WO2014017288A1 - Composition de formation de film conducteur et procédé de production de film conducteur - Google Patents

Composition de formation de film conducteur et procédé de production de film conducteur Download PDF

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Publication number
WO2014017288A1
WO2014017288A1 PCT/JP2013/068719 JP2013068719W WO2014017288A1 WO 2014017288 A1 WO2014017288 A1 WO 2014017288A1 JP 2013068719 W JP2013068719 W JP 2013068719W WO 2014017288 A1 WO2014017288 A1 WO 2014017288A1
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group
conductive film
composition
formula
mass
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PCT/JP2013/068719
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English (en)
Japanese (ja)
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渡辺　徹
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富士フイルム株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints

Definitions

  • the present invention relates to a conductive film forming composition, and more particularly to a conductive film forming composition containing a polymer having a predetermined reducing group and copper oxide particles.
  • the present invention also relates to a method for producing a conductive film, and more particularly to a method for producing a conductive film using the conductive film forming composition.
  • a dispersion of metal particles or metal oxide particles is applied to the base material by a printing method, and heat treatment is performed to sinter the metal film or wiring on a circuit board.
  • a technique for forming an electrically conductive portion is known. Since the above method is simpler, energy-saving, and resource-saving than conventional high-heat / vacuum processes (sputtering) and plating processes, it is highly anticipated in the development of next-generation electronics.
  • Patent Document 1 discloses a method for producing a conductive pattern by forming a coating film using a dispersion containing a polyhydrazone compound and copper fine particles, and further performing a heat treatment. ing.
  • a coating film is formed using the dispersion containing the reducing organic polymer represented by the aliphatic polyether compound which has a hydroxyl group at the terminal, and a metal oxide particle, and also heat processing Has disclosed a method for producing a metal thin film.
  • An object of this invention is to provide the composition for electrically conductive film formation which can form the electrically conductive film which shows the outstanding electroconductivity in view of the said situation, and is excellent in storage stability.
  • Another object of the present invention is to provide a method for producing a conductive film using the composition for forming a conductive film.
  • the present inventors have found that the above problems can be solved by using a vinyl polymer having a predetermined reducing group bonded through a linking group. That is, it has been found that the above object can be achieved by the following configuration.
  • the repeating unit represented by formula (1) includes the repeating unit represented by formula (2) described later or the repeating unit represented by formula (3) described later.
  • composition For forming a conductive film according to any one of (1) to (4), wherein the content of the repeating unit represented by the formula (1) is 60 to 100 mol% with respect to all the repeating units. Composition. (6) The composition for forming a conductive film according to any one of (1) to (5), wherein the average particle diameter of the copper oxide particles is 100 nm or less.
  • a mass ratio of the vinyl polymer to the copper oxide particles is 3.0 or less.
  • the electrically conductive film which shows the outstanding electroconductivity can be formed, and the composition for electrically conductive film formation which is excellent in storage stability can be provided.
  • the manufacturing method of the electrically conductive film using this composition for electrically conductive film formation can also be provided.
  • one feature of the present invention is that a vinyl polymer having a reducing group containing a hydroxyl group is used.
  • a hydroxyl group functioning as a reducing group is bonded as a side chain to the main chain portion of the vinyl polymer via a methylene group and a linking group.
  • the reducing action of the hydroxyl group is suppressed, and the reducing action is produced only by an external action such as heat treatment or light irradiation treatment.
  • the vinyl polymer used in the present invention acts as a latent reducing agent. Therefore, simply mixing the vinyl polymer and the copper oxide particles hardly causes a reducing action on the copper oxide particles, and the occurrence of precipitation in the composition is suppressed. As a result, the storage stability of the composition is improved. improves. Furthermore, this vinyl polymer has a strong reducing action on the copper oxide particles after the heat treatment or the light irradiation treatment, and as a result, a conductive film containing metallic copper having excellent conductive properties can be produced.
  • the vinyl polymer contained in the composition for forming a conductive film contains a repeating unit represented by the following formula (1).
  • the side chain part containing the OH group in the formula (1) functions as a reducing group having an action of reducing the copper oxide particles. That is, the vinyl polymer corresponds to a latent reducing agent that acts as a reducing agent for the copper oxide particles when heat treatment or light irradiation treatment is performed. Therefore, even if the vinyl-based polymer and the copper oxide particles coexist, the reduction of the copper oxide particles does not substantially proceed unless the predetermined heat treatment or light irradiation treatment is performed. Excellent storage stability.
  • a vinyl polymer intends the polymer (polymer) obtained by superposing
  • R 1 represents a hydrogen atom or an alkyl group.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms from the viewpoint of easy synthesis and excellent handleability. Of these, a methyl group and an ethyl group are preferable.
  • L 1 represents a divalent linking group (organic group) which may have a substituent.
