WO2010095672A1 - Metal thin film production method and metal thin film - Google Patents
Metal thin film production method and metal thin film Download PDFInfo
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- WO2010095672A1 WO2010095672A1 PCT/JP2010/052405 JP2010052405W WO2010095672A1 WO 2010095672 A1 WO2010095672 A1 WO 2010095672A1 JP 2010052405 W JP2010052405 W JP 2010052405W WO 2010095672 A1 WO2010095672 A1 WO 2010095672A1
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- thin film
- metal
- fine particles
- metal thin
- superheated steam
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/102—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by bonding of conductive powder, i.e. metallic powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1105—Heating or thermal processing not related to soldering, firing, curing or laminating, e.g. for shaping the substrate or during finish plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1157—Using means for chemical reduction
Definitions
- the present invention relates to a method for producing a low volume resistivity metal thin film having excellent conductivity from a metal fine particle dispersion, and a metal thin film produced by this method.
- Conductive paste using conductive particles is used in screen printing and dispensers to form conductive circuits.
- the conductive particles used flaky metal powder having a particle size of several ⁇ m or more is used, and the thickness of the circuit is set to 10 ⁇ m or more to ensure conductivity.
- the density of conductive circuits has been rapidly increasing. In order to enable the formation of higher density circuits, finer metal fine particles have been developed.
- the fine particle production method is classified into a solid phase method, a gas phase method, and a liquid phase method depending on the phase to be generated.
- the particle size is limited to about 0.1 ⁇ m.
- the gas phase method and the liquid phase method which are build-up processes, are suitable.
- the gas phase method include a physical condensation method by cooling a high temperature steam and a particle generation method by a gas phase chemical reaction.
- Patent Document 1 discloses that metal fine particles having a particle diameter of several nanometers to several tens of nanometers were obtained by a vapor phase method.
- the liquid phase method is generally not only cheaper to manufacture than the gas phase method, but also can be applied not only to a single component of the particle but also to a multi-component system, and the manufacturing process can be diversified.
- Various methods have been studied with advantages such as relatively easy control of particle size and easy surface modification of particles.
- a coprecipitation method, a sol-gel method, a gel-sol method, a reverse micelle method, a hot soap method, a spray pyrolysis method, and the like have been proposed.
- Metal fine particles are also synthesized in a colloidal state by a method of reducing a metal salt in a solution in the presence of a protective polymer.
- Patent Document 2 discloses that copper fine particles of 20 to 41 nm were obtained by a liquid phase method.
- Patent Document 3 discloses that cuprous oxide fine particles having a particle diameter of 20 nm were obtained by a liquid phase method.
- Patent Document 4 discloses a method for producing metal fine particles from a metal compound in a liquid phase using a polyol as a reducing agent.
- Patent Document 1 discloses a method of forming a metal thin film by preparing a metal paste using a dispersion in which metal fine particles having a particle size of 100 nm or less are dispersed, and sintering a metal paste coating film, An electric circuit or wiring can be formed by this method.
- Patent Documents 2 and 3 also disclose that a thin film having excellent conductivity was obtained by subjecting a copper paste coating to a heat treatment at 300 ° C. or 350 ° C. for 1 hour in a nitrogen atmosphere.
- fine particles typified by nanoparticles are very large in surface area, and therefore easily aggregate and difficult to disperse.
- the dispersibility of the metal fine particles can be improved by adsorbing the binder resin or dispersant to the metal fine particles, and the effect of preventing the aggregation of the fine particles to increase the storage stability and ensuring the fluidity of the dispersion. I can expect.
- the binder resin or dispersant tends to prevent the metal fine particles from contacting each other and hinder the improvement in conductivity. In such a case, it may be necessary to remove the binder resin or the dispersant by sublimation or decomposition evaporation.
- the adhesiveness with a substrate such as a film or glass tends to deteriorate due to firing.
- Patent Document 5 As a measure to avoid the influence of the oxide film on the surface of the metal fine particles, in Patent Document 5, a copper thin film having excellent conductivity is obtained with hydrogen gas at 250 ° C. using a cupric oxide dispersion containing ethylene glycol. .
- high temperature treatment in highly explosive hydrogen gas is not a highly productive method.
- An object of the present invention is to provide a method for forming a metal thin film, in which a conductive layer having a low volume resistivity can be obtained on an insulating substrate using a dispersion of fine metal particles.
- metal oxide fine particles and metal fine particles having a metal oxide film can also be used as the metal fine particles.
- the metal thin film excellent in electroconductivity can be obtained also about the coating film formed from the metal fine particle dispersion containing a lot of resin binders and a dispersing agent.
- the heat treatment temperature can be made lower than before, and a resin film or the like can be used as an insulating substrate.
- the present invention (1) The manufacturing method of a metal thin film including the process of heat-processing with superheated steam to the coating film containing a metal microparticle dispersion. (2) The method for producing a metal thin film according to (1), wherein the metal fine particle dispersion is a metal fine particle dispersion containing a reducing agent. (3) The method for producing a metal thin film according to (1), wherein the superheated steam is superheated steam containing an alcohol compound. (4) The method for producing a metal thin film according to (1), wherein the coating film is obtained by applying or printing a metal fine particle dispersion.
- the method for forming a metal thin film of the present invention includes a step of heat-treating a coating film containing a metal fine particle dispersion with superheated steam.
- the treatment atmosphere becomes oxygen-free or low-oxygen, and even metal fine particles that easily oxidize in the air, such as copper fine particles, can be prevented from being oxidized in the heat treatment step. .
- the deterioration of conductivity due to oxidation hardly occurs.
- the oxide layer on the surface of the fine particles may be reduced, and the conductivity may be improved.
- the superheated steam is used to promote desorption of organic substances adsorbed on the metal fine particles, and as a result, the opportunity for contact between the metal fine particles May be increased, and the conductivity is further improved.
- superheated steam since superheated steam has higher heating efficiency than heated air or heated nitrogen gas, firing may occur in a short time and / or at a low temperature. Furthermore, in the case where the heat treatment temperature can be lowered than before, it may be possible to use a resin film or the like having poor heat resistance as an insulating substrate.
- the metal thin film formed by the method of the present invention becomes a metal thin film having a low electric resistance value, and can be used for a metal / resin laminate, a conductive material for plating, a metal wiring material, a conductive circuit material and the like. .
- a preferred embodiment of the present invention includes a step of forming a coating film made of a metal fine particle dispersion containing a reducing agent on an insulating substrate and further heat-treating with superheated steam.
- superheated steam By using superheated steam, desorption of organic substances adsorbed on the metal fine particles is promoted to increase the chance of contact between the metal fine particles, and as a result, the conductivity may be improved.
- superheated steam has higher heating efficiency than heated air and heated nitrogen gas, so that the oxide film on the surface of metal fine particles can be reduced even by compounds with relatively weak reducing power such as alcohol and polyether, improving conductivity. May occur.
- heat treatment with superheated steam may cause evaporation of the reducing agent decomposition residue and unreacted substances, resulting in improved conductivity.
- the method for forming a metal thin film of the present invention one or more of these actions occur, thereby obtaining a metal thin film having a low volume resistivity, reducing the superheated steam treatment temperature, shortening the superheated steam treatment time, etc.
- One or more of the effects are exhibited.
- a substrate having poor heat resistance such as a resin film as the base material of the metal thin film. There is a case.
