WO2015111615A1 - レーザーエッチング加工用導電性ペースト、導電性薄膜、導電性積層体 - Google Patents

レーザーエッチング加工用導電性ペースト、導電性薄膜、導電性積層体 Download PDF

Info

Publication number
WO2015111615A1
WO2015111615A1 PCT/JP2015/051521 JP2015051521W WO2015111615A1 WO 2015111615 A1 WO2015111615 A1 WO 2015111615A1 JP 2015051521 W JP2015051521 W JP 2015051521W WO 2015111615 A1 WO2015111615 A1 WO 2015111615A1
Authority
WO
WIPO (PCT)
Prior art keywords
conductive
thin film
laser
resin
laser etching
Prior art date
Application number
PCT/JP2015/051521
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
憲一 江口
康博 坂本
Original Assignee
東洋紡株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to CN201580005656.5A priority Critical patent/CN105993050B/zh
Priority to KR1020167021704A priority patent/KR102312236B1/ko
Priority to JP2015518694A priority patent/JP6582982B2/ja
Publication of WO2015111615A1 publication Critical patent/WO2015111615A1/ja

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0448—Details of the electrode shape, e.g. for enhancing the detection of touches, for generating specific electric field shapes, for enhancing display quality
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens
    • 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
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • 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
    • G06F3/045—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means using resistive elements, e.g. a single continuous surface or two parallel surfaces put in contact

Definitions

  • the present invention relates to a method for producing a conductive pattern capable of producing a conductive pattern having a high arrangement density in a planar direction, and a conductive paste that can be suitably used for this production method.
  • the conductive pattern of the present invention can typically be used for electrode circuit wiring of a transparent touch panel.
  • the L / S requirement is about 100/100 ⁇ m or less, and there are cases where the L / S is required to be 50/50 ⁇ m or less. The situation is becoming difficult to deal with.
  • a photolithography method As an example of a candidate electrode circuit wiring forming technique that replaces screen printing, a photolithography method can be cited. If a photolithography method is used, it is possible to form a thin line having an L / S of 50/50 ⁇ m or less. However, there are also problems with photolithography.
  • the most typical example of photolithography is a method using a photosensitive resist. Generally, a photosensitive resist is applied to a copper foil portion of a surface substrate on which a copper foil layer is formed, and a photomask or a laser beam is used.
  • a desired pattern is exposed by a method such as direct drawing, the photosensitive resist is developed, and then a copper foil portion other than the desired pattern is dissolved and removed with a chemical to form a fine line pattern of the copper foil. For this reason, the environmental load by waste liquid processing is large, and also the process is complicated, and it has many problems including the viewpoint of production efficiency and the viewpoint of cost.
  • Patent Documents 1 and 2 There is also a photolithography method that does not use a photosensitive resist.
  • a dry coating film is formed using a conductive paste, and this is directly drawn with a laser beam.
  • a technique is disclosed in which a portion irradiated with is fixed on a substrate, an unirradiated portion is developed and removed, and a desired pattern is formed. If such a method is used, the process is simplified as compared with a general photolithography method because the photosensitive resist is not used.
  • the conventional photolithography method using a photosensitive resist is used.
  • the laser etching method disclosed in Patent Document 3 has recently attracted attention as an example of a candidate for electrode circuit wiring forming technology that replaces screen printing. If the laser etching method is used, it is possible to form a thin line having an L / S of 50/50 ⁇ m or less.
  • the laser etching method is a method in which a layer consisting of a binder resin and conductive powder (hereinafter referred to as a conductive thin film) is formed on an insulating substrate, and a part thereof is removed from the insulating substrate by laser light irradiation. That is.
  • the Ag nanowire base material can reduce resistance compared to the conventional ITO base material, and can realize a large touch panel. In addition, it has excellent flexibility and is suitable for the roll-to-roll method, which is advantageous in mass production.
  • the Ag nanowire layer has a higher contact resistance with the conductive thin film than the ITO layer, and a conductive paste applicable to the ITO film is not always applicable.
  • An object of the present invention is to provide a production method capable of producing high-density electrode circuit wiring without problems even when the laser etching method is applied to an Ag nanowire substrate. Moreover, it is providing the electrically conductive paste which can be used suitably for such a manufacturing method.
  • this invention consists of the following structures.
  • a binder resin As a
  • a conductive paste for laser etching characterized by containing a phenoxy resin.
  • the binder resin (a) contains 60% by weight or more of phenoxy resin.
