WO2020202969A1 - Procédé de fabrication de motif électroconducteur - Google Patents

Procédé de fabrication de motif électroconducteur Download PDF

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Publication number
WO2020202969A1
WO2020202969A1 PCT/JP2020/008649 JP2020008649W WO2020202969A1 WO 2020202969 A1 WO2020202969 A1 WO 2020202969A1 JP 2020008649 W JP2020008649 W JP 2020008649W WO 2020202969 A1 WO2020202969 A1 WO 2020202969A1
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Prior art keywords
acid
pattern
aqueous solution
conductive
conductive pattern
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PCT/JP2020/008649
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English (en)
Japanese (ja)
Inventor
兒玉年矢
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東レ株式会社
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Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2020513351A priority Critical patent/JP7371620B2/ja
Priority to KR1020217024256A priority patent/KR20210144666A/ko
Priority to CN202080013564.2A priority patent/CN113412688A/zh
Publication of WO2020202969A1 publication Critical patent/WO2020202969A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks

Definitions

  • the present invention relates to a method for manufacturing a conductive pattern.
  • the touch panel is composed of a display unit such as a liquid crystal panel or an organic EL (electroluminescence) panel, and a touch sensor or the like that detects information input at a specific position.
  • the touch panel method is roughly classified into a resistive film method, a capacitance method, an optical method, an electromagnetic induction method, an ultrasonic method, and the like, depending on the input position detection method.
  • a capacitive touch panel is widely used because of its optical brightness, excellent design, simple structure, and excellent functionality.
  • the capacitance type touch sensor has a second electrode that is orthogonal to the first electrode via an insulating layer, and when a voltage is applied to the electrode on the touch panel surface, the capacitance when a conductor such as a finger touches it.
  • the contact position obtained by detecting the change is output as a signal.
  • a transparent wiring electrode such as indium tin oxide was generally used from the viewpoint of making the wiring electrode difficult to see, but in recent years, the sensitivity has been increased and the screen has been increased. Due to the increase in size, opaque wiring electrodes using metal materials have become widespread.
  • the conductive pattern layer is subjected to a strong acid treatment step of contacting the conductive pattern layer with a strong acid aqueous solution at room temperature and a weak acid treatment step of contacting the conductive pattern layer with a weak acid aqueous solution having a temperature higher than room temperature.
  • a method has been proposed in which at least a part of the metal particles in the layer are fused to form a chain to reduce the surface resistivity of the conductive pattern layer (see, for example, Patent Document 2).
  • an object of the present invention is to provide a method for producing a conductive pattern having excellent conductivity even at a low temperature of 100 ° C. or lower.
  • the present invention (1) A step of forming a pattern containing the conductive particles (a) and the resin (b) on the base material, and (2)
  • the formed pattern contains at least one salt having an acid dissociation constant (pKa) of an anionic conjugate acid at 25 ° C. of 1.0 or less, and has a pH of 1.2 to 3.5 at 25 ° C.
  • It is a method for producing a conductive pattern which comprises a step of bringing a certain acidic aqueous solution into contact with each other.
  • the method for producing a conductive pattern of the present invention is (1) A step of forming a pattern containing the conductive particles (a) and the resin (b) on the base material (hereinafter, may be referred to as step (1)).
  • the formed pattern contains at least one salt having an acid dissociation constant (pKa) of an anionic conjugate acid at 25 ° C. of 1.0 or less, and has a pH of 1.2 to 3.5 at 25 ° C. It has a step of bringing a certain acidic aqueous solution into contact (hereinafter, may be referred to as step (2)).
  • the conductive pattern obtained by the production method of the present invention is a composite of an organic component of the resin (b) and an inorganic component of the conductive particles (a), and the conductive particles (a) are brought together by an atomic diffusion phenomenon. Conductivity is developed by contacting each other.
  • the resin (b) has an action of improving the adhesion between the pattern and the base material.
  • the pattern is brought into contact with an acidic aqueous solution containing at least one salt having an acid dissociation constant (pKa) of an anionic conjugate acid at 25 ° C. of 1.0 or less and having a pH of 1.2 to 3.5 at 25 ° C.
  • pKa acid dissociation constant
  • polyester films such as polyethylene terephthalate (hereinafter, may be referred to as "PET") films, polyimide films, aramid films, epoxy resin films, polyetherimide films, polyether ketone films, and polysulfone films.