- a preferred embodiment of the present invention includes a step of forming a coating film made of a metal fine particle dispersion on an insulating substrate and further heat-treating with superheated steam containing an alcohol compound.
- Superheated steam treatment may show desorption of organic substances adsorbed on metal fine particles and depending on the type of metal. However, by adding an alcohol compound to superheated steam, the function of these superheated steam is increased, and the metal fine particles are treated. There are cases where the desorption of the adsorbed organic matter is promoted, or the reduction of the surface oxide film of the metal fine particles is promoted to increase the contact between the metal fine particles.
- One or more of these actions are produced by the method for producing a metal thin film of the present invention, and a metal thin film having a low volume resistivity is obtained, the superheated steam treatment temperature is lowered, and the superheated steam treatment time is shortened. One or more are demonstrated. Further, when the effect of lowering the superheated steam treatment temperature and shortening the superheated steam treatment time is exhibited, it is possible to use a substrate having poor heat resistance such as a resin film as the base material of the metal thin film. There is a case.
- a metal thin film is produced by subjecting a coating film containing a metal fine particle dispersion to a heat treatment with superheated steam.
- the coating film is preferably one obtained by applying or printing a metal fine particle dispersion on an insulating substrate.
- the metal fine particle dispersion of the present invention is a dispersion of metal fine particles dispersed in a dispersion medium, and may contain a binder resin capable of adsorbing the metal fine particles if necessary.
- the average particle size of the metal fine particles used in the present invention is preferably 0.5 ⁇ m or less, more preferably 0.25 ⁇ m or less, still more preferably 0.1 ⁇ m or less, and particularly preferably 0.08 ⁇ m or less.
- the average particle diameter is measured by measuring the particle diameter of 100 particles using any one of a transmission electron microscope, a field emission transmission electron microscope, and a field emission scanning electron microscope to obtain an average value.
- the average particle diameter of the metal fine particles is larger than 0.5 ⁇ m, the metal fine particles are precipitated in the dispersion, and the printability of the fine circuit is deteriorated.
- the minimum of an average particle diameter is not specifically limited, It is preferable that it is 0.01 micrometer or more. If it is less than 0.01 ⁇ m, it may be difficult to obtain a highly conductive metal thin film because a large amount of a dispersion medium is required in order to limit the economical efficiency of metal fine particles and to obtain a stable dispersion.
- the metal fine particles used in the present invention have a particle diameter of 0.5 ⁇ m or less, they may be used by mixing different particle diameters.
- metal fine particles used in the present invention either fine particles fused by heat treatment or those not fused can be used.
- the metal include copper, nickel, cobalt, silver, platinum, gold, molybdenum, and titanium, and silver and copper are particularly preferable. These metal fine particles may be a commercially available product or can be prepared using a known method. In addition, a structure in which different kinds of metals are stacked, or an organic or inorganic material plated with metal may be used.
- the metal fine particles used in the present invention also include metal fine particles whose surfaces are covered with an oxide and metal oxide fine particles, unless otherwise specified.
- the metal fine particle dispersion used in the present invention can contain a reducing agent.
- a reducing agent means what has the capability to reduce
- the reducing agent include sodium borohydride, lithium borohydride, hydrazines, aldehydes such as formalin and acetaldehyde, sulfites, formic acid, oxalic acid, carboxylic acids such as succinic acid and ascorbic acid, or lactones, ethanol, Aliphatic monoalcohols such as butanol and octanol, monoalcohols such as alicyclic monoalcohols such as terpineol, polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin and trimethylolpropane, Polyethers such as polyethylene glycol and polypropylene glycol,
- Residue of the reducing agent or the reducing agent decomposition product on the metal thin layer may cause deterioration of properties such as conductivity of the obtained metal thin layer and adhesion to the insulating substrate. Therefore, it is desirable that the reducing agent is evaporated by superheated steam treatment. In addition, when the coating layer of the metal fine particle dispersion is subjected to the superheated steam treatment, it is desirable that the reducing agent remains in the coating layer. Therefore, when the reducing agent is a liquid volatile substance, the boiling point is desirably 150 ° C. or higher.
- the dispersion medium used in the metal fine particle dispersion used in the present invention is selected from those that dissolve the resin when a binder resin that functions to stabilize the dispersion is used. It may be.
- the dispersion medium has a role of adjusting the viscosity of the dispersion in addition to the role of dispersing the metal fine particles in the dispersion.
- organic solvents that are suitably used as the dispersion medium include alcohols, ethers, ketones, esters, aromatic hydrocarbons, amides, and the like.
- binder resin used as necessary in the metal fine particle dispersion used in the present invention examples include polyester, polyurethane, polycarbonate, polyether, polyamide, polyamideimide, polyimide, and acrylic.
- a resin having an ester bond, a urethane bond, an amide bond, an ether bond, an imide bond or the like is preferable from the viewpoint of the stability of the metal fine particle dispersion.
- the metal fine particle dispersion used in the present invention is usually composed of metal fine particles, a solvent, and a binder resin.
- the proportion of each component is preferably in the range of 20 to 400 parts by weight of solvent and 5 to 20 parts by weight of binder resin with respect to 100 parts by weight of metal fine particles.
- the proportion of each component is more preferably in the range of 60 to 180 parts by weight of solvent and 8 to 14 parts by weight of binder resin, and in the range of 80 to 120 parts by weight of solvent and 9 to 12 parts by weight of binder resin with respect to 100 parts by weight of metal fine particles. Further preferred.
- the binder resin is not necessarily required because the metal fine particles exist stably in the solution due to Brownian motion.
- the metal fine particle dispersion used in the present invention may be mixed with a curing agent as necessary.
- the curing agent that can be used in the present invention include phenol resins, amino resins, isocyanate compounds, and epoxy resins.
- the amount of the curing agent used is preferably in the range of 1 to 50% by weight of the binder resin, more preferably in the range of 3 to 28% by weight, and still more preferably in the range of 6 to 18% by weight.
- the metal fine particle dispersion used in the present invention preferably contains a polymer containing a functional group capable of adsorbing to a metal such as a sulfonate group or a carboxylate group. Furthermore, you may mix
- the dispersant include higher fatty acids such as stearic acid, oleic acid, and myristic acid, fatty acid amides, fatty acid metal salts, phosphoric acid esters, and sulfonic acid esters.
- the amount of the dispersant used is preferably in the range of 0.1 to 10% by weight of the binder resin, more preferably in the range of 0.3 to 6% by weight, and still more preferably in the range of 0.6 to 3% by weight. Use of the dispersant may exhibit an effect of improving the dispersibility of the metal fine particles and the storage stability of the dispersion.
- a general method for dispersing powder in a liquid can be used. For example, after mixing a mixture of metal fine particles and a binder resin solution and, if necessary, an additional solvent, dispersion may be performed by an ultrasonic method, a mixer method, a three-roll method, a ball mill method, or the like. Of these dispersing means, a plurality of dispersing means can be combined for dispersion. These dispersion treatments may be performed at room temperature, or may be performed by heating in order to reduce the viscosity of the dispersion.
- a general method used when the dispersion is applied or printed on a substrate can be used.
- the metal fine particle dispersion is applied or printed by a method such as a screen printing method, a dip coating method, a spray coating method, a spin coating method, a roll coating method, a die coating method, an ink jet method, a relief printing method, an intaglio printing method, and then air-dried.
- the coating film can be formed by evaporating at least a part of the dispersion medium by heating or decompression.
- the coating film may be provided on the entire surface of the insulating substrate or may be provided partially, or may be a pattern formed product such as a conductive circuit.
