Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/52—Electrically conductive inks
• • 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

Definitions

• the present invention relates to a conductive ink used for forming a wiring or an electrode pattern of a semiconductor integrated circuit or the like and capable of forming a wiring or an electrode pattern on an organic thin film transistor substrate.
• a method using a printing method such as a relief printing method, an intaglio printing method, a screen printing method or an inkjet printing method has been proposed as a simpler and cheaper method for forming a conductive film pattern.
• a printing technique capable of forming a higher-definition pattern a method using a reverse printing method, a microcontact printing method, or the like has been proposed, and a conductive ink suitable for these printing methods, an insulating property, and the like.
• Various inks such as ink and resistance ink have been actively researched and developed.
• Patent Document 1 Japanese Patent Application Laid-Open No. 2011-044509
• the conductive particles have an average particle diameter of 1 nm.
• It contains nano silver particles that are less than 100 nm and flaky copper particles having an average flake diameter of 0.1 ⁇ m or more and 3 ⁇ m or less, and the conductive particles contain the flaky copper particles in a mass ratio from the nano silver particles
• Patent Document 2 Japanese Patent Application Laid-Open No. 2012-184407
• an ink that realizes a reduction in the coffee ring effect, an improvement in adhesion to a substrate, and an increase in the decap time or waiting time of the print head.
• Compositions have been proposed. More specifically, “including metal nanoparticles containing silver, an optional resin, and two or more types of ink media, and at least one of the ink media has a vapor pressure of less than 4 mmHg at 25 ° C.
• An ink composition that is an aliphatic hydrocarbon.
• an object of the present invention has been made in view of the above-described problems of the prior art, and is a conductive material capable of firing a conductive film pattern having sufficient conductivity and good adhesion to a substrate at a low temperature. It is another object of the present invention to provide an ink, and further to provide a conductive ink that is easy to handle and excellent in dispersibility.
• the present inventor has obtained a conductive ink capable of firing a conductive film having sufficient conductivity and good adhesion to a substrate at low temperature, In order to obtain a conductive ink that is easy to handle and excellent in dispersibility, it has been found that the use of a terpene resin satisfying specific conditions is extremely effective in achieving the above object, and the present invention provides Reached.
• the present invention Silver nanoparticles, A dispersion medium; There is provided a conductive ink comprising a terpene resin having a softening point of 90 ° C. or higher, which is attached to the surface of the silver nanoparticles or contained in the dispersion medium.
• the terpene resin is an ⁇ -pinene polymer, ⁇ -pinene polymer, ⁇ , ⁇ pinene copolymer, limonene polymer, rosin, rosin ester, modified rosin, terpene phenol. It is preferably at least one selected from the group consisting of a polymer, a hydrogenated terpene polymer, an aromatic modified terpene polymer, and a rosin modified phenolic resin.
• the dispersion medium contains the terpene resin and a polymer dispersant.
• the terpene resin contained in the conductive ink is 10% by weight or less based on the silver solid content.
• the conductive pattern having sufficient conductivity and good adhesion to the substrate can be fired at a low temperature, and it is easy to handle and has excellent dispersibility. Conductive ink can be realized.
• the conductive ink of the present embodiment is a softening agent that adheres to or is contained in the surface of silver nanoparticles (silver fine particles), a dispersion medium, and the silver nanoparticles. And a terpene resin having a point of 90 ° C. or higher.
• a terpene resin having a point of 90 ° C. or higher.
• it includes a solid content mainly composed of silver nanoparticle dispersion (silver colloid liquid) particles composed of silver nanoparticles and an organic component, and a dispersion medium for dispersing these solid contents.
• the “dispersion medium” in the conductive ink may dissolve a part of the solid content.
• the dispersibility of the silver colloid particles in the silver colloid liquid can be improved. Therefore, the content of the silver component in the silver colloid liquid can be reduced. Even if it is increased, the colloidal silver particles are less likely to aggregate, and good dispersion stability can be maintained.
• the term “dispersibility” as used herein indicates whether or not the dispersion state of silver nanoparticles in the silver colloid liquid is excellent immediately after the silver colloid liquid is prepared (whether it is uniform). "Dispersion stability” indicates whether or not the dispersion state of silver nanoparticles in the silver colloid liquid is maintained after a predetermined time has elapsed after the silver colloid liquid has been prepared. It can also be said to be “low sedimentation aggregation” or “dilution”.
• the “organic component” in the silver colloid particles is an organic substance that substantially constitutes the silver colloid particles together with the metal component (provided that the “surface of the silver nanoparticles” Or a terpene-based resin having a softening point of 90 ° C. or higher contained in the dispersion medium ”.
• the organic component includes trace organic substances contained in the silver as impurities from the beginning, organic substances adhering to the silver component of trace organic substances mixed in the manufacturing process described later, residual reducing agent that could not be removed in the cleaning process, residual dispersion It does not include organic substances that adhere to trace amounts of silver components such as agents.
• the “trace amount” is specifically intended to be less than 1% by mass in the silver colloid particles.
• the silver colloid particles in this embodiment contain an organic component, the dispersion stability in the silver colloid liquid is high. For this reason, even if the content of the silver component in the silver colloid liquid is increased, the silver colloid particles are less likely to aggregate, and as a result, good dispersibility is maintained.
• the “solid content” of the silver colloid liquid in the present embodiment means that after removing the dispersion medium from the silver colloid liquid using silica gel or the like, for example, it is dried at a room temperature of 30 ° C. or lower (for example, 25 ° C.) for 24 hours. In general, it contains silver nanoparticles, residual organic components and residual reducing agent, and the above-mentioned terpene resin.