  • PET polyethylene terephthalate
  • examples thereof include films, glass substrates, silicon wafers, alumina substrates, aluminum nitride substrates, silicon carbide substrates, decorative layer forming substrates, and insulating layer forming substrates.
  • the pattern formed in step (1) contains conductive particles (a).
  • the conductive particles (a) include particles such as silver, gold, copper, platinum, lead, tin, nickel, aluminum, tungsten, molybdenum, chromium, titanium, indium, and alloys of these metals. Two or more of these may be contained. Among these, metal particles selected from silver, gold and copper are preferable from the viewpoint of conductivity, and silver particles are more preferable from the viewpoint of cost and stability.
  • the conductive particles (a) may have a layer structure of two or more layers. For example, it may have a core-shell structure having a shell made of silver on the surface of a core made of copper. Further, the surface of the conductive particles (a) may be coated with an organic component, an inorganic oxide, or the like.
  • the organic component functions as a dispersant or a conductive auxiliary agent for conductive particles having a small particle size. Examples of the organic component include fatty acids, amines, thiols, and cyanide.
  • the volume average particle diameter of the conductive particles (a) is preferably 0.1 ⁇ m or more from the viewpoint of appropriately suppressing the interaction between the particles and improving the dispersibility of the conductive particles (a) in the pattern.
  • the volume average particle diameter of the conductive particles (a) is preferably 2.0 ⁇ m or less from the viewpoint of improving the surface smoothness and dimensional accuracy of the conductive pattern and forming a fine conductive pattern.
  • the volume average particle diameter of the conductive particles (a) is determined by dissolving the formed pattern with a solvent in which a resin component such as THF (tetrahydrofluorocarbon) is soluble, centrifuging the particles, and removing the resin component. The particles are precipitated and collected.
  • the recovered solid content was observed with a scanning electron microscope (SEM) or a transmission electron microscope (TEM) for the conductive particles (a), and 100 primary particles of the conductive particles (a) were randomly selected. This can be obtained by acquiring an image, obtaining a circle-converted diameter of each primary particle by image analysis, and calculating an average diameter weighted by volume.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the content of the conductive particles (a) in the pattern is preferably 65 to 90% by mass.
  • the content of the conductive particles (a) is 65% by mass or more, the contact probability between the conductive particles (a) in the step (2) described later is improved, and the conductivity can be further improved.
  • the content of the conductive particles (a) is 90% by weight or less, a fine pattern can be formed by photolithography.
  • the proportion of the conductive particles (a) in the conductive pattern is determined by scraping off the formed pattern and burning an organic component at 400 to 600 ° C. with a TG-DTA (differential thermal balance) to obtain an inorganic solid in the conductive pattern. It can be calculated by determining the ratio of minutes, dissolving the remaining inorganic solid content in nitrate or the like, and measuring the ratio of the conductive particles (a) in the inorganic solid content by ICP emission spectroscopic analysis.
  • the pattern formed in step (1) contains resin (b).
  • the resin include acrylic resin, polyester resin, phenol resin, epoxy resin, acrylic urethane resin, polyether urethane resin, phenoxy resin, polycarbonate resin, polyimide resin, polyamide resin, polyamideimide resin and the like. Two or more of these may be contained.
  • the resin (b) preferably has a carboxyl group, and it is preferable to use a photosensitive paste described later.
  • the resin containing a carboxyl group examples include an acrylic copolymer, a carboxylic acid-modified epoxy resin, a carboxylic acid-modified phenol resin, a polyamic acid, and a carboxylic acid-modified siloxane polymer. Two or more of these may be contained. Among these, an acrylic copolymer having a high ultraviolet light transmittance or a carboxylic acid-modified epoxy resin is preferable.
  • acrylic copolymer a copolymer of an acrylic monomer and an unsaturated acid or an acid anhydride thereof is preferable, and a copolymer with another monomer having an unsaturated double bond may be used.
  • acrylic monomer examples include methyl acrylate, ethyl acrylate (hereinafter, may be referred to as “EA”), 2-ethylhexyl acrylate, n-butyl acrylate (hereinafter, may be referred to as “BA”), and the like.
  • EA methyl acrylate
  • BA 2-ethylhexyl acrylate
  • BA n-butyl acrylate
  • Examples of unsaturated acids or acid anhydrides thereof include acrylic acid (hereinafter, may be referred to as “AA”), methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate, and the like.