- the thickness of the metal thin film of the present invention can be appropriately set according to necessary properties such as electric resistance and adhesiveness, and is not particularly limited.
- the range of the thickness of the metal thin film that can be formed varies depending on the dispersion composition and the method of coating or printing, it is preferably 0.05 to 30 ⁇ m, more preferably 0.1 to 20 ⁇ m, still more preferably 0.2 to 10 ⁇ m. is there.
- it is necessary to increase the thickness of the coating film, which is likely to cause economic deterioration such as an adverse effect due to residual solvent and a need to reduce the coating film forming speed.
- the coating film is too thin, the occurrence of pinholes tends to be significant.
- overprinting refers to printing the same pattern a number of times, thereby increasing the thickness of the metal thin film, or a metal thin film having a high aspect ratio (ratio of film pressure to line width).
- Multi-layer printing refers to printing different patterns in a superimposed manner, whereby different functions can be exhibited for each layer. Partial overprinting and / or multilayer printing may be performed, and overprinting and multilayer printing may be performed in combination. It is also possible to perform multilayer printing with a thin film different from the metal thin film of the present invention, such as an insulating layer.
- the insulating substrate is made of a polyimide resin
- a coating film of the metal fine particle dispersion is formed on the primary dried product of the polyimide precursor solution or the primary dried product of the polyimide solution or the polyamideimide solution, and then by superheated steam. It is preferable to take a method of performing heat treatment. With the 10-30 wt% solvent remaining in the polyimide precursor solution or the primary dry product of the polyimide solution, the metal fine particle dispersion is subsequently applied and dried to form a coating film. Then, the subsequent heat treatment with superheated steam tends to strengthen the adhesion between the polyimide resin layer and the coating film.
- the coating film formed from the metal fine particle dispersion is preferably subjected to a heat treatment with superheated steam after a drying treatment.
- a heat treatment with superheated steam after a drying treatment.
- the drying process and the superheated steam process may be performed continuously or may be performed with another process interposed therebetween. Examples of the process sandwiched between the drying process and the superheated steam process include a process of applying a reducing agent to the coating film.
- the coating film may or may not contain a reducing agent in advance, and if it is contained, any of the same type, different type, and a mixture of the same type and different type It is also possible to do.
- a calendar process can be mentioned as a process pinched
- the coating film containing the metal fine particle dispersion After forming the coating film containing the metal fine particle dispersion, it is preferable to perform pressure treatment (calendar treatment) within a range where the coating film is not destroyed.
- pressure treatment calendar treatment
- the calendering process is performed by applying a linear pressure corresponding to the material between the metal roll and the elastic roll, for example, 1-100 kg / cm.
- the calendar treatment is particularly preferably performed by heating to a temperature equal to or higher than the glass transition temperature of the binder resin.
- the calendar treatment may be performed in a state where another layer is laminated on the coating film of the metal fine particle dispersion.
- the metal thin film of the present invention can be obtained by subjecting the coating film containing the metal fine particle dispersion to heat treatment with superheated steam.
- Superheated steam refers to steam that has been heated by heating saturated steam without increasing the pressure. Superheated steam can heat a substance in a short time because the radiant heat energy becomes remarkably larger than that of ordinary heated air at a temperature of 150 ° C. or higher.
- superheated steam containing an alcohol compound can be used as superheated steam.
- Alcohol compounds contained in superheated steam are aliphatic monoalcohols such as methanol, ethanol, 1-propanol and 2-propanol, monoalkyl aliphatic diols such as ethylene glycol monoethyl ether, ethylene glycol monoethyl ether and propylene glycol monomethyl ether.
- Monoalcohol compounds such as alicyclic monoalcohols such as ether, cyclohexanol and terpineol, aliphatic diols such as ethylene glycol, propylene glycol, diethylene glycol and butanediol, alicyclic diols such as cyclohexanedimethanol, glycerin and trimethylolpropane
- polyhydric alcohol compounds such as pentaerythritol, and hydroxycarboxylic acids such as tartaric acid, hydroxybutyric acid and malic acid.
- methanol, ethanol, ethylene glycol, and propylene glycol are preferred.
- Examples of the method for producing superheated steam containing an alcohol compound include a method of heating a saturated vapor of a solution in which an alcohol compound is dissolved in water, and a method of mixing and heating each saturated vapor of an alcohol compound and water.
- the content of the alcohol compound in the superheated steam is preferably in the range of 0.01 to 20% by weight, although the optimum range varies depending on the type of compound.
- the binder resin may be significantly dissolved or decomposed.
- a more preferred range is 0.1 to 5% by weight.
- the superheated steam treatment is preferably performed as a baking treatment of the coating film containing the metal fine particle dispersion.
- the firing treatment tends to exhibit a particularly high effect when the particle size of the metal fine particles is 100 nm or less. Although it varies depending on the surface state such as crystallinity and oxidation degree of the metal fine particles, so-called nanoparticles have a large surface activity and start to be fused at a temperature much lower than the generally known melting point of the bulk.
- the firing treatment refers to a heat treatment in which at least a part of the metal fine particles is fused, and it is not necessarily required to decompose or volatilize the binder resin and the dispersant.
- the temperature of the superheated steam used in the present invention is 150 ° C or higher, particularly 200 ° C or higher, and the upper limit of temperature is preferably 500 ° C or lower.
- the upper limit of the temperature is also limited by the heat resistance characteristics of the insulating substrate and binder resin to be used, but when the binder resin is used, it is more preferably 400 ° C. or lower, and further preferably 350 ° C. or lower.
- the heating time is also selected from the amount and characteristics of the object to be treated, but is preferably 10 seconds to 30 minutes. When the temperature of the superheated steam is too low, a conductive layer having a low volume resistivity cannot be obtained. If the temperature of the superheated steam is too high, most or all of the binder resin is removed, the adhesion between the metal thin film and the substrate may be impaired, and the substrate may be deteriorated. Care must be taken when using a substrate.
- the heat treatment operation with superheated steam can be handled in the same manner as the heat treatment operation with heated air in hot air drying.
- air is completely replaced with superheated steam, an oxygen-free state similar to that of an inert gas is obtained, and an oxidation reaction can be prevented.
- the reduction of the surface activity due to the formation of fine particles may cause a reduction reaction, and the conductivity may be dramatically improved.
- copper fine particles a remarkable improvement in conductivity is recognized, and it is considered that reduction of the oxide layer formed on the surface of the copper fine particles occurs.
- the effect of improving the conductivity considered to be due to this reduction tends to increase as the particle diameter decreases.
- metal fine particles such as copper fine particles, where the oxide film is easily formed, the conductive portion and the insulating portion can be patterned on the same surface by patterning the portion to be treated with superheated steam and the portion not to be treated. .
- the metal thin film obtained in the present invention may be subjected to a surface treatment with a rust inhibitor such as a benzotriazole compound or a chromate compound after undergoing a heat treatment step with superheated steam.
- a rust inhibitor such as a benzotriazole compound or a chromate compound
- the insulating substrate used in the present invention may be either an organic material or an inorganic material.
- the material used for the insulating substrate include glass, ceramics, polyimide resin, and tetrafluoroethylene resin.
- substrate which are normally used for an electrical wiring circuit board, are also mentioned.
- heat treatment with superheated steam is performed, it is essential to have heat resistance that can withstand this. For this reason, it is preferable to use a film, sheet, or ceramic made of a polyimide resin having excellent heat resistance as an insulating substrate.