  • the divalent linking group include a divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms), and a divalent aromatic hydrocarbon group (preferably having 6 to 6 carbon atoms). 12), —O—, —S—, —SO 2 —, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof Groups (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, and the like).
  • divalent aliphatic hydrocarbon group examples include a methylene group, an ethylene group, a propylene group, or a butylene group.
  • divalent aromatic hydrocarbon group examples include a phenylene group and a naphthylene group.
  • the linking group may have a substituent, and the type thereof is not particularly limited.
  • halogen atom alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, Alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto Group, alkylthio group, arylthio group, sulfamoyl group, sulfo group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group
  • the repeating unit represented by Formula (2) or the repeating unit represented by Formula (3) is mentioned.
  • the polyol group (HOCH 2 CHOH—) in the repeating unit represented by the formula (2) or the hydroxyketone group (HOCH 2 CO—) in the repeating unit represented by the formula (3) is contained in the vinyl polymer.
  • the polymer has a high reducing power, and an excellent conductive film can be obtained at a low temperature.
  • R 1 of formula (2) and (3) has the same definition as R 1 in formula (1).
  • L 2 in Formula (2) and Formula (3) represents a divalent linking group. The definition of the linking group is as described above.
  • both the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) may be contained. When both are included, a conductive film having more excellent conductive properties can be obtained.
  • the repeating unit represented by the formula (5) or the formula (6) is preferable in terms of high production suitability and easy adjustment of physical properties. ).
  • Equation (5) and R 1 in the formula (6) has the same meaning as R 1 in the formula (1).
  • L 4 in Formula (5) and Formula (6) represents a divalent linking group.
  • the definition of the linking group is as described above.
  • L 4 is preferably a divalent aliphatic hydrocarbon group (preferably having 1 to 6 carbon atoms).
  • both the repeating unit represented by the formula (5) and the repeating unit represented by the formula (6) may be contained. When both are included, a conductive film having more excellent conductive properties can be obtained.
  • the content of the repeating unit represented by the formula (1) in the vinyl polymer is not particularly limited, but it is excellent in the storage stability of the composition for forming a conductive film, and a conductive film excellent in conductive characteristics can be obtained. It is preferably 60 to 100 mol%, more preferably 80 to 100 mol%, based on all repeating units.
  • the vinyl polymer may contain a repeating unit other than the repeating unit represented by the above formula (1), and preferably has a repeating unit represented by the following formula (4).
  • the repeating unit represented by the formula (4) contains a metal coordinating group, and can be coordinated to the copper oxide particles via the group.
  • the storage stability of the copper oxide particles in the composition is improved by the vinyl polymer being coordinated and approaching the copper oxide particles via the metal coordinating group. Furthermore, in the reduction step described later, the reduction effect on the copper oxide particles can be easily achieved, and a conductive film having better conductive properties can be obtained in some cases.
  • R 2 represents a hydrogen atom or an alkyl group.
  • the definition and preferred embodiments of the alkyl group are synonymous with the alkyl group represented by R 1 in formula (1).
  • L 3 represents a divalent linking group which may have a substituent. Definition of L 3 are the same as those defined L 1 in Formula (1).
  • X represents a metal coordinating group.
  • the metal coordinating group intends a group capable of coordinating with a metal. The type is not particularly limited.
  • a substituted or unsubstituted amino group, a substituted or unsubstituted amide group, or a substituted or unsubstituted amino group is superior in terms of storage stability of the composition for forming a conductive film, and a conductive film having excellent conductive properties.
  • a substituted carboxyl group is preferred, and any of the groups represented by the following formulas (X) to (Z) is more preferred.
  • * represents a bonding position with L 3 .
  • R 3 to R 7 each independently represents a hydrogen atom or a monovalent organic group.
  • the type of the monovalent organic group is not particularly limited, and examples thereof include aliphatic hydrocarbon groups (for example, alkyl groups, alkenyl groups, alkynyl groups, etc.), aromatic hydrocarbon groups (for example, aryl groups), heterocyclic groups ( For example, an azole group, a pyridyl group), etc. are mentioned, A hydrogen atom, a methyl group, or an ethyl group is preferable.
  • the content is not particularly limited, but a conductive film excellent in the storage stability of the composition for forming a conductive film and having excellent conductive properties is obtained. Therefore, the content is preferably 1 to 40 mol%, more preferably 5 to 20 mol%, based on all repeating units.
  • the weight-average molecular weight of the vinyl polymer is not particularly limited, but is preferably from 1,000 to 1,000,000, more preferably from 3,000 to 100,000, from the viewpoint that a conductive film excellent in the storage stability of the conductive film-forming composition and the conductive properties can be obtained. preferable.
  • a gel permeation chromatograph (GPC) manufactured by Tosoh Corporation is used and measured in terms of polystyrene using N-methylpyrrolidone as a solvent.