  • Examples include acid anhydrides. Two or more of these may be used.
  • the acid value of the acrylic copolymer can be adjusted by the copolymerization ratio of the unsaturated acid.
  • Examples of the monomer having an unsaturated double bond include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene and the like. Two or more of these may be used.
  • the carboxylic acid-modified epoxy resin a reaction product of an epoxy compound and an unsaturated acid or an unsaturated acid anhydride is preferable.
  • the carboxylic acid-modified epoxy resin is one in which the epoxy group of the epoxy compound is modified with a carboxylic acid or a carboxylic acid anhydride, and does not contain an epoxy group.
  • Examples of the epoxy compound include glycidyl ethers, glycidyl amines, and epoxy resins. More specifically, examples of the glycidyl ethers include methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and tripropylene glycol diglycidyl ether.
  • glycidyl amines include tert-butyl glycidyl amine.
  • the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin and the like. Two or more of these may be used.
  • Examples of unsaturated acids or unsaturated acid anhydrides include those exemplified above as raw materials for acrylic copolymers.
  • An unsaturated double bond can be introduced by reacting the above-mentioned acrylic copolymer or carboxylic acid-modified epoxy resin with a compound having an unsaturated double bond such as glycidyl (meth) acrylate.
  • a compound having an unsaturated double bond such as glycidyl (meth) acrylate.
  • a resin having a phenolic hydroxyl group can also be preferably used.
  • a hydrogen bond can be formed with a polar group such as a hydroxyl group or an amino group on the surface of the base material, and the adhesion between the pattern and the base material can be improved.
  • the acid value of the resin (b) is preferably 50 to 250 mgKOH / g.
  • the acid value is more preferably 60 mgKOH / g or more.
  • the acid value is 250 mgKOH / g or less, excessive dissolution in the developing solution can be suppressed and film loss of the pattern can be suppressed.
  • the acid value is more preferably 200 mgKOH / g or less.
  • the acid value of the resin (b) can be measured in accordance with JIS K0070 (1992).
  • a paste containing the above-mentioned conductive particles (a), resin (b), and other components if necessary is printed by screen printing, gravure printing, flexographic printing, inkjet printing, or the like.
  • Examples thereof include a method of forming a pattern and a method of forming a pattern by photolithography having exposure and development steps.
  • Examples of the method of forming a pattern by photolithography include a method of applying a photosensitive resist on a non-photosensitive paste coating film and forming a pattern by the steps of exposure, development, etching and resist removal, and exposure from a photosensitive paste coating film. And a method of directly forming a pattern by a developing process and the like. Among them, from the viewpoint of thinning the pattern and shortening the number of manufacturing steps, a method of forming a pattern from a photosensitive paste coating film by photolithography having exposure and developing steps is preferable.
  • the content of the conductive particles (a) in the paste is preferably 65 to 90% by weight in the solid content.
  • the method for forming a conductive pattern of the present invention has conductive particles (a), a carboxyl group-containing resin (B) (also referred to as a carboxyl group-containing resin (B)), and an unsaturated double bond on a substrate. It has a photolithography step of forming a coating film by applying a photosensitive paste containing a reactive monomer (c) and a photopolymerization initiator (d), and forming a pattern by exposing and developing the coating film. Is preferable. By forming the conductive pattern in this way, a fine pattern can be easily formed by a simple method.
  • Examples of the carboxyl group-containing resin (B) include the above-mentioned resin (b) having a carboxy group. Two or more of these may be contained.
  • the acid value of the carboxyl group-containing resin (B) can be adjusted to a desired range by the ratio of unsaturated acids in the constituent components.
  • a carboxylic acid-modified epoxy resin it can be adjusted to a desired range by reacting with a polybasic acid anhydride.
  • a carboxylic acid-modified phenolic resin it can be adjusted to a desired range by the ratio of the polybasic acid anhydride in the constituents.
  • Examples of the reactive monomer (c) having an unsaturated double bond include the acrylic monomer exemplified above as a raw material for the acrylic copolymer, styrene "hereinafter (St)" and the like. Two or more of these may be contained.
  • the reactive monomer (c) having an unsaturated double bond in the paste contains an acrylic copolymer and a reactive monomer (c) having an unsaturated double bond
  • the reactive monomer (c) having an unsaturated double bond in the paste is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the acrylic copolymer.