  • the binder resin (a) has a number average molecular weight of 3,000 to 100,000. Or 2.
  • the conductive paste is filtered. ⁇ 3.
  • the conductive paste of the present invention is a conductive paste containing an organic component (A) containing a thermoplastic and / or thermosetting resin, silver powder (B), and an organic solvent (C).
  • A organic component
  • B thermoplastic and / or thermosetting resin
  • C organic solvent
  • An excellent conductive thin film can be formed.
  • FIG. 1 It is a schematic diagram showing the pattern which irradiates a laser beam to the laser-etching process appropriate evaluation test piece used by the Example of this invention and the comparative example.
  • the white portion is irradiated with laser light, and the conductive thin film formed on the substrate is removed.
  • the halftone dots are not irradiated with laser light.
  • the unit of dimension display in the figure is mm.
  • a white part is an Ag nanowire base material or an ITO base material, and a halftone dot part is an Ag paste.
  • the unit of dimension display in the figure is mm.
  • the conductive paste according to the present invention comprises an organic component (A) composed of thermoplastic and / or thermosetting components, silver powder (B) and an organic solvent (C) as essential components, and a binder resin in the organic component (A). (a), and (a) contains a phenoxy resin as an essential component.
  • the organic component (A) in the present invention refers to all parts excluding the inorganic component and the organic solvent (C) in the conductive paste.
  • the type of the binder resin (a) is not particularly limited as long as it is a thermoplastic resin, but is not limited to polyester resin, epoxy resin, phenoxy resin, polyamide resin, polyamideimide resin, polycarbonate resin, polyurethane resin, phenol resin, acrylic resin, polystyrene, styrene.
  • -Acrylic resin styrene-butadiene copolymer, phenol resin, polyethylene resin, polycarbonate resin, phenol resin, alkyd resin, styrene-acrylic resin, styrene-butadiene copolymer resin, polysulfone resin, polyethersulfone resin, vinyl chloride -Vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer, polystyrene, silicone resin, fluorine resin, etc., and these resins can be used alone or as a mixture of two or more. Can.
  • One or a mixture of two or more selected from the group consisting of a polyester resin, a polyurethane resin, an epoxy resin, a phenoxy resin, a vinyl chloride resin, and a fiber derivative resin is preferable.
  • a phenoxy resin is preferable as the binder resin (A) and essential as a component.
  • the reason why the phenoxy resin is preferable is that it is excellent in laser etching suitability and at the same time excellent in heat resistance and has high circuit reliability after laser etching.
  • the conductive paste using the phenoxy resin is applied to the Ag nanowire substrate.
  • the point that contact resistance is favorable is mentioned. This is thought to be due to the interaction between the OH groups rich in phenoxy resin and the Ag nanowire layer.
  • the phenoxy resin is a polyhydroxy polyether synthesized from bisphenols and epichlorohydrin and having a molecular weight of 3,000 to 100,000.
  • the phenoxy resin used as the binder resin (A) in the present invention include bisphenol A type, bisphenol A / F copolymer type, bisphenol S type, and bisphenol A / S copolymer type.
  • bisphenol A type is preferable from the viewpoint of substrate adhesion.
  • the number average molecular weight of the binder resin (a) in the present invention is not particularly limited, but the number average molecular weight is preferably 3,000 to 100,000, more preferably 8,000 to 50,000. If the number average molecular weight is too low, it is not preferable in terms of durability and heat and humidity resistance of the formed conductive thin film. On the other hand, if the number average molecular weight is too high, the cohesive strength of the resin increases and the durability as a conductive thin film is improved, but the suitability for laser etching is significantly deteriorated.
  • the glass transition temperature of the binder resin (a) in the present invention is preferably 60 ° C. or higher, more preferably 65 ° C. or higher. If the glass transition temperature is low, the laser etching processability may be improved, but the reliability after wet heat as a conductive thin film may be reduced, and the surface hardness will be lowered, and the tackiness will cause contact during use. There is a possibility that the transfer of the paste-containing component to the other side occurs and the reliability of the conductive thin film is lowered.
  • the glass transition temperature of the binder resin (A) is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 100 ° C. or lower in consideration of printability, adhesion, solubility, paste viscosity, and laser etching processing suitability. preferable.
  • the acid value of the organic component (A) in the present invention is not particularly limited, it is preferably 20 equivalents / 10 6 g or more and 500 equivalents / 10 6 g or less, and preferably 50 equivalents / 10 6 g or more and 400 equivalents / 10 6 g. The following is more preferable.