  • the production method of the vinyl polymer is not particularly limited, and a known method can be adopted.
  • a desired vinyl polymer can be obtained by performing radical polymerization, cationic polymerization, or anionic polymerization using a vinyl monomer that forms a desired repeating unit.
  • various initiators such as radical polymerization initiators
  • the composition for forming a conductive film contains copper oxide particles.
  • the “copper oxide” in the present invention is a compound that substantially does not contain copper that has not been oxidized. Specifically, in a crystal analysis by X-ray diffraction, a peak derived from copper oxide is detected, and is derived from a metal. Refers to a compound for which no peak is detected. Although not containing copper substantially, it means that content of copper is 1 mass% or less with respect to copper oxide particles.
  • copper oxide copper (I) oxide or copper (II) oxide is preferable, and copper (II) oxide is more preferable because it is available at low cost and has low resistance.
  • the average particle size of the copper oxide particles is not particularly limited, but is preferably 100 nm or less, and more preferably 50 nm or less.
  • the lower limit is not particularly limited, but is preferably 1 nm or more.
  • An average particle size of 1 nm or more is preferable because the activity on the particle surface does not become too high, does not dissolve in the composition, and is easy to handle. Moreover, if it is 100 nm or less, it becomes easy to form a pattern such as wiring by a printing method using the composition as an ink-jet ink composition, and when the composition is made into a conductor, reduction to metal copper is sufficient. Therefore, it is preferable because the conductivity of the obtained conductive film is good.
  • the average particle diameter in this invention points out an average primary particle diameter.
  • the average particle diameter is determined by measuring the particle diameter (diameter) of at least 50 or more copper oxide particles by observation with a transmission electron microscope (TEM) or scanning electron microscope (SEM) and arithmetically averaging them. In the observation diagram, when the shape of the copper oxide particles is not a perfect circle, the major axis is measured as the diameter.
  • the copper oxide particles for example, CuO nanoparticles made by Kanto Chemical Co., CuO nanoparticles made by Sigma-Aldrich, etc. can be preferably used.
  • the composition for forming a conductive film contains a solvent.
  • the solvent functions as a dispersion medium for the copper oxide particles.
  • the type of the solvent is not particularly limited.
  • water, organic solvents such as alcohols, ethers, and esters can be used.
  • an aliphatic alcohol having a monovalent to trivalent hydroxyl group from the viewpoint of better compatibility with the vinyl polymer and the copper oxide particles, water, an aliphatic alcohol having a monovalent to trivalent hydroxyl group, an alkyl ether derived from the aliphatic alcohol, derived from the aliphatic alcohol.
  • Alkyl esters or mixtures thereof are preferably used.
  • aliphatic alcohols having a monovalent to trivalent hydroxyl group include methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, and 1-nonanol.
  • aliphatic alcohols having 1 to 3 carbon atoms having 1 to 3 valent hydroxyl groups have a high boiling point and are difficult to remain after formation of the conductive film, and are compatible with the vinyl polymer and the copper oxide particles.
  • Methanol, ethylene glycol, glycerin, 2-methoxyethanol, diethylene glycol, and isopropyl alcohol are more preferable.
  • ethers examples include alkyl ethers derived from the above alcohols, such as diethyl ether, diisobutyl ether, dibutyl ether, methyl-t-butyl ether, methyl cyclohexyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl.
  • alkyl ethers having 2 to 8 carbon atoms derived from aliphatic alcohols having 1 to 3 carbon atoms and having 1 to 3 valent hydroxyl groups are preferred.
  • diethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran are more preferred.
  • esters examples include alkyl esters derived from the above alcohols, such as methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, and ⁇ -butyrolactone. Illustrated. Among these, alkyl esters having 2 to 8 carbon atoms derived from aliphatic alcohols having 1 to 3 carbon atoms and having 1 to 3 valent hydroxyl groups are preferable, and specifically, methyl formate, ethyl formate, and methyl acetate are more preferable. .
  • the main solvent is a solvent having the highest content in the solvent.
  • the composition for forming a conductive film may contain other components in addition to the vinyl polymer, the copper oxide particles, and the solvent.
  • the composition for forming a conductive film may contain a surfactant.
  • the surfactant plays a role of improving the dispersibility of the copper oxide particles.
  • the type of the surfactant is not particularly limited, and examples thereof include an anionic surfactant, a cationic surfactant, a nonionic surfactant, a fluorine surfactant, and an amphoteric surfactant. These surfactants can be used alone or in combination of two or more.
  • composition for forming a conductive film contains the above-described vinyl polymer, copper oxide particles, and a solvent.
  • the content of the vinyl polymer in the composition for forming a conductive film is not particularly limited, but is preferably 5 to 50% by mass with respect to the total mass of the composition from the viewpoint of obtaining a conductive film having superior conductive characteristics. 35 mass% is more preferable.