  • a fine pattern can be formed by containing 1 part by weight or more of the reactive monomer (c) having an unsaturated double bond.
  • curing shrinkage can be appropriately suppressed and conductivity can be further improved.
  • the photopolymerization initiator (d) is a compound that absorbs light having a short wavelength such as ultraviolet rays and causes a decomposition or hydrogen abstraction reaction to generate radicals.
  • Examples of the photopolymerization initiator (d) include benzophenone derivatives, acetophenone derivatives, thioxanthone derivatives, benzyl derivatives, benzoin derivatives, oxime compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoalkylphenone compounds, and phosphine oxide compounds. , Antron compounds, anthraquinone compounds and the like.
  • benzophenone derivative examples include benzophenone, methyl O-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-dichlorobenzophenone, fluorenone, 4 -Benzoyl-4'-methyldiphenylketone and the like can be mentioned.
  • acetophenone derivative examples include pt-butyldichloroacetophenone, 4-azidobenzalacetophenone, 2,2'-diethoxyacetophenone and the like.
  • Examples of the thioxanthone derivative include thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone and the like.
  • Examples of the benzyl derivative include benzyl, benzyl dimethyl ketal, benzyl- ⁇ -methoxyethyl acetal and the like.
  • Examples of the benzoin derivative include benzoin, benzoin methyl ether, benzoin butyl ether and the like.
  • oxime compounds include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] and ethanone-1- [9-ethyl-6- (2-methylbenzoyl)].
  • Examples of the ⁇ -hydroxyketone compound include 2-hydroxy-2-methyl-1-phenyl-propane-1-one and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-. Examples thereof include methyl-1-propane-1-one.
  • Examples of the ⁇ -aminoalkylphenone compound include 2-methyl- (4-methylthiophenyl) -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl).
  • 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butane-1-one and the like can be mentioned.
  • Examples of the phosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like.
  • Examples of the anthrone compound include anthrone, benzanthrone, dibenzosverone, methyleneanthrone and the like.
  • Examples of the anthraquinone compound include anthraquinone, 2-t-butyl anthraquinone, 2-amyl anthraquinone, ⁇ -chloroanthraquinone and the like. Two or more of these may be contained. Among these, oxime compounds having high photosensitivity are preferable.
  • the content of the photopolymerization initiator (d) in the photosensitive paste is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin (B).
  • the content of the photopolymerization initiator (d) is 1 part by weight or more, the curing density of the exposed part is increased, and the residual film ratio after development can be increased.
  • the content of the photopolymerization initiator (d) is 30 parts by weight or less, excessive light absorption by the photopolymerization initiator (d) at the upper part of the pattern is suppressed. As a result, the pattern can be easily tapered, and the adhesion to the base material can be improved.
  • the paste used for pattern formation can also contain additives such as solvents, plasticizers, leveling agents, surfactants, silane coupling agents, defoamers, and pigments.
  • plasticizer examples include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, glycerin and the like.
  • leveling agent examples include a special vinyl-based polymer and a special acrylic-based polymer.
  • silane coupling agent examples include methyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and vinyltrimethoxysilane. , 3-Glycydoxypropylmethyldiethoxysilane and the like.
  • solvent examples include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, 2-dimethylaminoethanol "hereinafter (DMEA)", dimethylimidazolidinone, dimethyl sulfoxide, and ⁇ .
  • DMEA 2-dimethylaminoethanol
  • the boiling point of the solvent is preferably 150 ° C. or higher. When the boiling point is 150 ° C. or higher, volatilization of the solvent is suppressed and thickening of the paste can be suppressed.
  • the step (1) will be described in more detail by taking as an example a method of forming a pattern from a photosensitive paste coating film by photolithography.
  • a paste is prepared by mixing conductive particles (a), resin (b), a solvent and, if necessary, other components.
  • the mixing device include a disperser such as a three-roller mill, a ball mill, and a planetary ball mill, and a kneader.
  • the obtained paste is applied onto the substrate and dried.
  • the method of applying the paste include rotary coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater or bar coater.
  • the drying method include heat drying using an oven, a hot plate, infrared rays, and vacuum drying.
  • the drying temperature is preferably 50 to 180 ° C., and the drying time is preferably 1 minute to several hours.
  • the obtained coating film is exposed to an arbitrary pattern-forming mask to form a latent image.
  • a light source for exposure i-line (365 nm), h-line (405 nm) or g-line (436 nm) of a mercury lamp is preferably used.