- the polyimide resin examples include a polyimide precursor resin, a solvent-soluble polyimide resin, and a polyamideimide resin.
- the polyimide resin can be polymerized by a usual method. For example, tetracarboxylic dianhydride and diamine are reacted in solution at a low temperature to obtain a polyimide precursor solution, and tetracarboxylic dianhydride and diamine are reacted in a high temperature solution to obtain a solvent-soluble polyimide solution. And a method using isocyanate as a raw material and a method using acid chloride as a raw material.
- Examples of raw materials used for the polyimide precursor resin and the solvent-soluble polyimide resin include the following.
- Examples of the acid component include pyromellitic acid, benzophenone-3,3 ′, 4,4′-tetracarboxylic acid, biphenyl-3,3 ′, 4,4′-tetracarboxylic acid, diphenylsulfone-3,3 ′, 4, 4'-tetracarboxylic acid, diphenyl ether-3,3 ', 4,4'-tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid, naphthalene-1,2,4,5-tetracarboxylic acid Monoanhydrides, dianhydrides, esterified products such as naphthalene-1,4,5,8-tetracarboxylic acid, hydrogenated pyromellitic acid, hydrogenated biphenyl-3,3 ′, 4,4′-tetracarboxylic acid Etc.
- the amine component examples include p-phenylenediamine, m-phenylenediamine, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 3,3′-diaminobenzanilide, 4,4′-diaminobenzanilide, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 3,4'-diaminobenzophenone, 2,6-tolylenediamine, 2,4-tolylenediamine, 4,4'-diaminodiphenyl sulfide, 3,3'-diamino
- Raw materials used for polyamideimide resin include trimellitic anhydride, diphenyl ether-3,3 ′, 4,4′-tricarboxylic acid anhydride, diphenylsulfone-3,3 ′, 4′-tricarboxylic acid anhydride as acid components And tricarboxylic acid anhydrides such as benzophenone-3,3 ′, 4′-tricarboxylic acid anhydride, naphthalene-1,2,4-tricarboxylic acid anhydride, hydrogenated trimellitic acid anhydride, and the like.
- the amine component include diamines mentioned for polyimide resins, or diisocyanates alone or as a mixture.
- a resin separately polymerized by a combination of these acid component and amine component can be mixed and used.
- N-methyl-2-pyrrolidone N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, tetramethylurea , Sulfolane, dimethyl sulfoxide, ⁇ -butyrolactone, cyclohexanone, and cyclopentanone.
- N-methyl-2-pyrrolidone and N, N-dimethylacetamide are preferred.
- a solvent such as toluene, xylene, diglyme, tetrahydrofuran, methyl ethyl ketone, etc. may be added as long as the solubility is not inhibited.
- Copper fine particles Copper (I) ions produced by adjusting the pH using copper (II) sulfate, ammonia, ammonium sulfate, and metal copper in water, copper (II) ions, and copper Metal copper fine particles obtained by disproportionation decomposition reaction. Observation with a transmission electron microscope reveals spherical particles having an average particle size of 80 nm. Copper fine particles (2): Copper fine particles produced by gas evaporation in a vacuum atmosphere. During the production of copper fine particles, the copper vapor generated in the crucible and the ⁇ -terpineol vapor were mixed to prevent the aggregation and chaining of the copper particles.
- Copper fine particles (3) Copper metal fine particles obtained by suspending copper (II) hydroxide in ethylene glycol and heating to reflux. Observation with a transmission electron microscope reveals spherical particles having an average particle size of 300 nm. Copper fine particles (4) Pure copper powder “HXR-Cu” manufactured by Nippon Atomizing Co., Ltd. Spherical particles with an average particle size of 1 ⁇ m. Copper fine particle (5): Copper hydroxide (II) and ethylene glycol were heated in a suspension state in a flask equipped with a reflux apparatus, and kept in a boiling state for 2 hours with stirring.
- Copper fine particles were centrifuged and washed with alcohol. Observation with a transmission electron microscope revealed spherical particles having an average particle diameter of 0.2 ⁇ m.
- Copper fine particles (6) In a flask with a reflux apparatus, a hydrazine aqueous solution was added to a suspension composed of copper hydroxide (II) and methyl alcohol with stirring and heated to maintain the boiling state for 30 minutes. The obtained copper fine particles were centrifuged and washed with acetone. Observation with a transmission electron microscope revealed spherical particles having an average particle size of 0.1 ⁇ m. Copper fine particles (7): Copper powder “1020Y” manufactured by Mitsui Mining & Smelting Co., Ltd.
- Silver fine particles (1) obtained by reducing silver nitrate in hexane with ascorbic acid and dodecylamine. Observation with a transmission electron microscope after washing and drying revealed spherical particles having an average particle diameter of 60 nm.
- Silver fine particles (2) Obtained by reducing silver nitrate in hexane with sodium borohydride and dodecylamine. Observation with a transmission electron microscope after washing and drying revealed spherical particles with an average particle diameter of 830 nm.
- Silver fine particles (3) obtained by reducing silver nitrate in hexane with ascorbic acid and dodecylamine.
- Silver fine particles (4) obtained by reducing silver nitrate in hexane with sodium borohydride and dodecylamine. Observation with a transmission electron microscope after washing and drying revealed spherical particles having an average particle diameter of 1.1 ⁇ m.
- Silver fine particles (5) obtained by reducing silver nitrate in hexane with ascorbic acid and dodecylamine. Observation with a transmission electron microscope after washing and drying revealed spherical particles with an average particle diameter of 40 nm.
- Silver fine particles (6) Obtained by reducing silver nitrate in hexane with sodium borohydride and dodecylamine. Observation with a transmission electron microscope after washing and drying revealed spherical particles having an average particle diameter of 700 nm.
- Experiment number Cu-1 (Example Cu-1) A composition having the following blending ratio was placed in a sand mill and dispersed at 800 rpm for 2 hours. As media, zirconia beads having a radius of 1 mm were used. The obtained copper fine particle dispersion was applied on a polyimide film with an applicator so that the thickness after drying was 2 ⁇ m, dried with hot air at 100 ° C. for 5 minutes, and then heated at 300 ° C. for 5 minutes as a coating film heat treatment. Went.
- a steam superheater (“DHF Super-Hi 10” manufactured by Daiichi High-Frequency Industry Co., Ltd.) was used as a superheated steam generator, and the heat treatment was performed in a heat treatment furnace supplying superheated steam at 10 kg / hour.
- Table 1 shows the electric resistance of the obtained metal thin film.
- Copper fine particles (1) (average particle size 80 nm) 9 parts ⁇ -butyrolactone (diluted solvent) 3.5 parts methyl ethyl ketone (diluted solvent) 5 parts
- Experiment Nos. Cu-2 to 14 (Example Cu-2 to 6, Comparative Example Cu-1 to 8, Example Ag-1 to 2, Comparative Example Ag-1 to 3) Similar to Experiment No. Cu-1, except that only the metal fine particles and coating film heat treatment conditions were changed to the conditions described in Tables 1 to 3 to prepare a metal fine particle dispersion, and then the same as Experiment No. Cu-1 A metal thin film was prepared, and the electrical resistance of the obtained metal thin film was evaluated. The results regarding the copper fine particles are shown in Tables 1 and 2, and the results regarding the silver fine particles are shown in Table 3.