• Various methods can be adopted as a method of removing the dispersion medium from the silver colloid liquid using silica gel. For example, a silver colloid liquid is applied on a glass substrate and the silica gel is put into a sealed container. What is necessary is just to remove a dispersion medium by leaving a glass substrate with a coating film for 24 hours or more.
• the preferred solid content concentration is 1 to 60% by mass.
• the silver content in the conductive ink can be ensured, and the conductive efficiency does not decrease.
• concentration of solid content is 60 mass% or less, the viscosity of a silver colloid liquid does not increase, handling is easy, it is industrially advantageous, and a flat thin film can be formed.
• a more preferable solid content is 5 to 40% by mass.
• the conductive ink of this embodiment includes a terpene resin having a softening point of 90 ° C. or higher, which is attached to the surface of the silver nanoparticles or contained in the dispersion medium.
• the present inventors have realized a conductive ink that is excellent in low-temperature sinterability, adhesion, and dispersibility by using such a terpene resin.
• terpene resins have a molecular weight of at least about 800 or more.
• the steric repulsion prevents the particles from aggregating. It was confirmed that the effect was exhibited and that this steric repulsion effect protected silver nanoparticles and contributed to the adhesion to the substrate.
• the terpene resin preferably has a softening point of 90 ° C. or higher.
• the reason why the “terpene resin having a softening point of 90 ° C. or higher” is preferable is not necessarily clear, but the present inventors consider as follows. It is well known that the glass transition point of a terpene resin is about 60 ° C. lower than the softening point of the terpene resin. Then, for example, the glass transition point of a terpene resin having a softening point of 80 ° C. or lower is about 20 ° C.
• the softening point of the terpene resin is set to a certain level so that its glass transition point is at room temperature (25 ° C.) or higher, and the molecular mobility. It is thought that the firm nature should be kept by restraining.
• the upper limit of the softening point of the terpene resin may be about the softening point of the terpene resin having the maximum softening point among commercially available terpene resins, and more reliably, for example, 160 ⁇ 5 ° C.
• the effects of the invention can be obtained.
• the terpene resin is an ⁇ -pinene polymer, ⁇ -pinene polymer, ⁇ , ⁇ -pinene copolymer, limonene polymer, rosin, rosin ester, modified rosin, terpene phenol polymer, hydrogenated terpene polymer. It is preferably at least one selected from the group consisting of an aromatic modified terpene polymer and a rosin modified phenolic resin. The reason is that it is highly compatible with various elastomers and organic solvents and exhibits excellent adhesive properties. When polyterpenes such as carotene and natural rubber are used, the conductivity is remarkably impaired and the adhesive properties are difficult to obtain.
• the terpene resin contained in the conductive ink needs to be added within a range that does not impair the conductivity. It is preferable that: The lower limit may be about 1.0% by mass. More preferably, it may be 1.0 to 3.0% by mass.
• the conductive ink of the present embodiment preferably has a surface tension of 22 mN / m or less.
• the surface tension of 22 mN / m or less can be realized by adjusting the component ratio of the conductive ink.
• the lower limit of the surface tension may be about 13 mN / m.
• the surface tension referred to in the present invention is obtained by measurement based on the principle of the plate method (Wilhelmy method). For example, the surface tension is measured by a fully automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. can do.
• the average particle diameter of the silver nanoparticles contained in the silver nanoparticle dispersion in the present embodiment is not particularly limited as long as the effects of the present invention are not impaired, but the average particle diameter that causes a melting point drop is generated.
• it may be 1 to 400 nm. Further, it is preferably 1 to 70 nm. If the average particle diameter of the silver nanoparticles is 1 nm or more, the silver nanoparticles have a good low-temperature sinterability, and the production of the silver nanoparticles is practical without increasing the cost.
• the dispersibility of a silver nanoparticle does not change easily with time, and it is preferable.
• the average particle diameter (median diameter) of the silver colloid particles (including silver nanoparticles) is substantially the same as this range ( Can be approximated).
• the particle size of the silver nanoparticles in the silver nanoparticle dispersion varies depending on the solid content concentration, and is not necessarily constant and may not be constant.
• the silver nanoparticle dispersion may contain a silver nanoparticle component having an average particle size of more than 400 nm.
• a silver nanoparticle component having an average particle diameter of more than 400 nm may be included as long as the effect is not significantly impaired.
• the average particle diameter of the silver nanoparticles in the silver nanoparticle dispersion of the present embodiment is based on a dynamic light scattering method (Doppler scattered light analysis).
• a dynamic light scattering type manufactured by Horiba, Ltd. It can be represented by a volume-based median diameter (D50) measured by a particle size distribution measuring device LB-550.
• D50 volume-based median diameter
• a metal colloid solution are dropped into 10 mL of ethanol, and are shaken and dispersed by hand to prepare a measurement sample.
• 3 mL of the measurement sample is put into a cell of a dynamic light scattering particle size distribution measuring device LB-550 manufactured by Horiba, Ltd., and measurement is performed under the following conditions.