  • the content of the copper oxide particles in the composition for forming a conductive film is not particularly limited, but a conductive film having a sufficient film thickness that is superior in conductive properties can be obtained, and an increase in viscosity is suppressed, so that the composition can be used as an ink jet ink composition.
  • the content of the solvent in the composition for forming a conductive film is not particularly limited, but is preferably 5 to 90% by mass with respect to the total mass of the composition from the viewpoint of suppressing an increase in viscosity and being excellent in handleability. 80 mass% is more preferable.
  • the mass ratio between the vinyl polymer and the copper oxide particles in the composition for forming a conductive film is not particularly limited. 10 or less is preferable and 3.0 or less is more preferable. In addition, although a minimum in particular is not restrict
  • the content of the surfactant is not particularly limited, but is 0.0001 to 1% by mass with respect to the total mass of the composition from the viewpoint of improving coating properties. Is preferable, and 0.001 to 0.1% by mass is more preferable.
  • the viscosity of the conductive film forming composition is preferably adjusted to a viscosity suitable for printing applications such as inkjet and screen printing.
  • a viscosity suitable for printing applications such as inkjet and screen printing.
  • inkjet discharge 1 to 50 cP is preferable, and 1 to 40 cP is more preferable.
  • screen printing it is preferably from 1,000 to 100,000 cP, more preferably from 10,000 to 80,000 cP.
  • the method for preparing the conductive film forming composition is not particularly limited, and a known method can be adopted.
  • a known method can be adopted.
  • the components are dispersed by a known means such as an ultrasonic method (for example, treatment with an ultrasonic homogenizer), a mixer method, a three-roll method, or a ball mill method.
  • a composition can be obtained.
  • the manufacturing method of the electrically conductive film of this invention has a coating-film formation process and a reduction process at least. Below, each process is explained in full detail.
  • This step is a step of forming a coating film by applying the above-described composition for forming a conductive film on a substrate.
  • the precursor film before the reduction treatment is obtained in this step.
  • the conductive film forming composition used is as described above.
  • a well-known thing can be used as a base material used at this process.
  • the material used for the substrate include resin, paper, glass, silicon-based semiconductor, compound semiconductor, metal oxide, metal nitride, wood, or a composite thereof. More specifically, low density polyethylene resin, high density polyethylene resin, ABS resin, acrylic resin, styrene resin, vinyl chloride resin, polyester resin (polyethylene terephthalate), polyacetal resin, polysulfone resin, polyetherimide resin, polyether ketone Resin base materials such as resin and cellulose derivatives; uncoated printing paper, fine coated printing paper, coated printing paper (art paper, coated paper), special printing paper, copy paper (PPC paper), unbleached wrapping paper ( Paper substrates such as double kraft paper for heavy bags, double kraft paper), bleached wrapping paper (bleached kraft paper, pure white roll paper), coated balls, chip balls, corrugated cardboard; soda glass, borosilicate glass, silica glass, Glass substrates such as quartz glass; silicon-based semiconductor
  • the method for applying the conductive film forming composition onto the substrate is not particularly limited, and a known method can be adopted.
  • coating methods such as a screen printing method, a dip coating method, a spray coating method, a spin coating method, and an ink jet method can be used.
  • the shape of application is not particularly limited, and may be a surface covering the entire surface of the substrate or a pattern (for example, a wiring or a dot).
  • the coating amount of the composition for forming a conductive film on the substrate may be appropriately adjusted according to the desired film thickness of the conductive film.
  • the film thickness of the coating film is preferably 0.01 to 5000 ⁇ m, 0.1 to 1000 ⁇ m is more preferable.
  • the conductive film-forming composition may be applied to the substrate and then dried to remove the solvent.
  • the drying method a hot air dryer or the like can be used.
  • the temperature is preferably a temperature at which the reduction of the copper oxide particles does not occur, and the heat treatment is preferably performed at 40 ° C. to 200 ° C.
  • the heat treatment is more preferably performed at a temperature of from 150 ° C. to less than 150 ° C., more preferably from 70 ° C. to 120 ° C.
  • This step is a step of performing a heat treatment and / or a light irradiation treatment on the coating film formed in the coating film forming step to reduce the copper oxide particles to form a conductive film containing metallic copper.
  • the vinyl polymer produces a reducing action on the copper oxide particles, the copper oxide in the copper oxide particles is reduced, and further sintered to obtain metallic copper.
  • metallic copper particles in the coating film obtained by reducing the copper oxide particles are fused to each other to form grains, and the grains are further bonded and fused. To form a thin film.
  • the vinyl polymer may remain in the conductive film.
  • the heating temperature is preferably 100 to 300 ° C., more preferably 150 to 250 ° C.
  • the heating time is 5 to 120 minutes in that a conductive film having superior conductivity can be formed in a short time.