- the obtained copper fine particle dispersion is polyimide with an applicator It applied so that the thickness after drying might be set to 2 micrometers on a film, and after carrying out hot-air drying at 100 degreeC for 5 minutes, the superheated steam process for 5 minutes was performed at 300 degreeC as a coating-film heat processing. In the coating layer before the superheated steam treatment, 50% by weight of dipropylene glycol in the coating solution remained.
- a steam superheater (“DHF Super-Hi 10” manufactured by Daiichi High-Frequency Industry Co., Ltd.) was used as a superheated steam generator, and the heat treatment was performed in a heat treatment furnace supplying superheated steam at 10 kg / hour.
- Table 1 shows the electric resistance of the obtained metal thin film.
- Experiment No. Cu-16 to 28 (Example Cu-8 to 13, Comparative Example Cu-9 to 15), Experiment No. Ag-6 to 14 (Example Ag-3 to 7, Comparative Example Ag-4 to 7)
- the composition of the metal fine particle dispersion and the coating heat treatment conditions were the same as those shown in Tables 4 to 7, and the other conditions were the same as in Experiment No. Cu-15.
- a metal thin film was prepared in the same manner as described above, and the electrical resistance of the obtained metal thin film was evaluated.
- the results for copper fine particles are shown in Tables 4 and 5, and the results for silver fine particles are shown in Tables 6 and 7, respectively.
- UR8300 Copolymer polyurethane resin manufactured by Toyobo Co., Ltd.
- Byron 300 Copolyester resin manufactured by Toyobo Co., Ltd.
- Coronate HX Polyisocyanate manufactured by Nippon Polyurethane Co., Ltd.
- UR8300 Copolymer polyurethane resin manufactured by Toyobo Co., Ltd.
- Byron 300 Copolyester resin manufactured by Toyobo Co., Ltd.
- Coronate HX Polyisocyanate manufactured by Nippon Polyurethane Co., Ltd.
- UR8300 Copolyurethane resin manufactured by Toyobo Co., Ltd.
- UR8300 Copolyurethane resin manufactured by Toyobo Co., Ltd.
- Copper fine particles (1) (average particle size 80 nm) 9 parts ⁇ -butyrolactone (diluted solvent) 6 parts
- “Coronate HX” manufactured by Nippon Polyurethane as a curing agent
- the thickness after drying might be set to 2 micrometers with an applicator, and it dried by hot air at 100 degreeC for 10 minutes, and then performed the superheated steam process for 5 minutes at 300 degreeC as a coating-film heat processing.
- a steam superheater (“DHF Super-Hi 10” manufactured by Daiichi High-Frequency Industry Co., Ltd.) was used as a superheated steam generator, and the heat treatment was performed in a heat treatment furnace supplying superheated steam at 10 kg / hour.
- a 1 wt% aqueous ethanol solution was used as a vapor source. Table 1 shows the electric resistance of the obtained metal thin film.
- Experiment No. Cu-30 to 41 (Example Cu-14 to 24, Comparative Example Cu-16 to 17), Experiment No. Ag-15 to 24 (Example Ag-8 to 15, Comparative Example Ag-8 to 9)
- the composition of the metal fine particle dispersion and the coating heat treatment conditions were the same as those shown in Tables 8 to 11, and the other conditions were the same as in Experiment No. Cu-29.
- a metal thin film was prepared in the same manner as described above, and the electrical resistance of the obtained metal thin film was evaluated.
- the results for copper fine particles are shown in Tables 8 and 9, and the results for silver fine particles are shown in Tables 10 and 11, respectively.
- HR13NX Polyamideimide resin manufactured by Toyobo Co., Ltd. Byron 300: Copolyester resin manufactured by Toyobo Co., Ltd.
- Coronate HX Polyisocyanate manufactured by Nippon Polyurethane
- HR13NX Polyamideimide resin manufactured by Toyobo Co., Ltd. Byron 300: Copolyester resin manufactured by Toyobo Co., Ltd.
- Coronate HX Polyisocyanate manufactured by Nippon Polyurethane
- HR13NX Polyamideimide resin manufactured by Toyobo Co., Ltd.
- HR13NX Polyamideimide resin manufactured by Toyobo Co., Ltd.
- a metal thin film having a low volume resistance value can be formed on an insulating substrate from fine metal fine particles.
- the metal thin film of the present invention is useful as a metal thin film forming material such as a metal / resin laminate, an electromagnetic shielding metal thin film, a conductive layer for plating, a metal wiring material, a conductive material and the like.
Abstract
Description
(1) 金属微粒子分散体を含有する塗膜に過熱水蒸気による加熱処理を施す工程を含む、金属薄膜の製造方法。
(2) 前記金属微粒子分散体が還元剤を含有する金属微粒子分散体である(1)に記載の金属薄膜の製造方法。
(3) 前記過熱水蒸気がアルコール化合物を含有する過熱水蒸気である(1)に記載の金属薄膜の製造方法。
(4) 前記塗膜が金属微粒子分散体を塗布または印刷したものである(1)に記載の金属薄膜の製造方法。
(5) 前記金属微粒子の平均粒径が500nm以下である(1)に記載の金属薄膜の製造方法。
(6) 前記金属微粒子が銅、銅酸化物、銀、銀酸化物のいずれかひとつ以上からなる(1)に記載の金属薄膜の製造方法。
(7) (1)~(6)のいずれかの製造方法で製造された金属薄膜。 As a result of intensive studies to solve the above-mentioned problems, the present inventor has completed the present invention. That is, the present invention
(1) The manufacturing method of a metal thin film including the process of heat-processing with superheated steam to the coating film containing a metal microparticle dispersion.
(2) The method for producing a metal thin film according to (1), wherein the metal fine particle dispersion is a metal fine particle dispersion containing a reducing agent.
(3) The method for producing a metal thin film according to (1), wherein the superheated steam is superheated steam containing an alcohol compound.
(4) The method for producing a metal thin film according to (1), wherein the coating film is obtained by applying or printing a metal fine particle dispersion.
(5) The method for producing a metal thin film according to (1), wherein the metal fine particles have an average particle size of 500 nm or less.
(6) The method for producing a metal thin film according to (1), wherein the metal fine particles are made of one or more of copper, copper oxide, silver, and silver oxide.
(7) A metal thin film produced by any one of the production methods (1) to (6).