• Measurement condition data read count 100 times Cell holder temperature: 25 ° C
• Display condition distribution form Standard number of repetitions: 50 times
• Particle size standard Volume-based refractive index of refractive index: 0.200-3.900i (in the case of silver)
• Refractive index of dispersion medium 1.36 (when ethanol is the main component)
• System condition setting strength criteria Dynamic Scattering intensity range upper limit: 10000.00 Scattering intensity range lower limit: 1.00
• an amine preferably a short-chain amine having 5 or less carbon atoms
• an amine is attached to at least a part of the surface of the silver nanoparticle.
• trace organic substances contained as impurities from the beginning, trace organic substances mixed in the manufacturing process described later, residual reducing agent that could not be removed in the cleaning process, residual dispersant, etc. A trace amount of organic matter may be attached.
• amine various amines can be used, which may be linear or branched, and may have a side chain.
• the short chain amine having 5 or less carbon atoms is not particularly limited, and examples of the short chain amine include ethylamine, propylamine, butylamine, N- (3-methoxypropyl) propane-1,3-diamine, Examples include 1,2-ethanediamine, ⁇ ⁇ ⁇ 2-methoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 1,4-butanediamine, 1,5-pentanediamine, pentanolamine, aminoisobutanol and the like.
• the short chain amine may be a compound containing a functional group other than an amine such as a hydroxyl group, a carboxyl group, an alkoxy group, a carbonyl group, an ester group, or a mercapto group.
• the said amine may be used independently, respectively and may use 2 or more types together.
• the boiling point at normal pressure is preferably 300 ° C. or lower, more preferably 250 ° C. or lower.
• the silver particle dispersion of the present embodiment may contain a carboxylic acid in addition to the short-chain amine having 5 or less carbon atoms as long as the effects of the present invention are not impaired.
• the carboxyl group in one molecule of the carboxylic acid has a relatively high polarity and tends to cause an interaction due to a hydrogen bond, but a portion other than these functional groups has a relatively low polarity. Furthermore, the carboxyl group tends to exhibit acidic properties.
• the carboxylic acid is localized (attached) to at least a part of the surface of the silver nanoparticle in the silver particle dispersion of the present embodiment (that is, when at least a part of the surface of the silver nanoparticle is coated).
• the solvent and the silver nanoparticles can be made sufficiently compatible, and aggregation of the silver nanoparticles can be prevented (dispersibility is improved).
• carboxylic acid compounds having at least one carboxyl group can be widely used, and examples thereof include formic acid, oxalic acid, acetic acid, hexanoic acid, acrylic acid, octylic acid, and oleic acid.
• a part of carboxyl groups of the carboxylic acid may form a salt with a metal ion.
• 2 or more types of metal ions may be contained.
• the carboxylic acid may be a compound containing a functional group other than a carboxyl group, such as an amino group, a hydroxyl group, an alkoxy group, a carbonyl group, an ester group, or a mercapto group.
• the number of carboxyl groups is preferably equal to or greater than the number of functional groups other than carboxyl groups.
• the said carboxylic acid may be used independently, respectively and may use 2 or more types together.
• the boiling point at normal pressure is preferably 300 ° C. or lower, more preferably 250 ° C. or lower.
• amines and carboxylic acids form amides. Since the amide group also adsorbs moderately on the surface of the silver nanoparticle, the amide group may be attached to the surface of the silver nanoparticle.
• (1-3) Dispersion medium The silver nanoparticle dispersion of the present embodiment is obtained by dispersing silver nanoparticles in various dispersion media.
• Various dispersion media can be used as long as the effects of the present invention are not impaired, and examples thereof include hydrocarbons and alcohols.
• the terpene resin may be dissolved in this dispersion medium.
• hydrocarbon examples include aliphatic hydrocarbons, cyclic hydrocarbons, and alicyclic hydrocarbons, which may be used alone or in combination of two or more.
• aliphatic hydrocarbon examples include saturated or unsaturated aliphatic hydrocarbons such as tetradecane, octadecane, heptamethylnonane, tetramethylpentadecane, hexane, heptane, octane, nonane, decane, tridecane, methylpentane, normal paraffin, and isoparaffin. Is mentioned.
• cyclic hydrocarbon examples include toluene and xylene.
• examples of the alicyclic hydrocarbon include limonene, dipentene, terpinene, terpinene (also referred to as terpinene), nesol, sinene, orange flavor, terpinolene, terpinolene (also referred to as terpinolene), ferrandylene, mentadiene, teleben, Examples thereof include dihydrocymene, moslen, isoterpinene, isoterpinene (also referred to as isoterpinene), clitomen, kautssin, cajeptene, oilimene, pinene, turpentine, menthane, pinane, terpene, and cyclohexane.
• Alcohol is a compound containing one or more OH groups in the molecular structure, and examples thereof include aliphatic alcohols, cyclic alcohols and alicyclic alcohols, and each may be used alone or in combination of two or more. Also good. Moreover, a part of OH group may be induced
• Examples of the aliphatic alcohol include heptanol, octanol (1-octanol, 2-octanol, 3-octanol, etc.), decanol (1-decanol, etc.), lauryl alcohol, tetradecyl alcohol, cetyl alcohol, 2-ethyl-1- Examples thereof include saturated or unsaturated C6-30 aliphatic alcohols such as hexanol, octadecyl alcohol, hexadecenol and oleyl alcohol.
• Examples of the cyclic alcohol include cresol and eugenol.
• alicyclic alcohol for example, cycloalkanol such as cyclohexanol, terpineol (including ⁇ , ⁇ , ⁇ isomers, or any mixture thereof), terpene alcohol such as dihydroterpineol (monoterpene alcohol etc. ), Dihydroterpineol, myrtenol, sobrerol, menthol, carveol, perillyl alcohol, pinocarveol, sobrerol, berbenol and the like.
