organic solvents include 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-octanol, α-terpineol, benzyl alcohol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, 1,2-dimethoxyethane , Methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, isophorone, ethyl acetate , Butyl acetate, isoamyl acetate, ethyl lactate, propylene carbonate, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, toluene, xylene, mesitylene , Decalin, tetralin, and the like. Furthermore, all additives used for paints and printing inks such as thixotropic agents, leveling agents, and antifoaming agents can be included. Furthermore, the compound represented by the above formula 1 may be included.

  In the present invention, the metal film is produced by heat-treating the composition in the presence of the compound represented by Formula 1. The metal film here refers to a film containing a metal in a form in which metal particles are fused to each other. The metal film here may contain components other than metals such as polymers.

  As an example of the film to be formed, a film having a large area or a pattern such as wiring may be used. Moreover, the thing which coat | covers the inner wall of the recessed part (for example, via hole of a multilayer substrate, etc.) of a board | substrate, or what fills the whole recessed part may be used. The film can be formed by applying or printing an ink or paste containing the composition. Preferred methods of coating include methods using apparatuses such as a bar coater, gravure roll coater, slit die coater, knife coater, lip coater, comma coater method, reverse roll coater, spray coater, dip coater, spin coater. it can. Preferable methods for printing include stencil printing methods (screen printing methods, etc.), relief printing methods (flexo printing methods, etc.), intaglio printing methods (gravure printing methods, etc.), lithographic printing methods, inkjet methods, dispenser methods, etc. Can do.

  When the ink or paste containing the composition is applied or printed, an operation of removing the volatile solvent by means such as heating may be performed thereafter.

  In the present invention, any material can be used as the substrate on which the metal film is formed, and any shape such as a flat surface, a curved surface, and an uneven surface can be used. The substrate surface includes not only a flat large-area surface but also a side surface of an uneven surface. Examples of the material used include a resin film, a resin plate, a glass plate, paper, and a green sheet. Specific examples of the resin film include polyester resin (polyethylene terephthalate, polyethylene naphthalate, liquid crystal polyester, etc.), polyimide resin, polyetherimide resin, polyaramid resin, polyethersulfone resin, polyphenylene sulfide resin, polyphenylene ether resin, and the like. be able to. Examples of the resin used for the resin plate include thermosetting resins (cured products) such as epoxy resins, phenol resins, cyanate resins, maleimide resins, and benzoxazine resins in addition to the same thermoplastic resins as exemplified in the resin film. Can do. The resin plate may be a fiber reinforced resin obtained by impregnating a reinforced fiber base material with a thermosetting resin and curing. At this time, paper, cotton cloth, polyester woven cloth, glass fiber woven cloth or the like is preferable as the reinforcing fiber base. The green sheet is a precursor that becomes a ceramic substrate by firing, and is usually formed by molding components such as an alumina aggregate, a glass material, and an organic binder into a sheet shape.

  Although there is no restriction | limiting in particular about the heating temperature in the heat processing in this invention, This invention is characterized by being able to perform heat processing at 250 degrees C or less, Preferably it heat-processes at 180 degrees C or less. As a heating method, in addition to direct heating by a hot plate, an oven or the like, local heat generated by irradiation with infrared rays, microwaves, or lasers can also be used. Moreover, when supplying the compound shown by Formula 1 to a coating layer with a vapor | steam, it is also possible to heat-process by spraying a heating vapor | steam.

In the present invention, the following (1) to (3) are mentioned as preferred embodiments in which the compound represented by the formula 1 is present in the system, but is not limited thereto. Moreover, it is also possible to implement combining these aspects.
(1) Present as vapor outside the composition (2) Present as liquid outside the composition (3) Present as a component of the composition.

  As a specific example of the embodiment in which the compound represented by Formula 1 is present as vapor outside the composition, the film of the composition is placed in a chamber, and the vapor of the compound represented by Formula 1 is placed in the chamber while heating. The supply method can be mentioned. Also, a method of putting the film of the composition and the compound represented by Formula 1 into a chamber and heating the inside of the chamber to vaporize the compound represented by Formula 1 is also possible.