銅微粒子(1):水中にて、硫酸銅(II)、アンモニア、硫酸アンモニウム、及び金属銅を用い、pH調節により生成した銅(I)イオンを、銅(II)イオン、および銅に不均化分解反応により得た金属銅微粒子。透過型電子顕微鏡により観察したところ、平均粒径80nmの球状の粒子である。
銅微粒子(2):真空雰囲気中でのガス中蒸発法にて生成させた銅微粒子。銅微粒子製造時、坩堝で発生させた銅蒸気とα-テルピネオールの蒸気を混合し銅粒子の凝集やチェーン化を防止した。透過型電子顕微鏡により観察したところ、平均粒径20nmの球状の粒子である。
銅微粒子(3):水酸化銅(II)をエチレングリコール中に懸濁させ、加熱還流させることにより得た金属銅微粒子。透過型電子顕微鏡により観察したところ、平均粒径300nmの球状の粒子である。
銅微粒子(4)日本アトマイズ加工社製純銅粉「HXR-Cu」。平均粒径1μmの球状粒子。
銅微粒子(5):還流装置つきフラスコに、水酸化銅(II)、エチレングリコールを懸濁状態で加熱し、撹拌下、2時間煮沸状態を保った。得られた銅微粒子を遠心分離し、アルコールで洗浄した。透過型電子顕微鏡により観察したところ、平均粒径0.2μmの球状の粒子であった。
銅微粒子(6):還流装置つきフラスコ中で、水酸化銅(II)とメチルアルコールからなる懸濁液に撹拌下、ヒドラジン水溶液を加え加熱し30分間煮沸状態を保った。得られた銅微粒子を遠心分離し、アセトンで洗浄した。透過型電子顕微鏡により観察したところ、平均粒径0.1μmの球状の粒子であった。
銅微粒子(7):三井金属鉱業社製銅粉「1020Y」。平均粒径360nmの湿式銅粉。
銀微粒子(1):硝酸銀をアスコルビン酸とドデシルアミンによりヘキサン中で還元することにより得た。洗浄、乾燥後、透過型電子顕微鏡により観察したところ、平均粒径60nmの球状の粒子であった。
銀微粒子(2):硝酸銀を水素化ホウ素ナトリウムとドデシルアミンによりヘキサン中で還元することにより得た。洗浄、乾燥後、透過型電子顕微鏡により観察したところ、平均粒径830nmの球状の粒子であった。
銀微粒子(3):硝酸銀をアスコルビン酸とドデシルアミンによりヘキサン中で還元することにより得た。洗浄、乾燥後、透過型電子顕微鏡により観察したところ、平均粒径50nmの球状の粒子であった。
銀微粒子(4):硝酸銀を水素化ホウ素ナトリウムとドデシルアミンによりヘキサン中で還元することにより得た。洗浄、乾燥後、透過型電子顕微鏡により観察したところ、平均粒径1.1μmの球状の粒子であった。
銀微粒子(5):硝酸銀をアスコルビン酸とドデシルアミンによりヘキサン中で還元することにより得た。洗浄、乾燥後、透過型電子顕微鏡により観察したところ、平均粒径40nmの球状の粒子であった。
銀微粒子(6):硝酸銀を水素化ホウ素ナトリウムとドデシルアミンによりヘキサン中で還元することにより得た。洗浄、乾燥後、透過型電子顕微鏡により観察したところ、平均粒径700nmの球状の粒子であった。 Metal fine particles used Copper fine particles (1): Copper (I) ions produced by adjusting the pH using copper (II) sulfate, ammonia, ammonium sulfate, and metal copper in water, copper (II) ions, and copper Metal copper fine particles obtained by disproportionation decomposition reaction. Observation with a transmission electron microscope reveals spherical particles having an average particle size of 80 nm.
Copper fine particles (2): Copper fine particles produced by gas evaporation in a vacuum atmosphere. During the production of copper fine particles, the copper vapor generated in the crucible and the α-terpineol vapor were mixed to prevent the aggregation and chaining of the copper particles. Observation with a transmission electron microscope reveals spherical particles having an average particle diameter of 20 nm.
Copper fine particles (3): Copper metal fine particles obtained by suspending copper (II) hydroxide in ethylene glycol and heating to reflux. Observation with a transmission electron microscope reveals spherical particles having an average particle size of 300 nm.
Copper fine particles (4) Pure copper powder “HXR-Cu” manufactured by Nippon Atomizing Co., Ltd. Spherical particles with an average particle size of 1 μm.
Copper fine particle (5): Copper hydroxide (II) and ethylene glycol were heated in a suspension state in a flask equipped with a reflux apparatus, and kept in a boiling state for 2 hours with stirring. The obtained copper fine particles were centrifuged and washed with alcohol. Observation with a transmission electron microscope revealed spherical particles having an average particle diameter of 0.2 μm.
Copper fine particles (6): In a flask with a reflux apparatus, a hydrazine aqueous solution was added to a suspension composed of copper hydroxide (II) and methyl alcohol with stirring and heated to maintain the boiling state for 30 minutes. The obtained copper fine particles were centrifuged and washed with acetone. Observation with a transmission electron microscope revealed spherical particles having an average particle size of 0.1 μm.
Copper fine particles (7): Copper powder “1020Y” manufactured by Mitsui Mining & Smelting Co., Ltd. Wet copper powder with an average particle size of 360 nm.
Silver fine particles (1): obtained by reducing silver nitrate in hexane with ascorbic acid and dodecylamine. Observation with a transmission electron microscope after washing and drying revealed spherical particles having an average particle diameter of 60 nm.
Silver fine particles (2): Obtained by reducing silver nitrate in hexane with sodium borohydride and dodecylamine. Observation with a transmission electron microscope after washing and drying revealed spherical particles with an average particle diameter of 830 nm.
Silver fine particles (3): obtained by reducing silver nitrate in hexane with ascorbic acid and dodecylamine. Observation with a transmission electron microscope after washing and drying revealed spherical particles having an average particle diameter of 50 nm.
Silver fine particles (4): obtained by reducing silver nitrate in hexane with sodium borohydride and dodecylamine. Observation with a transmission electron microscope after washing and drying revealed spherical particles having an average particle diameter of 1.1 μm.
Silver fine particles (5): obtained by reducing silver nitrate in hexane with ascorbic acid and dodecylamine. Observation with a transmission electron microscope after washing and drying revealed spherical particles with an average particle diameter of 40 nm.
Silver fine particles (6): Obtained by reducing silver nitrate in hexane with sodium borohydride and dodecylamine. Observation with a transmission electron microscope after washing and drying revealed spherical particles having an average particle diameter of 700 nm.
下記の配合割合の組成物をサンドミルにいれ、800rpmで、2時間分散した。メディアは半径1mmのジルコニアビーズを用いた。得られた銅微粒子分散体をアプリケーターによりポリイミドフィルム上に乾燥後の厚みが2μmになるように塗布し、100℃で5分熱風乾燥後、塗膜加熱処理として300℃で5分間の過熱水蒸気処理を行った。過熱水蒸気の発生装置として蒸気過熱装置(第一高周波工業株式会社製「DHF Super-Hi 10」)を用い、10kg/時間の過熱水蒸気を供給する熱処理炉で行った。得られた金属薄膜の電気抵抗を表1に示す。
バインダー樹脂の溶液 2.5部
トルエン/シクロヘキサノン=1/1(重量比)の40重量%溶液
バインダー樹脂:共重合ポリエステル、東洋紡積社製バイロン300
銅微粒子(1)(平均粒径80nm) 9部
γ-ブチロラクトン(希釈溶剤) 3.5部
メチルエチルケトン(希釈溶剤) 5部 Experiment number Cu-1 (Example Cu-1)
A composition having the following blending ratio was placed in a sand mill and dispersed at 800 rpm for 2 hours. As media, zirconia beads having a radius of 1 mm were used. The obtained copper fine particle dispersion was applied on a polyimide film with an applicator so that the thickness after drying was 2 μm, dried with hot air at 100 ° C. for 5 minutes, and then heated at 300 ° C. for 5 minutes as a coating film heat treatment. Went. A steam superheater (“DHF Super-Hi 10” manufactured by Daiichi High-Frequency Industry Co., Ltd.) was used as a superheated steam generator, and the heat treatment was performed in a heat treatment furnace supplying superheated steam at 10 kg / hour. Table 1 shows the electric resistance of the obtained metal thin film.
Binder resin solution 2.5 parts Toluene / cyclohexanone = 40% by weight solution of 1/1 (weight ratio) Binder resin: Copolyester, Byron 300 manufactured by Toyobo Co., Ltd.