• cycloalkanol such as cyclohexanol, terpineol (including ⁇ , ⁇ , ⁇ isomers, or any mixture thereof)
• terpene alcohol such as dihydroterpineol (monoterpene alcohol etc. ), Dihydroterpineol, myrtenol, sobrerol, menthol, carveol, perillyl alcohol, pinocarveol, sobrerol, berbenol and the
• the silver particle dispersion of the present embodiment further includes a dispersant added after the synthesis of silver nanoparticles in order to disperse the silver nanoparticles.
• a dispersant added after the synthesis of silver nanoparticles in order to disperse the silver nanoparticles.
• the dispersion stability of silver nanoparticles in a solvent can be improved.
• the acid value of the dispersant is more preferably from 5 to 200, and it is further preferable that the dispersant has a functional group derived from phosphoric acid.
• the acid value of the dispersing agent is 5 or more, it will be adsorbed by the acid-base interaction to silver which coordinates with the amine and the particle surface is basic, and if it is 200 or less, it will be excessively adsorbed. It is because it does not have a site and adsorbs in a suitable form.
• the dispersing agent since the dispersing agent has a functional group derived from phosphoric acid, phosphorus P interacts with and attracts silver through oxygen O, so it is most effective for adsorption with silver and silver compounds, and the minimum necessary adsorption. This is because suitable dispersibility can be obtained in an amount.
• Examples of the polymer dispersant having an acid value of 5 to 200 include SOLPERSE-16000, 21000, 41000, 41090, 43000, 44000, 46000, and 54000 in the SOLSPERSE series of Lubrizol.
• DISPERBYK-102, 110, 111, 170, 190.194N, 2015.2090, 2096 and the like are listed, and in Evonik's TEGO® Dispers series, 610, 610S, 630, 651, 655, 750W, 755W and the like are listed.
• Disparon series manufactured by Enomoto Kasei Co., Ltd. DA-375, DA-1200 and the like are listed.
• In the Floren series manufactured by Kyoei Chemical Industry Co., Ltd., WK-13E, G-700, -900 can be exemplified GW-1500, GW-1640, WK-13E.
• the content in the case where the silver nanoparticle dispersion of this embodiment contains a dispersant may be adjusted according to desired properties such as viscosity.
• the content of the dispersant is preferably 0.5 to 20% by mass, and when used as a silver paste, the content of the dispersant is preferably 0.1 to 10% by mass.
• the content of the polymer dispersant is preferably 0.1 to 15% by mass.
• the content of the polymer dispersant is 0.1% or more, the dispersion stability of the obtained silver nanoparticle dispersion is improved.
• the content is too large, the low-temperature sinterability is lowered.
• the more preferable content of the polymer dispersant is 0.3 to 10% by mass, and still more preferable content is 0.5 to 8% by mass.
• the silver nanoparticle dispersion of the present embodiment preferably has a weight loss of 15% by mass or less at 100 to 500 ° C. when thermogravimetric analysis is performed at a heating rate of 10 ° C./min with respect to the solid content. .
• thermogravimetric analysis is performed at a heating rate of 10 ° C./min with respect to the solid content.
• decrease by heating to 500 degreeC can correspond to the quantity of the organic substance in solid content substantially.
• the weight loss is preferably 20% by mass or less.
• the content is preferably 0.1% by mass or more.
• a more preferred weight loss is 0.5 to 15% by mass.
• the silver nanoparticle dispersion of this embodiment may further contain a dispersant (protective dispersant) having an acid value as a protective agent added before the synthesis of silver nanoparticles.
• a dispersant protecting dispersant
• the “protective dispersant” referred to here may be the same or different type of the above-mentioned dispersant (dispersant having an acid value) added after the synthesis of the silver nanoparticles.
• the silver nanoparticle dispersion of the present embodiment has an appropriate viscosity, adhesion, and drying depending on the purpose of use within a range not impairing the effects of the present invention.
• Such optional components are not particularly limited.
• the resin component examples include polyester resins, polyurethane resins such as blocked isocyanate, polyacrylate resins, polyacrylamide resins, polyether resins, melamine resins, and the like. You may use, and may use 2 or more types together.
• the thickener examples include clay minerals such as clay, bentonite or hectorite, for example, emulsions such as polyester emulsion resins, acrylic emulsion resins, polyurethane emulsion resins or blocked isocyanates, methyl cellulose, carboxymethyl cellulose, and hydroxyethyl cellulose. , Hydroxypropylcellulose, cellulose derivatives of hydroxypropylmethylcellulose, polysaccharides such as xanthan gum or guar gum, etc., and these may be used alone or in combination of two or more.
• clay minerals such as clay, bentonite or hectorite
• emulsions such as polyester emulsion resins, acrylic emulsion resins, polyurethane emulsion resins or blocked isocyanates, methyl cellulose, carboxymethyl cellulose, and hydroxyethyl cellulose.
• Hydroxypropylcellulose cellulose derivatives of hydroxypropylmethylcellulose
• polysaccharides such as
• a surfactant different from the above organic components may be added.
• the coating surface becomes rough and the solid content tends to be uneven due to the difference in volatilization rate during drying.
• the surfactant that can be used in the present embodiment is not particularly limited, and any of an anionic surfactant, a cationic surfactant, and a nonionic surfactant can be used.
• an anionic surfactant for example, alkylbenzene sulfonic acid Salt, quaternary ammonium salt and the like.