  As a specific example of an embodiment in which the compound represented by Formula 1 is present as a liquid outside the composition, a method in which a film of the composition is immersed in a liquid compound represented by Formula 1 and heated, or the composition And a method of spraying a liquid compound represented by Formula 1 on the film.

  The metal film obtained by the method for producing a metal film of the present invention includes wiring for circuit boards, wiring for membrane wiring boards, wiring for film connectors, interlayer wiring for multilayer boards, conductor mesh for electromagnetic wave shielding materials, wiring for flat panel displays ( (Gate bus line and source bus line), collector electrode of plasma display, collector electrode of solar cell, antenna of IC tag, printed coil, etc., and can be used suitably.

Hereinafter, the present invention will be described with reference to examples. The resistivity of the conductive film was measured by a 4-terminal 4-probe method using a Lorester GP manufactured by Dia Instruments Co., Ltd. In addition, M-50 manufactured by Exact Technologies Co., Ltd. was used for the three rolls, and Awatori Rentaro AR-100 manufactured by Shinky Co., Ltd. was used for the mixer. ¹ H-NMR was measured using JEOL AL400 manufactured by JEOL Ltd., and chemical shift was expressed in δ (unit: ppm) based on tetramethylsilane (TMS). Moreover, when there is no description in particular about the compound shown by Formula 1, what was purchased as a reagent from Tokyo Chemical Industry Co., Ltd. was used.

(Reference Examples 1 to 5) Solubility in binder polymer In the conductive paste used in the production of a metal film, an epoxy resin is often used as a binder polymer. Table 1 shows the results of examining the solubility of typical epoxy resins and compounds of formula 1. As a representative example of a group of compounds having different structural characteristics among the compounds of formula 1, the compounds of formulas 23, 26, and 33 were tested, and these compounds were easily dissolved in an epoxy resin, and the epoxy resin was converted into metal particles, It has been shown to be suitable for being present as a component of a composition containing at least one or more selected from metal particles having an oxide film and metal oxide particles. On the other hand, it was shown that it was difficult to produce a uniform paste with these compounds because the compounds other than those of Formula 1 were separated. Further, when the compound represented by Formula 1 is present as a vapor or liquid outside the composition containing at least one selected from metal particles, metal particles having an oxide film, and metal oxide particles, Formula 1 In order for the compound shown to function effectively, it is necessary that the compound shown by Formula 1 diffuses inside the film of the composition, but the compound shown by Formula 1 as shown in this Reference Example However, it was shown that this diffusion is easy due to the excellent solubility in epoxy resin.

(Examples 1-14) Method for producing a metal film in the case where the compound represented by Formula 1 is present as a vapor-Preparation of copper paste 0.72 g of 0.28 g of polyvinylpyrrolidone (Tokyo Kasei Co., Ltd. P0471) having an average molecular weight of 10,000 Of N-methyl-2-pyrrolidone (Kanto Chemical Co., Inc. 25336-00), 4 g of copper nanoparticles having an average particle size of 50 nm (Sigma Aldrich Japan Co., Ltd. 684007-25G), three rolls and a mixer were used. And kneaded.

-Coating film preparation The prepared copper paste (0.1 g) was placed on a Kapton film (manufactured by Toray DuPont Co., Ltd., Kapton 500V) and coated using a # 5 bar coater. The coating was placed in a vacuum oven and dried at 70 ° C. for 2 hours.

-Heat processing The produced coating film was put into reaction container, and the vapor | steam of various compounds was filled up. Heat treatment was performed at 250 ° C. for 5 minutes, and after cooling to 100 ° C. or lower, the product was taken out. The results of measuring the resistivity of the metal film are shown in Table 2.

Synthesis of Compound 20 Synthesis was performed with reference to “Chemical Berichte”, 101, 41 (1968). The inside of the distillation apparatus was assembled, and the inside was replaced with argon. Dimethylacetamidodimethylacetal (containing 5-10% methanol, Tokyo Kasei D1652, 11 mL) and dehydrated ethylene glycol (3.6 mL) were mixed and stirred. When heated in an oil bath, steam at 50 to 65 ° C began to be emitted from around 100 ° C. This was discarded as a forerunner. The temperature gradually increased, and when the oil bath reached 160 ° C, steam at 120 ° C began to come out. This was recovered as a main distillate to obtain 8.0 g of a colorless liquid.