  • the acid value in the organic component (A) improves the substrate adhesion, but if it is too high, the hydrolysis of the organic component is promoted and the conductivity and substrate adhesion may be impaired.
  • the silver powder used in the present invention consists of silver alone, and does not include silver-coated alloy fine particles such as silver-coated copper powder which is copper powder plated or alloyed with silver.
  • the shape of the silver powder (B) used in the present invention is not particularly limited.
  • Examples of conventionally known shapes include flakes (flakes), spheres, dendrites (dendrites), and spherical primary particles described in JP-A-9-306240 are three-dimensional.
  • the center diameter (D50) of the silver powder (B) used in the present invention is preferably 4 ⁇ m or less.
  • the center diameter (D50) of the silver powder (B) used in the present invention is preferably 4 ⁇ m or less.
  • silver powder (B) having a center diameter of 4 ⁇ m or less the thin line shape of the laser etching processed portion tends to be good.
  • silver powder having a center diameter larger than 4 ⁇ m is used, the shape of the fine wire after laser etching is deteriorated, and as a result, the fine wires may come into contact with each other, possibly causing a short circuit. Furthermore, there is a possibility that the conductive thin film once peeled and removed by the laser etching process may adhere to the processing site again.
  • the lower limit of the center diameter of the silver powder (B) is not particularly limited, but it is preferable that the center diameter is 80 nm or more because it is easy to agglomerate when the particle diameter is small and dispersion becomes difficult as a result.
  • the center diameter is smaller than 80 nm, the cohesive force increases, the laser etching processing suitability deteriorates, and it is not preferable from the viewpoint of cost.
  • the central diameter (D50) is the particle diameter ( ⁇ m) at which the cumulative value is 50% in the cumulative distribution curve (volume) obtained by some measurement method.
  • the cumulative distribution curve is measured in the total reflection mode using a laser diffraction / scattering particle size distribution measuring apparatus (MICROTRAC HRA manufactured by Nikkiso Co., Ltd.).
  • binder components (a) 400 mass parts or more are preferable with respect to 100 mass parts of binder components (a), and, as for content of silver powder (B), from the viewpoint that the electroconductivity of the formed conductive thin film is favorable, it is 560 mass parts or more. More preferred. Further, the content of the component (B) is preferably 1,900 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin (A), from the viewpoint of good adhesion to the base material, Less than the mass part is more preferable.
  • Organic solvent (C) that can be used in the present invention is not particularly limited, but from the viewpoint of keeping the volatilization rate of the organic solvent within an appropriate range, the boiling point is preferably 100 ° C. or more and less than 300 ° C., more preferably. Has a boiling point of 150 ° C. or higher and lower than 280 ° C.
  • the conductive paste of the present invention is typically prepared by dispersing the thermoplastic resin (A), silver powder (B), organic solvent (C) and other components as necessary with a three-roll mill or the like.
  • the boiling point of the organic solvent is too low, the solvent volatilizes during the dispersion, and there is a concern that the component ratio constituting the conductive paste changes.
  • the boiling point of the organic solvent is too high, a large amount of the solvent may remain in the coating film depending on the drying conditions, which may cause a decrease in the reliability of the coating film.
  • the organic solvent (C) that can be used in the present invention is preferably one in which the binder (a) is soluble and the silver powder (B) can be dispersed well.
  • specific examples include ethyl diglycol acetate (EDGAC), butyl glycol acetate (BMGAC), butyl diglycol acetate (BDGAC), cyclohexanone, toluene, isophorone, ⁇ -butyrolactone, benzyl alcohol, Exson Chemical's Solvesso 100, 150, 200, a mixture of dimethyl ester of propylene glycol monomethyl ether acetate, adipic acid, succinic acid and glutaric acid (for example, DBE manufactured by DuPont Co., Ltd.), terpionol, and the like.
  • binder component (a EDGAC, BMGAC, BDGAC, and mixed solvents thereof are preferred from the viewpoints of excellent solubility in), moderate solvent volatility during continuous printing, and good suitability for printing
  • the content of the organic solvent (C) is preferably 5 parts by weight or more and 40 parts by weight or less, more preferably 10 parts by weight or more and 35 parts by weight or less with respect to 100 parts by weight of the total paste. .
  • the content of the organic solvent (C) is too high, the paste viscosity becomes too low, and the sagging tends to occur during fine line printing.