• fluorine-based surfactants and silicone-based surfactants are preferred because an effect can be obtained with a small amount of addition. If the content of the surfactant is too small, the effect cannot be obtained. If the content is too large, the remaining amount of impurities in the coating becomes an impurity, so that the conductivity may be hindered.
• a preferable content of the surfactant is 0.01 to 5 parts by mass with respect to 100 parts by mass of the dispersion medium of the silver nanoparticle dispersion.
• amine is attached to at least a part of the surface of the silver nanoparticle, and the terpene resin is attached to the surface of the silver nanoparticle or dispersed in the dispersion medium (or Dissolved).
• amine is attached to at least a part of the surface of the silver nanoparticles, and the terpene resin is included in some form, so that the silver nanoparticles have excellent dispersibility in various dispersion media and low-temperature sintering. Can be imparted.
• the viscosity of the silver nanoparticle dispersion of this embodiment is preferably in the viscosity range of 1 to 100 cps, and more preferably in the viscosity range of 1 to 20 cps. By setting it as the said viscosity range, a silver nanoparticle dispersion can be apply
• a general-purpose coating method can be used as the coating method, and examples include an applicator method, a bar coater method, a capillary coater method, and a spin coating method.
• the adjustment of the viscosity of the silver nanoparticle dispersion of the present embodiment can be performed by adjusting the solid content concentration, adjusting the blending ratio of each component, adding a thickener, and the like.
• the viscosity can be measured with a vibration viscometer (for example, VM-100A-L manufactured by CBC Corporation). The measurement is performed by immersing the liquid in the vibrator, and the measurement temperature may be normal temperature (20 to 25 ° C.).
• the conductive ink of this embodiment (2) Manufacturing method of conductive ink
• a silver nanoparticle dispersion metal colloid liquid
• the conductive ink of this embodiment can be obtained by mixing this metal colloid liquid and the above-mentioned various components.
• the terpene resin which is an essential component, may be added as a protective dispersant not only after the addition to the dispersion medium but also before the synthesis of the silver nanoparticles.
• the silver nanoparticle dispersion of the present embodiment includes a step of generating silver nanoparticles and a step of adding and mixing a dispersant having an acid value for dispersing the silver nanoparticles to the silver nanoparticles. And. Furthermore, a first pre-process for preparing a mixed solution of a silver compound that can be decomposed by reduction to form metallic silver and an amine, and reducing the silver compound in the mixed solution to reduce at least one of the surfaces. And a second pre-process for producing silver nanoparticles having amine attached to the part.
• the first pre-process it is preferable to add 2 mol or more of amine to 1 mol of metal silver.
• an appropriate amount of amine can be attached to the surface of the silver nanoparticles produced by the reduction, and the silver nanoparticles are excellent for various dispersion media. Dispersibility and low-temperature sinterability can be imparted.
• the particle size of the silver nanoparticles obtained is a nanometer that causes a melting point drop.
• the size is preferable, and 1 to 200 nm is more preferable.
• particles of micrometer size may be included as necessary.
• the method for taking out silver nanoparticles from the silver nanoparticle dispersion obtained in the second pre-process is not particularly limited, and examples thereof include a method for washing the silver nanoparticle dispersion.
• silver compounds metal salts or hydrates thereof
• silver salts such as silver oxide, silver acetate, silver oxalate, silver formate, silver nitrite, silver chlorate, and silver sulfide. These are not particularly limited as long as they can be reduced, and may be dissolved in an appropriate solvent or may be used as dispersed in a solvent. These may be used alone or in combination.
• the method for reducing these silver compounds in the raw material liquid is not particularly limited.
• a method using a reducing agent a method of irradiating light such as ultraviolet rays, an electron beam, ultrasonic waves or thermal energy, a method of heating, etc. Is mentioned.
• a method using a reducing agent is preferable from the viewpoint of easy operation.
• Examples of the reducing agent include amine compounds such as dimethylaminoethanol, methyldiethanolamine, triethanolamine, phenidone, and hydrazine; for example, hydrogen compounds such as sodium borohydride, hydrogen iodide, and hydrogen gas; for example, carbon monoxide.
• amine compounds such as dimethylaminoethanol, methyldiethanolamine, triethanolamine, phenidone, and hydrazine
• hydrogen compounds such as sodium borohydride, hydrogen iodide, and hydrogen gas
• carbon monoxide for example, carbon monoxide.
• Oxides such as sulfurous acid; for example, ferrous sulfate, iron oxide, iron fumarate, iron lactate, iron oxalate, iron sulfide, tin acetate, tin chloride, tin diphosphate, tin oxalate, tin oxide, sulfuric acid
• Low valent metal salts such as tin; for example, sugars such as ethylene glycol, glycerin, formaldehyde, hydroquinone, pyrogallol, tannin, tannic acid, salicylic acid, D-glucose, etc.
• sugars such as ethylene glycol, glycerin, formaldehyde, hydroquinone, pyrogallol, tannin, tannic acid, salicylic acid, D-glucose, etc.
• light and / or heat may be added to promote the reduction reaction.
• the metal salt is dissolved in an organic solvent (for example, toluene) to form a metal.
• organic solvent for example, toluene
• examples include a method in which a salt solution is prepared, an amine as a protective dispersant or a protective dispersant having an acid value is added to the metal salt solution, and then a solution in which the reducing agent is dissolved is gradually added dropwise.