  • 10 to 60 minutes are more preferable.
  • the heating means is not particularly limited, and known heating means such as an oven and a hot plate can be used.
  • the conductive film can be formed by heat treatment at a relatively low temperature, and therefore, the process cost is low.
  • the light irradiation treatment enables reduction and sintering of the copper oxide by irradiating light on the portion to which the coating film has been applied at room temperature for a short time, and is due to long-time heating.
  • the base material is not deteriorated, and the adhesion of the conductive film to the base material becomes better.
  • the copper oxide particles absorb light and convert it into heat, and the heat causes the hydroxyl group in the vinyl polymer to undergo a reducing action, and the formed copper metal Progression of fusion proceeds.
  • the light source used in the light irradiation treatment is not particularly limited, and examples thereof include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp.
  • Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays.
  • g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used.
  • Specific examples of preferred embodiments include scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.
  • the light irradiation is preferably light irradiation with a flash lamp, and more preferably pulsed light irradiation with a flash lamp. Irradiation with high-energy pulsed light can concentrate and heat the surface of the portion to which the coating film has been applied in a very short time, so that the influence of heat on the substrate can be extremely reduced.
  • the irradiation energy of the pulse light is preferably 1 ⁇ 100J / cm 2, more preferably 1 ⁇ 30J / cm 2, preferably from 1 ⁇ sec ⁇ 100 m sec as a pulse width, and more preferably 10 ⁇ sec ⁇ 10 m sec.
  • the irradiation time of the pulsed light is preferably 1 to 100 milliseconds, more preferably 1 to 50 milliseconds, and further preferably 1 to 20 milliseconds.
  • the above heat treatment and light irradiation treatment may be performed alone or both may be performed simultaneously. Moreover, after performing one process, you may perform the other process further.
  • the atmosphere in which the heat treatment and the light irradiation treatment are performed is not particularly limited, and examples include an air atmosphere, an inert atmosphere, or a reducing atmosphere.
  • the inert atmosphere is, for example, an atmosphere filled with an inert gas such as argon, helium, neon, or nitrogen
  • the reducing atmosphere is a reducing gas such as hydrogen or carbon monoxide. It refers to the atmosphere.
  • a conductive film (metal copper film) containing metal copper is obtained.
  • the film thickness of the conductive film is not particularly limited, and an optimum film thickness is appropriately adjusted according to the intended use. Of these, 0.01 to 1000 ⁇ m is preferable and 0.1 to 100 ⁇ m is more preferable from the viewpoint of printed wiring board use.
  • the film thickness is a value (average value) obtained by measuring three or more thicknesses at arbitrary points on the conductive film and arithmetically averaging the values.
  • the volume resistance value of the conductive film is preferably 1 ⁇ 10 ⁇ 2 ⁇ cm or less, more preferably 1 ⁇ 10 ⁇ 3 ⁇ cm or less, and further preferably 5 ⁇ 10 ⁇ 4 ⁇ cm or less from the viewpoint of conductive characteristics.
  • the volume resistance value can be calculated by multiplying the obtained surface resistance value by the film thickness after measuring the surface resistance value of the conductive film by the four-probe method.
  • the conductive film may be provided on the entire surface of the base material or in a pattern.
  • the patterned conductive film is useful as a conductor wiring (wiring) such as a printed wiring board.
  • wiring conductor wiring
  • the above-mentioned composition for forming a conductive film was applied to a substrate in a pattern, and the above heat treatment and / or light irradiation treatment was performed, or the entire surface of the substrate was provided.
  • a method of etching the conductive film in a pattern may be used.
  • the etching method is not particularly limited, and a known subtractive method, semi-additive method, or the like can be employed.
  • an insulating layer (insulating resin layer, interlayer insulating film, solder resist) is further laminated on the surface of the patterned conductive film, and further wiring (metal) is formed on the surface. Pattern) may be formed.
  • the material of the insulating film is not particularly limited.
  • epoxy resin epoxy resin, aramid resin, crystalline polyolefin resin, amorphous polyolefin resin, fluorine-containing resin (polytetrafluoroethylene, perfluorinated polyimide, perfluorinated amorphous resin, etc.) , Polyimide resin, polyether sulfone resin, polyphenylene sulfide resin, polyether ether ketone resin, liquid crystal resin and the like.
  • an epoxy resin a polyimide resin, or a liquid crystal resin, and more preferably an epoxy resin.
  • Specific examples include ABF GX-13 manufactured by Ajinomoto Fine Techno Co., Ltd.
  • solder resist which is a kind of insulating layer material used for wiring protection, is described in detail in, for example, Japanese Patent Application Laid-Open No. 10-204150 and Japanese Patent Application Laid-Open No. 2003-222993. These materials can also be applied to the present invention if desired.