  • the content of the organic solvent (C) is too low, the viscosity as a paste becomes extremely high, and, for example, the screen printability when forming the conductive thin film is significantly reduced. The film thickness becomes thick and the laser etching processability may be reduced.
  • ⁇ Laser light absorber (D)> You may mix
  • the laser light absorber (D) is an additive having strong absorption at the wavelength of the laser light, and the laser light absorber (D) itself may be conductive or non-conductive. Good.
  • a YAG laser having a fundamental wave wavelength of 1064 nm is used as a light source
  • a dye and / or pigment having strong absorption at a wavelength of 1064 nm can be used as the laser light absorber (D).
  • the conductive thin film of the present invention absorbs the laser light with high efficiency, and the volatilization and thermal decomposition of the binder component (a) due to heat generation is promoted. Will improve.
  • examples of those having conductivity include carbon-based fillers such as carbon black and graphite powder.
  • the compounding of the carbon-based filler has the effect of increasing the conductivity of the conductive thin film of the present invention.
  • carbon black since carbon black has an absorption wavelength in the vicinity of 1060 nm, it has a wavelength of 1064 nm such as YAG laser and fiber laser.
  • the conductive thin film When irradiated with laser light, the conductive thin film absorbs laser light with high efficiency, so the sensitivity to laser light irradiation increases, and it is good even when the scanning speed of laser irradiation is increased and / or when the laser light source is low power The effect that laser etching processing suitability is obtained can be expected.
  • the content of the carbon-based filler is preferably 0.1 to 5 parts by weight and more preferably 0.3 to 2 parts by weight with respect to 100 parts by weight of the silver powder (B). When the blending ratio of the carbon filler is too low, the effect of increasing the conductivity and the effect of increasing the sensitivity to laser light irradiation are small.
  • the conductivity of the conductive thin film tends to be lowered, and further, the resin is adsorbed to the void portion of the carbon and the adhesion with the substrate is lowered. Dots may occur.
  • nonconductive materials include conventionally known dyes, pigments, and infrared absorbers. More specifically, azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc.
  • the dyes and pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymer-bonded pigments.
  • infrared absorbers examples include NIR-IM1, which is a diimonium salt type infrared absorber, and NIR-AM1, an aminium salt type (both manufactured by Nagase ChemteX Corporation).
  • NIR-IM1 which is a diimonium salt type infrared absorber
  • NIR-AM1 an aminium salt type (both manufactured by Nagase ChemteX Corporation).
  • These non-conductive laser light absorbers (D) are contained in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight.
  • the blending ratio of the non-conductive laser light absorber (D) is too low, the effect of increasing the sensitivity to laser light irradiation is small.
  • the blending ratio of the non-conductive laser light absorber (D) is too high, the conductivity of the conductive thin film may be lowered, and the color of the laser light absorber becomes remarkable, which is not preferable depending on the application. There is.
  • inorganic substances can be added to the conductive paste of the present invention.
  • inorganic substances include silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, tantalum carbide, niobium carbide, tungsten carbide, chromium carbide, molybdenum carbide, calcium carbide, diamond carbon lactam, and other carbides; boron nitride , Various nitrides such as titanium nitride and zirconium nitride, various borides such as zirconium boride; titanium oxide (titania), calcium oxide, magnesium oxide, zinc oxide, copper oxide, aluminum oxide, silica, fumed silica (for example, Japan) Aerosil) and other oxides such as colloidal silica; various titanate compounds such as calcium titanate, magnesium titanate and strontium titanate; sulfides such as molybdenum disulfide; magnesium fluoride and
  • a fumed silica is preferable from a viewpoint of providing durability, printability, especially screen printability.
  • the following acid component can be added to the conductive paste of the present invention.
  • the acid component includes aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, and aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, and azelaic acid.
  • Dibasic acids having 12 to 28 carbon atoms such as acids and dimer acids, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic anhydride, 3 -Methylhexahydrophthalic anhydride, 2-methylhexahydrophthalic anhydride, dicarboxy hydrogenated bisphenol A, dicarboxy hydrogenated bisphenol S, dimer acid, hydrogenated dimer acid, hydrogenated naphthalene dicarboxylic acid, tricyclodecane dicarboxylic acid Alicyclic dicarboxylic acids such as Dorokishi benzoic acid, and hydroxycarboxylic acids such as lactic acid.
  • Trivalent or higher carboxylic acids such as trimellitic anhydride and pyromellitic anhydride, unsaturated dicarboxylic acids such as fumaric acid, and carboxylic acid diols such as dimethylolbutanoic acid and dimethylolpropionic acid can be added.