_{^{1 H NMR (CDCl 3);}} δ1.42 (3H, s), 2.31 (6H, s), 3.9-4.1 (4H, m). .

Synthesis of Compound 25 Synthesis was performed with reference to “Journal of Organic Chemistry”, Volume 60, 2931 (1995). A Dean-Stark apparatus was assembled, and trans-cinnamaldehyde (7.08 g) and L-tartaric acid (0.035 g) were added to dehydrated benzene (50 mL) and stirred. A mixture of dehydrated benzene (10 mL) and ethylene glycol (5.6 mL) (separated) was added and heating was started in an oil bath. During the heating, the heating was terminated at 130 ° C. for 6 hours while removing generated water. After standing to cool, sodium hydrogen carbonate (0.042 g) was added. After stirring at room temperature for 30 minutes, the solid was removed by filtration. The filtrate was concentrated under reduced pressure to obtain 5.71 g of a colorless liquid.

¹ H NMR (CDCl ₃ ); δ 3.9-4.1 (4H, m), 5.43 (1H, d), 6.16 (1H, dd), 6.75 (1H, d), 7. 2-7.6 (5H, m). .

(Example 15)
It carried out similarly to Example 3 except having changed heat processing temperature into 150 degreeC. The resistivity of the metal film was 80 μΩ · cm.

(Example 16)
It carried out like Example 6 except having changed heat processing temperature into 175 degreeC. The resistivity of the metal film was 100 μΩ · cm.

(Example 17)
It carried out similarly to Example 8 except having changed heat processing temperature into 200 degreeC. The resistivity of the metal film was 100 μΩ · cm.

  (Example 18) A method for producing a metal film in the case where the compound represented by the formula 1 is present outside the composition as a liquid.

-Copper paste and coating film preparation The copper paste and coating film were prepared in the same manner as in Example 1.

-Heat treatment The prepared coating film was immersed in dimethylformamide dipropyl acetal (compound of formula 35), subjected to heat treatment at 250 ° C for 5 minutes, cooled to 100 ° C or less, and then taken out. Dirt on the surface was wiped dry with gauze containing methanol. The resistivity of the metal film was measured and found to be 50 μΩ · cm.

(Example 19) Method of metal film in the case where the compound represented by formula 1 is present as a component of the composition-Preparation of copper paste 0.72 g of 0.28 g of polyvinylpyrrolidone (Tokyo Chemical Industry Co., Ltd. P0471) having an average molecular weight of 10,000 Was dissolved in dimethylformamide ethylene acetal (compound of formula 15), and kneaded using 4 g of copper nanoparticles having an average particle diameter of 50 nm (Sigma Aldrich Japan Co., 684007-25G), 3 rolls and a mixer.

-Coating film preparation The prepared copper paste (0.1 g) was placed on a Kapton film (manufactured by Toray DuPont Co., Ltd., Kapton 500V) and coated using a # 5 bar coater.

-Heat processing The produced coating film was put in the container with a non-return valve, heat processing was performed at 250 degreeC for 5 minute (s), and it took out, after cooling to 100 degrees C or less. The resistivity of the metal film was measured and found to be 20 μΩ · cm.

Below, the comparative example at the time of heat-processing at 150 degreeC using ethylene glycol is shown.
(Comparative Example 1)
The same procedure as in Example 15 was performed except that ethylene glycol was used instead of dimethylformamide ethylene acetal. The coating film after the heat treatment did not show conductivity.

Claims (13)

Metal obtained by heat-treating a composition containing at least one selected from metal particles formed on a substrate surface, metal particles having an oxide film, and metal oxide particles in the presence of a compound represented by Formula 1 A method for producing a membrane.