  • solder resist commercially available products may be used. Specific examples include PFR800 manufactured by Taiyo Ink Manufacturing Co., Ltd., PSR4000 (trade name), SR7200G manufactured by Hitachi Chemical Co., Ltd., and the like.
  • the base material (base material with a conductive film) having the conductive film obtained above can be used for various applications.
  • a printed wiring board, TFT, FPC, RFID, etc. are mentioned.
  • the obtained polymer was dissolved in IPA to obtain a polymer solution 2 having a solid content of 50 wt%.
  • the weight average molecular weight Mw of the obtained polymer was 31000.
  • the weight average molecular weight was measured in terms of polystyrene using a gel permeation chromatograph (GPC) manufactured by Tosoh Corporation using N-methylpyrrolidone as a solvent.
  • the obtained polymer was dissolved in IPA to obtain a polymer solution 4 having a solid content of 50 wt%.
  • the weight average molecular weight Mw of the obtained polymer was 30000.
  • the weight average molecular weight was measured in terms of polystyrene using a gel permeation chromatograph (GPC) manufactured by Tosoh Corporation using N-methylpyrrolidone as a solvent.
  • the obtained polymer was dissolved in IPA to obtain a polymer solution 5 having a solid content of 50 wt%.
  • the weight average molecular weight Mw of the obtained polymer was 28000.
  • the weight average molecular weight was measured in terms of polystyrene using a gel permeation chromatograph (GPC) manufactured by Tosoh Corporation using N-methylpyrrolidone as a solvent.
  • the obtained polymer was dissolved in IPA to obtain a polymer solution 6 having a solid content of 50 wt%.
  • the weight average molecular weight Mw of the obtained polymer was 31000.
  • the weight average molecular weight was measured in terms of polystyrene using a gel permeation chromatograph (GPC) manufactured by Tosoh Corporation using N-methylpyrrolidone as a solvent.
  • the obtained polymer was dissolved in IPA to obtain a polymer solution 7 having a solid content of 50 wt%.
  • the weight average molecular weight Mw of the obtained polymer was 110,000.
  • the weight average molecular weight was measured in terms of polystyrene using a gel permeation chromatograph (GPC) manufactured by Tosoh Corporation using N-methylpyrrolidone as a solvent.
  • GPC gel permeation chromatograph
  • the obtained polymer was dissolved in IPA to obtain a polymer solution 8 having a solid content of 50 wt%.
  • the weight average molecular weight Mw of the obtained polymer was 1500.
  • the weight average molecular weight was measured in terms of polystyrene using a gel permeation chromatograph (GPC) manufactured by Tosoh Corporation using N-methylpyrrolidone as a solvent.
  • the obtained polymer was dissolved in IPA to obtain a polymer solution 9 having a solid content of 50 wt%.
  • the weight average molecular weight Mw of the obtained polymer was 34000.
  • the weight average molecular weight was measured in terms of polystyrene using a gel permeation chromatograph (GPC) manufactured by Tosoh Corporation using N-methylpyrrolidone as a solvent.
  • Dispersion 2 was obtained according to the same procedure as in Dispersion Preparation Example 1, except that polymer solution 1 (420 parts by mass) was replaced with polymer solution 2 (380 parts by mass).
  • Dispersion 3 was obtained according to the same procedure as in Dispersion Preparation Example 1, except that polymer aqueous solution 1 (420 parts by mass) was replaced with polymer aqueous solution 3 (420 parts by mass).
  • Dispersion 4 was obtained according to the same procedure as Dispersion Preparation Example 1, except that polymer solution 1 (420 parts by mass) was replaced with polymer solution 4 (420 parts by mass).
  • Dispersion 5 was obtained according to the same procedure as Dispersion Preparation Example 1, except that polymer solution 1 (420 parts by mass) was replaced with polymer solution 5 (320 parts by mass).
  • Dispersion 6 was obtained according to the same procedure as in Preparation 1 for dispersion except that polymer solution 1 (420 parts by mass) was replaced with polymer solution 6 (290 parts by mass).
  • Dispersion 7 was obtained in the same manner as in Dispersion Preparation Example 1, except that aqueous polymer solution 1 (420 parts by mass) was replaced with an aqueous solution (420 parts by mass) containing 50 wt% polyethylene glycol (average molecular weight 300).
  • Dispersion Preparation Example 8 Dispersion was carried out according to the same procedure as in Preparation Example 1 except that the aqueous polymer solution 1 (420 parts by mass) was replaced with an aqueous solution (420 parts by mass) containing 50 wt% poly (methyl vinyl ketone dimethylhydrazone) (average molecular weight 6000). Liquid 8 was obtained.
  • the poly (methyl vinyl ketone dimethylhydrazone) corresponds to the polymer disclosed in Patent Document 1.
  • Dispersion 9 was obtained according to the same procedure as Dispersion Preparation Example 1 except that polymer aqueous solution 1 (420 parts by mass) was replaced with polymer solution 7 (290 parts by mass).