  • the unexposed portion is dissolved and removed by developing with a developing solution to form a desired pattern.
  • the developing solution for alkaline development include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, and dimethyl acetate.
  • examples thereof include aqueous solutions of aminoethyl, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like. Two or more of these may be used.
  • polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, and ⁇ -butyrolactone are added to these aqueous solutions; methanol, ethanol, isopropanol, etc. Alcohols; Esters such as ethyl lactate and propylene glycol monomethyl ether acetate; Ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone; One or more surfactants may be added.
  • a developing method for example, a method of spraying a developing solution on a coating film surface while allowing or rotating a base material having an exposed paste coating film, or immersing a base material having an exposed paste coating film in a developing solution.
  • a method of spraying a developing solution on a coating film surface while allowing or rotating a base material having an exposed paste coating film, or immersing a base material having an exposed paste coating film in a developing solution examples thereof include a method of applying ultrasonic waves while immersing a base material having an exposed paste coating film in a developing solution.
  • rinsing treatment with a rinsing solution may be performed.
  • the rinsing solution include water or an aqueous solution obtained by adding alcohols such as ethanol and isopropyl alcohol or esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water.
  • the thickness of the pattern obtained in the step (1) is preferably 3 ⁇ m or less. By making the thickness 3 ⁇ m or less, a fine conductive pattern can be formed. In addition, the acidic aqueous solution can easily permeate, and better conductivity can be obtained even in a short time.
  • step (2) will be described.
  • the pattern formed in the step (1) contains at least one salt having an acid dissociation constant (pKa) of an anionic conjugate acid at 25 ° C. of 1.0 or less, and has a pH at 25 ° C.
  • pKa acid dissociation constant
  • the acidic aqueous solution contains at least one salt having an acid dissociation constant (pKa) of an anionic conjugate acid at 25 ° C. of 1.0 or less.
  • the “salt” refers to a component composed of cations and anions other than protons, and in the present invention, the “salt” also includes those in a state of being ionized into cations and anions in an aqueous solution.
  • the cation may partially exist as an ion bonded to a hydroxyl group, and the aqueous solution in this case becomes acidic.
  • the presence of the anion contained in the salt in the aqueous acid solution promotes the diffusion of atoms from the surface of the conductive particles (a) and improves the conductivity.
  • the concentration of anions can be increased even if the pH is 1.2 or higher, as described later. As a result, it is possible to suppress a decrease in conductivity due to corrosion of the conductive particles (a) contained in the conductive pattern.
  • the pKa of the anionic conjugate acid contained in the salt at 25 ° C. is more preferably ⁇ 5.0 or less.
  • the pKa of the conjugate acid of the anion contained in the salt is -2 or less, the literature value or the like can be referred to.
  • the salt having a pKa of the anion conjugate acid at 25 ° C. of 1.0 or less is not particularly limited as long as it is water-soluble.
  • the salt concentration is preferably 0.05 mol / L or more.
  • the salt concentration refers to the total concentration of salts when two or more kinds of salts are contained.
  • the type and concentration of salts contained in an acidic aqueous solution in which the pKa of the anionic conjugate acid at 25 ° C. is 1.0 or less can be analyzed by ion chromatography, inductively coupled plasma mass spectrometry, or the like.
  • the pH of the acidic aqueous solution at 25 ° C. is 1.2 to 3.5.
  • the pH is more preferably 2.5 or less.
  • the pH can be measured by the glass electrode method from the potential difference generated between the two electrodes, the glass electrode and the comparison electrode.
  • the acidic aqueous solution may contain an acid as a component other than the above salt so as to have a predetermined pH range.
  • the acid preferably contains an acid having an acid dissociation constant (pKa) of 2 to 5 at 25 ° C., that is, a weak acid.
  • pKa acid dissociation constant
  • the pKa of the first stage which is most easily ionized, is preferably 2 to 5, and when two or more kinds of acids are contained, the pKa of the acid most easily ionized is 2 to 5. It is preferably 5.
  • the pKa is more preferably 3.5 or less.
  • Examples of the acid having a pKa of 2 to 5 at 25 ° C. include phosphoric acid, citric acid, acetic acid, propionic acid, ascorbic acid, formic acid, and lactic acid.
  • pKa can be measured by identifying the acid by analysis and using absorptiometry for that acid.