• the dispersion liquid containing silver nanoparticles coated with an amine or a protective dispersant having an acid value obtained as described above in addition to silver nanoparticles, a counterion of a metal salt, a residue of a reducing agent, There is a dispersant, and the concentration of the electrolyte and the organic matter in the whole liquid tend to be high.
• the liquid in such a state is likely to precipitate due to the coagulation of the metal particles due to high electrical conductivity.
• the conductivity of the metal salt may deteriorate if the counter ion of the metal salt, the residue of the reducing agent, or an excessive amount of dispersant remaining in the amount necessary for dispersion remains. Therefore, by washing the solution containing the silver nanoparticles to remove excess residues, silver nanoparticles coated with an organic substance can be reliably obtained.
• a dispersion containing silver nanoparticles coated with an organic component is allowed to stand for a certain period of time, and the resulting supernatant is removed, and then a solvent that precipitates silver nanoparticles (for example, water, Methanol, a methanol / water mixed solvent, etc.) and re-stirring, and a method of repeating the process of removing the supernatant obtained by standing still for a certain period of time, a method of performing centrifugation instead of the above-mentioned standing, Examples thereof include a method of desalting with an ultrafiltration device or an ion exchange device. By removing excess residues and removing the organic solvent by such washing, metal particles coated with the “short-chain amine or the dispersant having an acid value” of the present embodiment can be obtained.
• a solvent that precipitates silver nanoparticles for example, water, Methanol, a methanol / water mixed solvent, etc.
• the silver nanoparticle dispersion is a silver nanoparticle coated with the amine obtained above or a protective dispersant (including the case of the terpene resin) and the above. It is obtained by mixing the dispersion medium described in this embodiment.
• the mixing method of the metal particles coated with the amine or the protective dispersant and the dispersion medium is not particularly limited, and can be performed by a conventionally known method using a stirrer or a stirrer.
• An ultrasonic homogenizer with an appropriate output may be applied by stirring with a spatula or the like.
• a first step of preparing a mixed solution of a silver compound capable of decomposing by reduction to form metallic silver and an amine, and reducing the silver compound in the mixed solution to reduce amine on at least a part of the surface Silver nanoparticles may be produced by a second step of producing attached silver nanoparticles.
• a silver compound such as silver oxalate containing silver and a complex compound produced from an amine are heated to agglomerate atomic silver produced by decomposing a metal compound such as oxalate ion contained in the complex compound By doing so, silver particles protected by an amine protective film can be produced.
• the silver amine complex decomposition method for producing silver nanoparticles coated with amine by thermally decomposing a silver compound complex compound in the presence of amine the silver amine complex which is a single type of molecule is decomposed. Since atomic silver is generated by the decomposition reaction, it is possible to generate atomic silver uniformly in the reaction system, and the reaction is composed compared to the case of generating silver atoms by reaction between multiple components. Inhomogeneity of the reaction due to fluctuations in the composition of the components to be controlled is suppressed, which is particularly advantageous when producing a large amount of silver powder on an industrial scale.
• an amine molecule is coordinated to the silver atom to be generated, and the movement of the silver atom during aggregation is controlled by the action of the amine molecule coordinated to the silver atom. Inferred.
• the metal amine complex decomposition method it is possible to produce metal particles that are very fine and have a narrow particle size distribution.
• amine molecules form a relatively weak coordination bond on the surface of the silver nanoparticles to be produced, and these form a dense protective film on the surface of the silver nanoparticles. It is possible to produce coated silver nanoparticles having a clean surface with excellent surface roughness.
• the amine molecules forming the film can be easily detached by heating or the like, silver nanoparticles that can be sintered at a very low temperature can be produced.
• the amine is mixed with the dispersant having an acid value constituting the coating of the coated silver nanoparticles. This facilitates the generation of a complex compound such as a complex compound, and the complex compound can be produced by mixing in a short time.
• coated silver nanoparticles having characteristics corresponding to various applications can be produced.
• Conductive layer (conductive film) pattern and manufacturing method thereof When the conductive ink of this embodiment is used, a conductive ink application step of applying the conductive ink to a substrate, and the conductive material applied to the substrate. Formed on at least a part of the substrate and the surface of the substrate by a conductive film pattern forming step of baking a conductive ink at a temperature of less than 140 ° C. (preferably 120 ° C. or less) to form a conductive film pattern. A conductive film pattern-containing substrate can be manufactured.
• the present inventor applied the conductive ink of the present embodiment described above as the conductive ink in the conductive ink application step, and applied it to the substrate in the conductive film pattern formation step. It has been found that a conductive film pattern having excellent conductivity can be reliably obtained even when the conductive ink is baked at a temperature of less than 140 ° C.
• the conductive ink of the present embodiment is used for transfer printing, in the reverse printing method among the transfer printing methods, first, the conductive ink application surface is formed on the blanket by applying the transfer printing conductive ink. .
• the blanket a silicone blanket made of silicone is preferable. By forming the conductive ink application surface on the surface of the blanket and leaving it for a predetermined time, the low boiling point solvent volatilizes and is absorbed into the blanket, thereby increasing the viscosity of the conductive ink.
• the portion of the conductive ink that contacts the relief plate is removed from the blanket.
• the conductive ink has an appropriate cohesiveness, the conductive ink is surely peeled off from the blanket and adhered to the relief plate without structural destruction, and undesirable residue on the blanket is prevented. It is suppressed.
• the conductive ink remaining on the blanket forms a conductive ink pattern corresponding to the relief pattern on the blanket.