Wherein R ¹ is hydrogen or an alkyl group having 1 to 6 carbon atoms, R ² is a nitrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent containing an oxygen atom, —NR ⁶ R ⁷ , —OR ⁸ , —CR ¹⁰ = CArR ⁹ or Ar, and R ³ and R ⁴ are each independently an alkyl group having 1 to 6 carbon atoms, or R ³ and R ⁴ together form a ring. A hydrocarbylene group having 2 to 12 carbon atoms which may be substituted with a hydroxyl group (wherein R ⁶ and R ⁷ are independently of each other a carbon atom having 1 to 6 carbon atoms which may contain an oxygen atom) An alkyl group (R ⁶ and R ⁷ may form a ring), R ⁸ is an alkyl group having 1 to 6 carbon atoms, and R ⁹ and R ¹⁰ are each independently hydrogen, phenyl group or carbon An alkyl group having 1 to 6 carbon atoms, and Ar is an alkyl group having 1 to 6 carbon atoms. A phenyl group optionally substituted by a cyclic substituent formed by an alkyloxy group, a hydroxyl group, a hydroxymethyl group, a formyl group, an amino group, a monoalkylamino group or a dialkylamino group, or a combination of these substituents, Pyridyl group or thienyl group.) The method for producing a metal film according to claim 1, wherein the compound represented by Formula 1 is a compound represented by Formula 2 below.

(In the formula, R ¹ and R ² are the same as defined above, and R ⁵ represents a hydrocarbylene group having 2 to 12 carbon atoms which may be substituted with a hydroxyl group.) R ⁵ is ethylene group, propylene group, propane-1,3-diyl group, 2,3-butylene group, 1,2-butylene group, butane-1,3-diyl group, 2,2-dimethylpropane-1 The method for producing a metal film according to claim 2, which is a 1,3-diyl group. R ² is —NR ⁶ R ⁷ , and R ⁶ and R ⁷ are each independently an alkyl group having 1 to 6 carbon atoms which may contain an oxygen atom (R ⁶ and R ^{7 form} a ring) The method of manufacturing a metal film according to any one of claims 1 to 3. Said ^{R 2} is an -OR ^{8, R 8} is an alkyl group having 1 to 6 carbon atoms, method for producing a metal film according to claim 1. R ² is —CR ¹⁰ ═CArR ⁹ , R ⁹ and R ¹⁰ are located in trans, and independently of each other are hydrogen, a phenyl group, or an alkyl group having 1 to 6 carbon atoms, and Ar is a carbon number 1-6 alkyl groups, alkyloxy groups, hydroxyl groups, hydroxymethyl groups, formyl groups, amino groups, monoalkylamino groups or dialkylamino groups, or substituted by cyclic substituents formed by combinations of these substituents. The manufacturing method of the metal film in any one of Claims 1-3 which is a phenyl group, pyridyl group, or thienyl group which may be sufficient. R ² is Ar, and Ar is an alkyl group having 1 to 6 carbon atoms, an alkyloxy group, a hydroxyl group, a hydroxymethyl group, a formyl group, an amino group, a monoalkylamino group or a dialkylamino group, or a substitution thereof. The manufacturing method of the metal film in any one of Claims 1-3 which is the phenyl group, pyridyl group, or thienyl group which may be substituted by the cyclic substituent formed by the combination of group.   The said metal is silver, copper, nickel, or tin, The manufacturing method of the metal film in any one of Claims 1-7.   The method for producing a metal film according to claim 1, wherein the metal particles, the metal particles having an oxide film, or the metal oxide particles have an average particle diameter of 1 to 200 nm. The presence of the compound represented by Formula 1 is
(1) Present as a vapor outside the composition part (2) Present as a liquid outside the composition (3) Present as a component of the composition or a combination thereof The manufacturing method of the metal film as described in any one of.   The manufacturing method of the metal film in any one of Claims 1-10 by which the temperature of the said heat processing is selected as 180 degrees C or less.   A composition comprising at least one selected from the metal particles, metal particles having an oxide film, and metal oxide particles and a compound represented by Formula 1. The metal film manufactured by the manufacturing method of the metal film of Claims 1-11.