  • Acid HX in an aqueous solution, HX and X - is present in both the state of HX and X - from the difference between the absorption spectrum of HX and X in aqueous solution - can measure the concentration of the lower formula ( It can be calculated based on 1).
  • the concentration of the acid having a pKa of 2 to 5 at 25 ° C. is preferably 0.05 to 1 mol / L.
  • the concentration can be appropriately adjusted to a desired pH depending on the type of acid contained.
  • the liquid temperature of the acidic aqueous solution brought into contact with the pattern is preferably 40 ° C. to 90 ° C.
  • the conductivity can be improved in a shorter time.
  • the liquid temperature is more preferably 60 ° C. or higher.
  • the evaporation of the acidic aqueous solution can be suppressed by setting the liquid temperature to 90 ° C. or lower.
  • the temperature of the acidic aqueous solution can be appropriately adjusted depending on the type of acid contained.
  • the acidic aqueous solution may be preheated and brought into contact with the pattern, or may be heated in a state where the pattern and the acidic aqueous solution are in contact with each other.
  • the heating method include heating with a hot plate, a hot air oven, an inert oven, an IR furnace, microwaves, and irradiation with a xenon flash lamp.
  • the concentration of the acidic aqueous solution is preferably 0.05 to 1 mol / L.
  • the concentration can be appropriately adjusted to a desired pH depending on the type of acid contained.
  • the conductive pattern obtained in step (2) may be rinsed with a rinsing solution.
  • a rinsing solution examples include water or an aqueous solution obtained by adding alcohols such as ethanol or isopropyl alcohol or esters such as ethyl lactate or propylene glycol monomethyl ether acetate to water.
  • alcohols such as ethanol or isopropyl alcohol or esters such as ethyl lactate or propylene glycol monomethyl ether acetate
  • a mixture of 20 g of EA, 40 g of 2-EHMA, 20 g of St, 15 g of AA, 0.8 g of 2,2'-azobisisobutyronitrile and 10 g of DMEA was added dropwise thereto over 1 hour. did. After completion of the dropping, the polymerization reaction was further carried out for 6 hours. Then, 1 g of hydroquinone monomethyl ether was added to terminate the polymerization reaction. Subsequently, a mixture consisting of 5 g of GMA, 1 g of triethylbenzylammonium chloride and 10 g of DMEA was added dropwise over 0.5 hours. After completion of the dropping, an addition reaction was carried out for another 2 hours.
  • the obtained reaction solution was purified with methanol to remove unreacted impurities, and further vacuum dried for 24 hours to obtain an acrylic copolymer (B-1).
  • the acid value of the obtained acrylic copolymer (B-1) was 103 mgKOH / g.
  • the obtained reaction solution was purified with methanol to remove unreacted impurities, and vacuum dried for 24 hours to obtain an acrylic copolymer (B-2).
  • the acid value of the obtained acrylic copolymer (B-2) was 96 mgKOH / g.
  • pKa of the acid was measured using an acidic aqueous solution prepared by adjusting the acid shown in Table 1 to 0.01 mol / L at a liquid temperature of 25 ° C. using a pKa analyzer (Sirius-T3; manufactured by Pion).
  • the pKa of the conjugate acid of the anion constituting the salt is adjusted to 0.01 mol / L by adjusting the acid composed of the anion and the proton constituting the salt to 0.01 mol / L, and then the aqueous solution is kept at a liquid temperature of 25 ° C. and a pKa analyzer (Siris-T3). Measured using (manufactured by Pion). If the pKa of the conjugate acid of the anion constituting the salt is -2 or less, "David A. Evans, [online], Internet ⁇ URL: http://evans.rc.fas.harvard.edu/pdf/evans_pKa_table. pdf> ”was referenced.
  • the pH of the acidic aqueous solution was measured by keeping the acidic aqueous solution shown in Table 1 at a liquid temperature of 25 ° C. and using a pH meter (F-71; manufactured by HORIBA, Ltd.).
  • the line width was calculated by observing the line widths at 10 randomly selected positions with an optical microscope, analyzing the image data, and obtaining the average value thereof.
  • Specific resistance resistance value x film thickness x line width / line length ... (2) The smaller the specific resistance, the better the conductivity.
  • Example 1 In a 100 mL clean bottle, put 10.0 g of acrylic copolymer (B-1), 2.0 g of light acrylate BP-4EA, 0.60 g of OXE01 and 9.0 g of DMEA, and put "Awatori Rentaro”. (ARE-310; manufactured by Shinky Co., Ltd.) was mixed to obtain 21.6 g of a resin solution (total solid content: 58.3% by mass).