  • Dispersion 10 was obtained according to the same procedure as Dispersion Preparation Example 1, except that polymer aqueous solution 1 (420 parts by mass) was replaced with polymer solution 8 (290 parts by mass).
  • Dispersion 11 was obtained in the same manner as Dispersion Preparation Example 1, except that polymer aqueous solution 1 (420 parts by mass) was replaced with polymer solution 9 (340 parts by mass).
  • Dispersion 12 was obtained according to the same procedure as Dispersion Preparation Example 1, except that the amount of polymer aqueous solution 1 used was changed from 420 parts by weight to 800 parts by weight.
  • Dispersion 13 was obtained in the same manner as in Dispersion Preparation Example 1, except that aqueous polymer solution 1 (420 parts by mass) was replaced with an aqueous solution (420 parts by mass) containing 50 wt% polyvinyl alcohol (average molecular weight 22000). When the obtained dispersion liquid 13 was allowed to stand at room temperature for 24 hours, the dispersion state was maintained.
  • Table 1 below collectively shows the results of the above-mentioned dispersion preparation examples 1 to 13.
  • the “reducing group” column and the “coordinating group” column in Table 1 mean the type of each functional group contained in the polymer in the polymer solution.
  • dispersions 1 to 6 and 9 to 12 corresponding to the composition for forming a conductive film of the present invention exhibited excellent storage stability.
  • Dispersion 7 when a polymer having a hydroxyl group at the terminal described in Patent Document 2 was used, the storage stability of the conductive film forming composition was poor.
  • Example 1 The dispersion 1 was printed on a 10 ⁇ 10 mm surface of a glass substrate using an inkjet printing apparatus (manufactured by FUJIFILM Dimatix, apparatus name: DMP-2831).
  • a copper thin film was obtained by drying in a glove box (oxygen concentration ⁇ 100 ppm) on a hot plate at 100 ° C. for 10 minutes and then sintering at 200 ° C. for 1 hour.
  • the film thickness was measured with a stylus type film thickness meter, it was 0.5 ⁇ m.
  • the volume resistivity was measured using a four-probe method resistivity meter, it was 6 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • Example 2 A copper thin film was obtained by performing the same operation as in Example 1 except that the glass substrate was replaced with a PET substrate.
  • the obtained copper thin film had a thickness of 0.5 ⁇ m and a volume resistivity of 4 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • Example 3 The copper thin film was obtained by performing the same operation as Example 1 except having changed the sintering method from 200 degreeC 1-hour heating sintering to the light sintering shown below.
  • the obtained copper thin film had a thickness of 0.4 ⁇ m and a volume resistivity of 5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • Light sintering Light irradiation was performed using an Xe flash lamp (set voltage 3 kV) at an irradiation energy of 2070 J and a pulse width of 2 msec.
  • Example 4 The copper thin film was obtained by performing the same operation as Example 1 except having changed the sintering temperature from 200 degreeC to 250 degreeC.
  • the obtained copper thin film had a thickness of 0.5 ⁇ m and a volume resistivity of 2 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • Example 5 The copper thin film was obtained by performing the same operation as Example 1 except having changed the sintering temperature from 200 degreeC to 300 degreeC.
  • the obtained copper thin film had a thickness of 0.5 ⁇ m and a volume resistivity of 5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • Example 6 A copper thin film was obtained by performing the same operation as in Example 1 except that Dispersion 1 was replaced with Dispersion 2.
  • the obtained copper thin film had a thickness of 0.6 ⁇ m and a volume resistivity of 3 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • Example 7 A copper thin film was obtained by performing the same operation as in Example 6 except that the sintering method was changed from heat sintering at 200 ° C. for 1 hour to light sintering.
  • the obtained copper thin film had a thickness of 0.5 ⁇ m and a volume resistivity of 5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the conditions for photosintering were the same as those performed in Example 3.
  • Example 8 A copper thin film was obtained by performing the same operation as in Example 7 except that the glass substrate was replaced with a PET substrate.
  • the obtained copper thin film had a thickness of 0.5 ⁇ m and a volume resistivity of 3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • Example 9 A copper thin film was obtained by performing the same operation as in Example 1 except that the dispersion 1 was replaced with the dispersion 4.
  • the obtained copper thin film had a thickness of 0.5 ⁇ m and a volume resistivity of 8 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • Example 10 A copper thin film was obtained by performing the same operation as in Example 9 except that the sintering method was changed from heat sintering at 200 ° C. for 1 hour to light sintering.
  • the obtained copper thin film had a thickness of 0.4 ⁇ m and a volume resistivity of 7 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the conditions for photosintering were the same as those performed in Example 3.
  • Example 11 A copper thin film was obtained by performing the same operation as in Example 1 except that the dispersion 1 was replaced with the dispersion 5.