• the substrate that can be used in the present embodiment is not particularly limited as long as it has at least one main surface on which a conductive ink can be applied and fired by heating to mount a conductive film pattern. Although it is not, it is preferable that it is a base material excellent in heat resistance.
• the conductive ink for transfer printing of this embodiment has a conductive film pattern that has sufficient conductivity even when heated and baked at a lower temperature than conventional conductive inks. Since it can be obtained, it is possible to use a substrate having a lower heat-resistant temperature than the conventional one in a temperature range higher than this low firing temperature.
• Examples of the material constituting such a base material include polyamide (PA), polyimide (PI), polyamideimide (PAI), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and the like.
• Polyester, polycarbonate (PC), polyethersulfone (PES), vinyl resin, fluororesin, liquid crystal polymer, ceramics, glass or metal can be used.
• the substrate may have various shapes such as a plate shape or a strip shape, and may be rigid or flexible. The thickness of the substrate can also be selected as appropriate. In order to improve adhesiveness or adhesion, or for other purposes, a substrate on which a surface layer is formed or a substrate that has been subjected to a surface treatment such as a hydrophilic treatment may be used.
• the coating film after coating as described above is baked by heating to a temperature of less than 140 ° C. (preferably 120 ° C. or less) to obtain the conductive film pattern (substrate with a conductive film pattern) of this embodiment. Can do.
• the method for firing is not particularly limited.
• the temperature of the conductive ink applied or drawn on the substrate using a conventionally known gear oven or the like is less than 140 ° C. (preferably 120 ° C. or less).
• the conductive film pattern can be formed by firing so as to be.
• the lower limit of the firing temperature is not necessarily limited, and is a temperature at which a conductive film pattern can be formed on a substrate, and a temperature at which the organic components and the like can be removed by evaporation or decomposition within a range that does not impair the effects of the present invention. (A part may remain within a range that does not impair the effects of the present invention, but it is desirable that all be removed desirably).
• a conductive film pattern exhibiting high conductivity can be formed even by a low-temperature heat treatment at about 120 ° C. Therefore, the conductive film pattern is also formed on a relatively heat-sensitive substrate. Can be formed. Moreover, baking time is not specifically limited, A conductive film pattern can be formed on a base material according to baking temperature.
• surface treatment of the base material may be performed in order to further improve the adhesion between the base material and the conductive film pattern.
• the surface treatment method include a method of performing a dry treatment such as a corona treatment, a plasma treatment, a UV treatment, and an electron beam treatment, and a method of previously providing a primer layer and a conductive ink receiving layer on a substrate.
• the conductive film pattern (substrate with conductive film pattern) of this embodiment can be obtained.
• the conductive film pattern of the present embodiment thus obtained is, for example, about 0.1 to 5 ⁇ m, more preferably 0.1 to 1 ⁇ m.
• a conductive film pattern having sufficient conductivity can be obtained even when the thickness is about 0.1 to 5 ⁇ m.
• the volume resistance value of the electrically conductive film pattern of this embodiment is 15 microhm * cm or less.
• the thickness t of the conductive film pattern of the present embodiment can be obtained using, for example, the following formula (the thickness t of the conductive film pattern is measured with a laser microscope (for example, a laser microscope VK-9510 manufactured by Keyence). It is also possible to do this.)
• Formula: t m / (d ⁇ M ⁇ w)
• m conductive film pattern weight (the weight of the conductive film pattern formed on the slide glass is measured with an electronic balance)
• d Conductive film pattern density (g / cm 3 ) (10.5 g / cm 3 in the case of silver)
• M conductive film pattern length (cm) (the length of the conductive film pattern formed on the slide glass is measured on a scale equivalent to JIS class 1)
• w Conductive film pattern width (cm) (The width of the conductive film pattern formed on the slide glass is measured on a scale equivalent to JIS class 1)
• Example and a comparative example are given and the manufacturing method of the electrically conductive ink of this invention and the electrically conductive film pattern (base material with an electrically conductive film pattern) using the said electrically conductive ink is further demonstrated, this invention is these implementation. It is not limited to examples.
• Example 1 1.7 g of butylamine (Wako Pure Chemical Industries, Ltd., first grade reagent, carbon number: 4) and hexylamine (Wako Pure Chemical Industries, Ltd., first grade reagent, carbon number: 6) 3.5 g and polymer dispersant SOLSPERSE21000 (manufactured by Nippon Lubrizol Co., Ltd.) was mixed with 0.2 g, and stirred well with a magnetic stirrer to prepare an amine mixture. Next, 3.0 g of silver oxalate was added while stirring.
• Adhesion test A silver nanoparticle dispersion 1 was formed on a 2.5 cm square glass slide by spin coating (2000 rpm / 20 sec) and heated in a gear oven at 120 ° C. for 30 minutes. The conductive film was formed by sintering by firing. As an adhesion test, the tape was attached to the thin film on the glass substrate by the pull-off method, and evaluation was performed based on the rupture state as a result of peeling. Five slide-coated samples were prepared using five slide glasses, and each of the five sheets was strongly rubbed against the film and peeled off in the vertical direction for evaluation.
• Example 2 >> Instead of using YS resin PX1150, 0.04 g of terpene phenol resin YS Polystar T160 (manufactured by Yashara Chemical Co., Ltd., softening point 160 ⁇ 5 ° C.) (2.0% by weight based on silver solid content) was used. In the same manner as in Example 1, a silver nanoparticle dispersion liquid 2 was prepared and evaluated. The results are shown in Table 1.