Copper fine particles (1) (average particle size 80 nm) 9 parts γ-butyrolactone (diluted solvent) 3.5 parts methyl ethyl ketone (diluted solvent) 5 parts
実験番号Cu-1と同様にして、ただし、金属微粒子と塗膜加熱処理条件だけを表1~3に記載した条件に変更して金属微粒子分散体を調製し、次いで実験番号Cu-1と同様にして金属薄膜を作成し、得られた金属薄膜の電気抵抗を評価した。銅微粒子に関する結果を表1、2に、銀微粒子に関する結果を表3に示す。 Experiment Nos. Cu-2 to 14 (Example Cu-2 to 6, Comparative Example Cu-1 to 8, Example Ag-1 to 2, Comparative Example Ag-1 to 3)
Similar to Experiment No. Cu-1, except that only the metal fine particles and coating film heat treatment conditions were changed to the conditions described in Tables 1 to 3 to prepare a metal fine particle dispersion, and then the same as Experiment No. Cu-1 A metal thin film was prepared, and the electrical resistance of the obtained metal thin film was evaluated. The results regarding the copper fine particles are shown in Tables 1 and 2, and the results regarding the silver fine particles are shown in Table 3.
下記の配合割合の組成物をサンドミルにいれ、800rpmで、2時間分散した。メディアは半径1mmのジルコニアビーズを用いた。
バインダー樹脂の溶液 3部
トルエン/メチルエチルケトン=1/1(重量比)の30重量%溶液
バインダー樹脂:共重合ポリウレタン樹脂、東洋紡積社製UR8300
銅微粒子(1)(平均粒径60nm) 9部
トルエン/シクロヘキサノン=1/1(重量比)(希釈溶剤) 6部
ジプロピレングリコール(還元剤) 1部
得られた銅微粒子分散体をアプリケーターによりポリイミドフィルム上に乾燥後の厚みが2μmになるように塗布し、100℃で5分熱風乾燥後、塗膜加熱処理として300℃で5分間の過熱水蒸気処理を行った。過熱水蒸気処理前の塗布層には塗布液中のジプロピレングリコールの50重量%が残留していた。過熱水蒸気の発生装置として蒸気過熱装置(第一高周波工業株式会社製「DHF Super-Hi 10」)を用い、10kg/時間の過熱水蒸気を供給する熱処理炉で行った。得られた金属薄膜の電気抵抗を表1に示す。 Experiment number Cu-15 (Example Cu-7)
A composition having the following blending ratio was placed in a sand mill and dispersed at 800 rpm for 2 hours. As media, zirconia beads having a radius of 1 mm were used.
Binder resin solution 3 parts Toluene / methyl ethyl ketone = 30% by weight solution of 1/1 (weight ratio) Binder resin: Copolymer polyurethane resin, UR8300 manufactured by Toyobo Co., Ltd.
Copper fine particles (1) (average particle size 60 nm) 9 parts Toluene / cyclohexanone = 1/1 (weight ratio) (diluting solvent) 6 parts Dipropylene glycol (reducing agent) 1 part The obtained copper fine particle dispersion is polyimide with an applicator It applied so that the thickness after drying might be set to 2 micrometers on a film, and after carrying out hot-air drying at 100 degreeC for 5 minutes, the superheated steam process for 5 minutes was performed at 300 degreeC as a coating-film heat processing. In the coating layer before the superheated steam treatment, 50% by weight of dipropylene glycol in the coating solution remained. A steam superheater (“DHF Super-Hi 10” manufactured by Daiichi High-Frequency Industry Co., Ltd.) was used as a superheated steam generator, and the heat treatment was performed in a heat treatment furnace supplying superheated steam at 10 kg / hour. Table 1 shows the electric resistance of the obtained metal thin film.
金属微粒子分散体の組成と塗膜加熱処理条件を表4~7に記載した条件とし、他の条件は実験番号Cu-15と同様にして金属微粒子分散体を調製し、次いで実験番号Cu-15と同様にして金属薄膜を作成し、得られた金属薄膜の電気抵抗を評価した。銅微粒子に関する結果を表4、5に、銀微粒子に関する結果を表6、7に示す。 Experiment No. Cu-16 to 28 (Example Cu-8 to 13, Comparative Example Cu-9 to 15), Experiment No. Ag-6 to 14 (Example Ag-3 to 7, Comparative Example Ag-4 to 7)
The composition of the metal fine particle dispersion and the coating heat treatment conditions were the same as those shown in Tables 4 to 7, and the other conditions were the same as in Experiment No. Cu-15. A metal thin film was prepared in the same manner as described above, and the electrical resistance of the obtained metal thin film was evaluated. The results for copper fine particles are shown in Tables 4 and 5, and the results for silver fine particles are shown in Tables 6 and 7, respectively.
バイロン300:東洋紡績社製共重合ポリエステル樹脂
コロネートHX:日本ポリウレタン社製ポリイソシアネート
バイロン300:東洋紡績社製共重合ポリエステル樹脂
コロネートHX:日本ポリウレタン社製ポリイソシアネート
PUI-1:ポリウレタンイミド樹脂(樹脂組成:ポリテトラメチレングリコール(分子量1000)/ジフェニルメタンジイソシアネート/ベンゾフェノンテトラカルボン酸二無水物=1/2/1.05(モル比)、数平均分子量:8600)
PUI-1:ポリウレタンイミド樹脂(樹脂組成:ポリテトラメチレングリコール(分子量1000)/ジフェニルメタンジイソシアネート/ベンゾフェノンテトラカルボン酸二無水物=1/2/1.05(モル比)、数平均分子量:8600)
下記の配合割合の組成物をサンドミルにいれ、800rpmで、2時間分散した。メディアは半径1mmのジルコニアビーズを用いた。
バインダー樹脂の溶液 3部
NMP/キシレン=1/1(重量比)の30重量%溶液
バインダー樹脂:ポリアミドイミド樹脂、東洋紡積社製HR13NX
銅微粒子(1)(平均粒径80nm) 9部
γ-ブチロラクトン(希釈溶剤) 6部
得られた銅微粒子分散体に硬化剤として日本ポリウレタン社製「コロネートHX」を0.2部加えた後、アプリケーターによりポリイミドフィルム上に乾燥後の厚みが2μmになるように塗布し、100℃で10分熱風乾燥後、塗膜加熱処理として300℃で5分間の過熱水蒸気処理を行った。過熱水蒸気の発生装置として蒸気過熱装置(第一高周波工業株式会社製「DHF Super-Hi 10」)を用い、10kg/時間の過熱水蒸気を供給する熱処理炉で行った。蒸気源として1重量%エタノール水溶液を用いた。得られた金属薄膜の電気抵抗を表1に示す。 Experiment No. Cu-29 (Example Cu-14)
A composition having the following blending ratio was placed in a sand mill and dispersed at 800 rpm for 2 hours. As media, zirconia beads having a radius of 1 mm were used.
Binder resin solution 3 parts NMP / xylene = 30% by weight solution of 1/1 (weight ratio) Binder resin: Polyamideimide resin, HR13NX manufactured by Toyobo Co., Ltd.