  • the obtained copper thin film had a thickness of 0.5 ⁇ m and a volume resistivity of 3 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • Example 12 A copper thin film was obtained by performing the same operation as in Example 11 except that the sintering method was changed from heat sintering at 200 ° C. for 1 hour to light sintering.
  • the obtained copper thin film had a thickness of 0.4 ⁇ m and a volume resistivity of 3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • the conditions for photosintering were the same as those performed in Example 3.
  • Example 13 A copper thin film was obtained by performing the same operation as in Example 1 except that the dispersion 1 was replaced with the dispersion 6.
  • the obtained copper thin film had a thickness of 0.5 ⁇ m and a volume resistivity of 1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • Example 14 The copper thin film was obtained by performing the same operation as Example 13 except having changed the sintering temperature from 200 degreeC to 150 degreeC.
  • the obtained copper thin film had a thickness of 0.5 ⁇ m and a volume resistivity of 1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • Example 15 A copper thin film was obtained by performing the same operation as in Example 14 except that the dispersion 6 was replaced with the dispersion 9.
  • the obtained copper thin film had a thickness of 0.5 ⁇ m and a volume resistivity of 4 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • Example 16 A copper thin film was obtained by performing the same operation as in Example 15 except that the dispersion 9 was replaced with the dispersion 10.
  • the obtained copper thin film had a thickness of 0.5 ⁇ m and a volume resistivity of 6 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • Example 17 A copper thin film was obtained by performing the same operation as in Example 1 except that the dispersion 1 was replaced with the dispersion 11.
  • the obtained copper thin film had a thickness of 0.5 ⁇ m and a volume resistivity of 9 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
  • Example 18 A copper thin film was obtained by performing the same operation as in Example 1 except that the dispersion 1 was replaced with the dispersion 12.
  • the obtained copper thin film had a thickness of 0.6 ⁇ m and a volume resistivity of 1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm.
  • Example 1 A thin film was prepared by performing the same operation as in Example 1 except that the dispersion 1 was replaced with the dispersion 8.
  • the film thickness of the obtained thin film was 0.5 ⁇ m.
  • the volume resistivity of the thin film obtained using the four-probe method resistivity meter was measured, it showed no conductivity.
  • Example 2 A thin film was prepared by performing the same operation as in Example 1 except that the dispersion 1 was replaced with the dispersion 13.
  • the film thickness of the obtained thin film was 0.5 ⁇ m.
  • the obtained copper thin film had a thickness of 0.5 ⁇ m and a volume resistivity of 3 ⁇ 10 2 ⁇ ⁇ cm.
  • Example 14 when the molecular weight of the vinyl polymer was within a predetermined range, a copper thin film having a smaller volume resistivity, that is, excellent electrical conductivity, was obtained.
  • Example 1 and Example 18 when the mass ratio of the vinyl polymer and the copper oxide particles (the mass of the vinyl polymer / the mass of the copper oxide particles) is 3 or less, the volume resistivity is further increased. Was obtained, that is, a copper thin film excellent in conductive properties was obtained.
  • Example 13 and Example 17 when the vinyl polymer has two kinds of reducing groups, a copper thin film having a smaller volume resistivity, that is, excellent electrical conductivity can be obtained. It was.
  • Comparative Example 1 using the dispersion 8 containing poly (methyl vinyl ketone dimethyl hydrazone) described in Patent Document 1 a film showing conductivity was not obtained.
  • Comparative Example 2 using the dispersion liquid 13 containing polyvinyl alcohol only a film having inferior conductive properties was obtained.

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Abstract

La présente invention concerne une composition à utiliser dans la formation d'un film conducteur et pouvant former un film conducteur, doté d'une excellente conductivité, et montrant une excellente stabilité à l'entreposage. La présente composition comprend : un polymère de vinyle comprenant des unités récurrentes représentées par la formule (1) ; des particules d'oxyde de cuivre ; et un solvant.
PCT/JP2013/068719 2012-07-24 2013-07-09 Composition de formation de film conducteur et procédé de production de film conducteur WO2014017288A1 (fr)

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JP5962520B2 (ja) 2013-01-15 2016-08-03 信越化学工業株式会社 単量体、高分子化合物、レジスト材料及びパターン形成方法

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Publication number Priority date Publication date Assignee Title
JP2005002418A (ja) * 2003-06-12 2005-01-06 Asahi Kasei Corp 金属酸化物微粒子分散体
JP2005220402A (ja) * 2004-02-05 2005-08-18 Asahi Kasei Corp 金属酸化物分散体

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005002418A (ja) * 2003-06-12 2005-01-06 Asahi Kasei Corp 金属酸化物微粒子分散体
JP2005220402A (ja) * 2004-02-05 2005-08-18 Asahi Kasei Corp 金属酸化物分散体

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