• Example 3 Instead of using YS resin PX1150, 0.04 g of modified terpene resin YS resin TO115 (manufactured by Yasuhara Chemical Co., Ltd., softening point 115 ⁇ 5 ° C.) (2.0% by weight based on silver solid content) was used. In the same manner as in Example 1, a silver nanoparticle dispersion 3 was prepared and evaluated. The results are shown in Table 1.
• Example 4 Implemented except that 0.04 g (2.0% by weight based on silver solid content) of terpene resin YS resin PX1000 (manufactured by Yashara Chemical Co., Ltd., softening point 100 ⁇ 5 ° C.) was used instead of YS resin PX1150.
• YS resin PX1000 manufactured by Yashara Chemical Co., Ltd., softening point 100 ⁇ 5 ° C.
• Example 5 Instead of YS resin PX1150, 0.04 g (2.0% by weight based on silver solid content) of terpene light-colored rosin ester KE-311 (Arakawa Chemical Industries, softening point 95 ⁇ 5 ° C.) was used. Except for this, a silver nanoparticle dispersion 5 was prepared in the same manner as in Example 1, and an evaluation test was performed. The results are shown in Table 1.
• Example 6 Instead of KE-311, 0.04 g of terpene-based rosin resin KE-604 (Arakawa Chemical Industries, softening point 129 ⁇ 5 ° C.) was used (2.0 wt% based on silver solid content). A silver nanoparticle dispersion liquid 6 was prepared in the same manner as in Example 5 except that the evaluation test was performed. The results are shown in Table 1.
• Example 7 1.7 g of butylamine (Wako Pure Chemical Industries, Ltd., first grade reagent, carbon number: 4) and hexylamine (Wako Pure Chemical Industries, Ltd., first grade reagent, carbon number: 6) 3.5 g and polymer dispersant SOLSPERSE21000 (manufactured by Nippon Lubrizol Co., Ltd.) and 0.08 g of terpene resin YS resin PX1150 (manufactured by Yasuhara Chemical Co., Ltd., softening point 115 ⁇ 5 ° C.) (4.0 based on silver solid content) (% By weight) was added and mixed, and stirred well with a magnetic stirrer to produce an amine mixture.
• SOLSPERSE21000 manufactured by Nippon Lubrizol Co., Ltd.
• terpene resin YS resin PX1150 manufactured by Yasuhara Chemical Co., Ltd., softening point 115 ⁇ 5 ° C.
• Example 8 A silver nanoparticle dispersion liquid 8 was prepared and evaluated in the same manner as in Example 7 except that SOLPERSE21000 was not used at the time of blending. The results are shown in Table 1.
• Example 9 A silver nanoparticle dispersion 9 was prepared in the same manner as in Example 7 except that 0.20 g of terpene resin YS resin PX1150 (10.0% by weight with respect to the silver solid content) was used at the time of blending. went. The results are shown in Table 1.
• Example 10 A silver nanoparticle dispersion liquid 10 was prepared and evaluated in the same manner as in Example 7 except that 0.02 g of YS resin PX1150 (1.0% by weight based on the silver solid content) was used. The results are shown in Table 1.
• Comparative Example 4 >> Acrylate 8UA-140 (made by Taisei Fine Chemical Co., Ltd.), which is a urethane-modified acrylic polymer solution, is added to 1.5 g of dihydroterpinyl acetate, 0.04 g in terms of solid content (2.0 weight based on silver solid content) %) Except that the silver nanoparticle dispersion liquid 13 was prepared in the same manner as in Example 1, and an evaluation test was performed. The results are shown in Table 2.
• Comparative Example 5 The resin added to 1.5 g of dihydroterpinyl acetate is 0.04 g of terpene resin YS resin PX800 (manufactured by Yashara Chemical Co., Ltd., softening point 80 ⁇ 5 ° C.) in terms of solid content (2.0 weight based on silver solid content) %) Except that the silver nanoparticle dispersion liquid 14 was prepared in the same manner as in Example 1, and an evaluation test was performed. The results are shown in Table 2.
• Comparative Example 6 The resin added to 1.5 g of dihydroterpinyl acetate is 0.04 g of terpene resin YS resin PX300N (manufactured by Yasuhara Chemical Co., Ltd., softening point 30 ⁇ 5 ° C.) in terms of solid content (2.0 weight based on silver solid content) %) Except that the silver nanoparticle dispersion liquid 15 was prepared in the same manner as in Example 1, and an evaluation test was performed. The results are shown in Table 2.
• terpene resins pinene polymer, terpene phenol resin, rosin, rosin ester, etc. can be widely applied.
• Example 8 it can be used in combination with a polymer dispersant.
• nanoparticles can be synthesized by adding a terpene resin at the time of synthesis, and it was not possible to synthesize nanoparticles in Comparative Example 1 because both the polymer dispersant and the terpene resin were absent.
• electrical_connection is possible from Example 9 if the terpene resin compounding quantity with respect to silver solid content is 10 mass% or less.
• a terpene resin when a terpene resin is not used from Comparative Example 2, it does not adhere to the glass substrate. Furthermore, even if a resin other than a terpene resin such as a polyester resin or an acrylic resin is added from Comparative Examples 3 and 4, adhesion is achieved. And conductivity are not compatible. It can also be seen from Comparative Examples 5 and 6 that if the softening point of the terpene resin is lower than 90 ° C., the adhesion is not expressed.

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