  • the conductive paste 1 was applied on a PET film having a thickness of 50 ⁇ m by a screen printing method so that the coating film thickness after drying was 1.5 ⁇ m, and the obtained coating film was dried in a drying oven at 80 ° C. for 15 minutes. .. The following patterning property and conductivity were evaluated.
  • Patterning property The coating film after drying is exposed through a photomask having a group of straight lines arranged at a constant L / S, that is, a translucent pattern, and each having three types of units having different L / S values. And developed to obtain three types of patterns having different L / S values. Then, the obtained three types of patterns were immersed in the acidic aqueous solution shown in Table 1 for a predetermined time, rinsed with ultrapure water to wash away the acid, drained with air cut, and dried in a drying oven at 80 ° C. for 3 minutes. Then, three types of conductive patterns having different L / S values were obtained, and these were used as samples for evaluating patterning property.
  • the L / S value of each unit of the photomask was set to 15/15, 10/10, and 7/7 (representing line width ( ⁇ m) / interval ( ⁇ m), respectively).
  • a full-line exposure was performed using an exposure apparatus (PEM-6M; manufactured by Union Optical Co., Ltd.) at an exposure amount of 300 mJ / cm 2 (wavelength 365 nm conversion), and development was carried out in a 0.20 mass% Na 2 CO 3 solution. Was immersed for 30 seconds and then rinsed with ultrapure water. Table 1 shows the evaluation results of the patterning property.
  • Conductivity A pattern was obtained by exposing and developing the dried coating film through a photomask having 100 translucent patterns 100 shown in FIG. Then, the obtained pattern is immersed in the acidic aqueous solution shown in Table 1 for the time shown in Table 1, the acid is washed away by rinsing treatment with ultrapure water, the water is drained by air cutting, and the drying oven at 80 ° C. is used for 3 minutes. The mixture was dried to obtain a sample for evaluating conductivity. The line width of the obtained conductive pattern was 0.10 mm, and the line length was 80 mm. The exposure and development conditions were the same as those described in the preparation of the sample for evaluation of patterning property. Table 1 shows the evaluation results for conductivity.
  • Example 2 A predetermined pattern was formed from the conductive paste having the composition shown in Table 1, and the conductive pattern was produced by the same method as in Example 1 using the acidic aqueous solution shown in Table 1, and the same evaluation as in Example 1 was performed.
  • Table 1 shows the evaluation results for patterning property and conductivity.
  • Example 25 Put 12.0 g of acrylic copolymer (B-2), 0.60 g of OXE01 and 9.0 g of DMEA in a 100 mL clean bottle, and put "Awatori Rentaro"(ARE-310; manufactured by Shinky Co., Ltd.). To obtain 21.6 g of a resin solution (total solid content: 58.3% by mass).
  • Example 27 A predetermined pattern is formed by the conductive paste having the composition shown in Table 1, and the obtained pattern is immersed in the acidic aqueous solution shown in Table 1 for the time shown in Table 1, and then dried in a drying oven at 100 ° C. without washing. Cure for 10 minutes. Then, the acid was washed away by rinsing with ultrapure water, the water was drained by air cutting, and the mixture was dried in a drying oven at 80 ° C. for 3 minutes to produce a conductive pattern, which was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results for patterning property and conductivity.
  • Example 28 Put 10.0 g of acrylic copolymer (B-1) and 8.0 g of DMEA in a 100 mL clean bottle, mix with "Awatori Rentaro"(ARE-310; manufactured by Shinky Co., Ltd.), and 18 A 0.0 g resin solution (total solid content 55.6% by mass) was obtained.
  • the L / S values of each unit of the intaglio used in the gravure printing were set to 15/15, 10/10, and 7/7 (representing line width ( ⁇ m) / interval ( ⁇ m), respectively).
  • Table 1 shows the evaluation results of the patterning property.
  • a pattern used for evaluation of conductivity was obtained by gravure printing the conductive paste 3 on a PET film having a thickness of 50 ⁇ m.
  • the intaglio used in the gravure printing has 100 patterns 100 shown in FIG.
  • the resulting pattern was dried in a drying oven at 80 ° C. for 15 minutes.