Copper fine particles (1) (average particle size 80 nm) 9 parts γ-butyrolactone (diluted solvent) 6 parts After adding 0.2 parts of “Coronate HX” manufactured by Nippon Polyurethane as a curing agent to the obtained copper fine particle dispersion, It coated so that the thickness after drying might be set to 2 micrometers with an applicator, and it dried by hot air at 100 degreeC for 10 minutes, and then performed the superheated steam process for 5 minutes at 300 degreeC as a coating-film heat processing. A steam superheater (“DHF Super-Hi 10” manufactured by Daiichi High-Frequency Industry Co., Ltd.) was used as a superheated steam generator, and the heat treatment was performed in a heat treatment furnace supplying superheated steam at 10 kg / hour. A 1 wt% aqueous ethanol solution was used as a vapor source. Table 1 shows the electric resistance of the obtained metal thin film.
金属微粒子分散体の組成と塗膜加熱処理条件を表8~11に記載した条件とし、他の条件は実験番号Cu-29と同様にして金属微粒子分散体を調製し、次いで実験番号Cu-29と同様にして金属薄膜を作成し、得られた金属薄膜の電気抵抗を評価した。銅微粒子に関する結果を表8、9に、銀微粒子に関する結果を表10、11に示す。 Experiment No. Cu-30 to 41 (Example Cu-14 to 24, Comparative Example Cu-16 to 17), Experiment No. Ag-15 to 24 (Example Ag-8 to 15, Comparative Example Ag-8 to 9)
The composition of the metal fine particle dispersion and the coating heat treatment conditions were the same as those shown in Tables 8 to 11, and the other conditions were the same as in Experiment No. Cu-29. A metal thin film was prepared in the same manner as described above, and the electrical resistance of the obtained metal thin film was evaluated. The results for copper fine particles are shown in Tables 8 and 9, and the results for silver fine particles are shown in Tables 10 and 11, respectively.
バイロン300:東洋紡績社製共重合ポリエステル樹脂
PUI-1:ポリウレタンイミド樹脂(樹脂組成:ポリテトラメチレングリコール(分子量1000)/ジフェニルメタンジイソシアネート/ベンゾフェノンテトラカルボン酸二無水物=1/2/1.05(モル比)、数平均分子量:8600)
コロネートHX:日本ポリウレタン社製ポリイソシアネート
Coronate HX: Polyisocyanate manufactured by Nippon Polyurethane
バイロン300:東洋紡績社製共重合ポリエステル樹脂
PUI-1:ポリウレタンイミド樹脂(樹脂組成:ポリテトラメチレングリコール(分子量1000)/ジフェニルメタンジイソシアネート/ベンゾフェノンテトラカルボン酸二無水物=1/2/1.05(モル比)、数平均分子量:8600)
コロネートHX:日本ポリウレタン社製ポリイソシアネート
Coronate HX: Polyisocyanate manufactured by Nippon Polyurethane
According to the present invention, a metal thin film having a low volume resistance value can be formed on an insulating substrate from fine metal fine particles. The metal thin film of the present invention is useful as a metal thin film forming material such as a metal / resin laminate, an electromagnetic shielding metal thin film, a conductive layer for plating, a metal wiring material, a conductive material and the like.
Claims (7)
- 金属微粒子分散体を含有する塗膜に過熱水蒸気による加熱処理を施す工程を含む、金属薄膜の製造方法。 The manufacturing method of a metal thin film including the process of heat-processing with superheated steam to the coating film containing a metal microparticle dispersion.
- 前記金属微粒子分散体が還元剤を含有する金属微粒子分散体である請求項1に記載の金属薄膜の製造方法。 The method for producing a metal thin film according to claim 1, wherein the metal fine particle dispersion is a metal fine particle dispersion containing a reducing agent.
- 前記過熱水蒸気がアルコール化合物を含有する過熱水蒸気である請求項1に記載の金属薄膜の製造方法。 The method for producing a metal thin film according to claim 1, wherein the superheated steam is superheated steam containing an alcohol compound.
- 前記塗膜が金属微粒子分散体を絶縁性基板に塗布または印刷したものである請求項1に記載の金属薄膜の製造方法。 The method for producing a metal thin film according to claim 1, wherein the coating film is obtained by applying or printing a metal fine particle dispersion on an insulating substrate.
- 前記金属微粒子の平均粒径が0.5μm以下である請求項1に記載の金属薄膜の製造方法。 The method for producing a metal thin film according to claim 1, wherein an average particle diameter of the metal fine particles is 0.5 µm or less.
- 前記金属微粒子が、銅、銀またはそれらの酸化物、のいずれかひとつ以上からなる請求項1に記載の金属薄膜の製造方法。 The method for producing a metal thin film according to claim 1, wherein the metal fine particles are made of one or more of copper, silver, or oxides thereof.
- 請求項1~6いずれかの製造方法で製造された金属薄膜。
A metal thin film produced by the production method according to any one of claims 1 to 6.
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CN2010800088116A CN102326213A (en) | 2009-02-18 | 2010-02-18 | Metal thin film production method and metal thin film |
JP2010512865A JP4853590B2 (en) | 2009-02-18 | 2010-02-18 | Metal thin film manufacturing method and metal thin film |
KR1020117021546A KR101132108B1 (en) | 2009-02-18 | 2010-02-18 | Metal thin film production method and metal thin film |
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JP2011060653A (en) * | 2009-09-11 | 2011-03-24 | Toyobo Co Ltd | Manufacturing method for metallic thin film, and metallic thin film |
JP2013175559A (en) * | 2012-02-24 | 2013-09-05 | Hitachi Chemical Co Ltd | Composite layer composed of adhesive layer and wiring layer and adhesive layer forming ink for printing for forming the same |
JP2014057028A (en) * | 2012-09-14 | 2014-03-27 | Shin Etsu Chem Co Ltd | Solar battery and manufacturing method therefor |
JPWO2012157704A1 (en) * | 2011-05-18 | 2014-07-31 | 戸田工業株式会社 | Copper powder, copper paste, method for producing conductive coating film and conductive coating film |
JP2015076232A (en) * | 2013-10-08 | 2015-04-20 | 東洋紡株式会社 | Conductive paste, conductive thin film and electric circuit |
JP2015181160A (en) * | 2014-03-05 | 2015-10-15 | トッパン・フォームズ株式会社 | Conducting pattern forming method, and conductive wiring line |
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US20210138541A1 (en) * | 2018-08-08 | 2021-05-13 | Mitsui Mining & Smelting Co., Ltd. | Bonding composition, conductor bonding structure, and method for producing same |
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- 2010-02-18 JP JP2010512865A patent/JP4853590B2/en not_active Expired - Fee Related
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JP2015076232A (en) * | 2013-10-08 | 2015-04-20 | 東洋紡株式会社 | Conductive paste, conductive thin film and electric circuit |
JP2015181160A (en) * | 2014-03-05 | 2015-10-15 | トッパン・フォームズ株式会社 | Conducting pattern forming method, and conductive wiring line |
KR20170032275A (en) | 2014-07-14 | 2017-03-22 | 도다 고교 가부시끼가이샤 | Method for producing conductive coating film, and conductive coating film |
US20210138541A1 (en) * | 2018-08-08 | 2021-05-13 | Mitsui Mining & Smelting Co., Ltd. | Bonding composition, conductor bonding structure, and method for producing same |
US11931808B2 (en) * | 2018-08-08 | 2024-03-19 | Mitsui Mining & Smelting Co., Ltd. | Bonding composition, conductor bonding structure, and method for producing same |
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JPWO2010095672A1 (en) | 2012-08-30 |
CN102326213A (en) | 2012-01-18 |
KR20110122187A (en) | 2011-11-09 |
KR101132108B1 (en) | 2012-04-05 |
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