  • the obtained pattern is immersed in the acidic aqueous solution shown in Table 1 for the time shown in Table 1, the acid is washed away by rinsing treatment with ultrapure water, the water is drained by air cutting, and the drying oven at 80 ° C. is used for 3 minutes.
  • the mixture was dried to obtain a sample for evaluating conductivity.
  • the line width of the obtained conductive pattern was 0.10 mm, and the line length was 80 mm. Table 1 shows the evaluation results for conductivity.
  • a predetermined pattern is formed by the conductive paste having the composition shown in Table 2, and the obtained pattern is immersed in a 0.2 mol / L hydrochloric acid aqueous solution at 25 ° C. for 1 minute and then heated to 70 ° C. at 0.2 mol /. It was immersed in an aqueous citric acid solution of L for 10 minutes, rinsed with ultra-pure water to wash away the acid, drained with an air cut, and dried in a drying oven at 80 ° C. for 3 minutes to produce a conductive pattern. A similar evaluation was made. Table 2 shows the evaluation results for patterning property and conductivity.
  • Example 5 A predetermined pattern is formed by the conductive paste having the composition shown in Table 2, and the obtained pattern is immersed in a 1 mol / L hydrochloric acid aqueous solution at 25 ° C. for 1 minute and then heated to 70 ° C. for 1 mol / L citric acid. Immerse in an aqueous solution for 10 minutes, rinse off the acid by rinsing with ultra-pure water, drain the water with an air cut, and dry in a drying oven at 80 ° C. for 3 minutes to produce a conductive pattern, and perform the same evaluation as in Example 1. did. Table 2 shows the evaluation results for patterning property and conductivity.

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Abstract

La présente invention concerne un procédé de fabrication d'un motif électroconducteur ayant une excellente conductivité électrique à une température basse de 100°C ou moins. L'invention concerne un procédé de fabrication d'un motif électroconducteur comportant (1) une étape de formation d'un motif comprenant des particules électroconductrices (a) et une résine (b) sur un substrat ; et (2) une étape de mise en contact d'une solution aqueuse acide avec le motif formé, la solution aqueuse acide contenant au moins un type de sel dans lequel la constante de dissociation acide (pKa) d'un acide conjugué d'anions à 25°C est de 1,0 ou moins et ayant un pH à 25°C de 1,2 à 3,5.
PCT/JP2020/008649 2019-03-29 2020-03-02 Procédé de fabrication de motif électroconducteur WO2020202969A1 (fr)

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JP2020513351A JP7371620B2 (ja) 2019-03-29 2020-03-02 導電パターンの製造方法
KR1020217024256A KR20210144666A (ko) 2019-03-29 2020-03-02 도전 패턴의 제조 방법
CN202080013564.2A CN113412688A (zh) 2019-03-29 2020-03-02 导电图案的制造方法

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CN113192665A (zh) * 2021-04-28 2021-07-30 北京梦之墨科技有限公司 一种电子器件及其制作方法
CN113203774A (zh) * 2021-04-28 2021-08-03 北京梦之墨科技有限公司 一种液体传感器及其制作方法、液体传感系统

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JP2008277250A (ja) * 2006-12-21 2008-11-13 Fujifilm Corp 導電膜およびその製造方法
JP2009155712A (ja) * 2007-12-27 2009-07-16 Omron Corp 金属膜の製造方法
JP2010272402A (ja) * 2009-05-22 2010-12-02 Konica Minolta Holdings Inc 導電膜パターン及び導電膜パターンの形成方法
JP2011140635A (ja) * 2009-12-10 2011-07-21 Riso Kagaku Corp 導電性エマルジョンインク及びそれを用いた導電性薄膜の形成方法
JP2012216535A (ja) * 2011-03-31 2012-11-08 Mitsubishi Chemicals Corp 金属ナノワイヤー含有透明導電膜及びその塗布液

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113192665A (zh) * 2021-04-28 2021-07-30 北京梦之墨科技有限公司 一种电子器件及其制作方法
CN113203774A (zh) * 2021-04-28 2021-08-03 北京梦之墨科技有限公司 一种液体传感器及其制作方法、液体传感系统
WO2022227839A1 (fr) * 2021-04-28 2022-11-03 北京梦之墨科技有限公司 Dispositif électronique et son procédé de fabrication

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TWI833933B (zh) 2024-03-01
TW202043296A (zh) 2020-12-01

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