  • the conductive paste of the present invention includes a thixotropic agent, an antifoaming agent, a flame retardant, a tackifier, a hydrolysis inhibitor, a leveling agent, a plasticizer, an antioxidant, an ultraviolet absorber, a flame retardant, and a pigment.
  • Dyes can be blended.
  • a carbodiimide, an epoxy, etc. can also be mix
  • ⁇ Curing agent (E)> You may mix
  • a curing agent By adding a curing agent, there is a possibility that the curing temperature becomes high and the load of the production process may increase.
  • the heat and humidity resistance of the coating film can be improved by crosslinking caused by heat generated during coating film drying or laser etching .
  • the type of the curing agent capable of reacting with the binder component (a) of the present invention is not limited, but is preferably an isocyanate compound and / or an epoxy resin in view of adhesion, flex resistance, curability and the like. Furthermore, regarding the isocyanate compound, it is preferable to use a blocked isocyanate group since the storage stability is improved.
  • curing agents other than isocyanate compounds include known compounds such as amino resins such as methylated melamine, butylated melamine, benzoguanamine, and urea resin, acid anhydrides, imidazoles, and phenol resins. These curing agents can be used in combination with a known catalyst or accelerator selected according to the type.
  • the blending amount of the curing agent is blended to such an extent that the effects of the present invention are not impaired, and is not particularly limited, but is 0.5 to 50 with respect to 100 parts by mass of the binder component (a). Part by mass is preferred, 1 to 30 parts by mass is more preferred, and 2 to 20 parts by mass is even more preferred.
  • aromatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate
  • aromatic diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, etc.
  • Alicyclic diisocyanates, or trimers of these isocyanate compounds, and excess amounts of these isocyanate compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine
  • Low molecular active hydrogen compounds such as Polyester polyols, polyether polyols, terminal isocyanate group-containing compounds obtained by reacting a polymeric active hydrogen compound such as polyamides and the like.
  • isocyanate group blocking agent examples include phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol; oximes such as acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime.
  • Alcohols such as methanol, ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol ; Lactams such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -propylolactam, and the like, as well as aromatic amines, imides, acetylacetone, Seto acetate, active methylene compounds such as malonic acid ethyl ester, mercaptans, imines, imidazoles, ureas, diaryl compounds, sodium bisulfite, etc. can be mentioned. Of these, oximes, imidazoles, and amines are particularly preferable from the viewpoint of curability.
  • Examples of the epoxy compound used as a curing agent in the present invention include glycidyl ether types such as bisphenol A glycidyl ether, bisphenol S glycidyl ether, novolak glycidyl ether, and bromo bromide, hexahydrophthalic acid glycidyl ester, and dimer acid glycidyl ester.
  • Examples include glycidyl ester type, triglycidyl isocyanurate, or 3,4 − alicyclic or aliphatic epoxides such as epoxy cyclohexyl methyl carboxylate, epoxidized polybutadiene, and epoxidized soybean oil.
  • bisphenol A glycidyl ether is most preferable, and among them, those having a molecular weight of less than 3000 and having two or more glycidyl ether groups in one molecule are more preferable.
  • the viscosity of the electrically conductive paste of this invention is not specifically limited, What is necessary is just to adjust suitably according to the formation method of a coating film.
  • the viscosity of the conductive paste is preferably 100 dPa ⁇ s or more, more preferably 150 dPa ⁇ s or more at the printing temperature.
  • the upper limit is not particularly limited, but if the viscosity is too high, the thickness of the conductive thin film becomes too thick, and the suitability for laser etching may deteriorate.
  • the conductive paste of the present invention preferably has an F value of 60 to 95%, more preferably 75 to 95%.
  • the filler mass part referred to here is the mass part of the conductive powder, and the solid content mass part is a mass part of components other than the solvent, and includes all of the conductive powder, organic components, other curing agents and additives. If the F value is too low, a conductive thin film showing good conductivity cannot be obtained. If the F value is too high, the adhesion between the conductive thin film and the substrate and / or the surface hardness of the conductive thin film tends to decrease. Yes, printability is inevitable.
  • the conductive powder refers to silver powder (B).
  • the conductive paste of the present invention can be prepared by dispersing the organic component (A), the silver powder (B), the organic solvent (C), and other components as necessary with a three roll or the like.
  • the binder component (a) is dissolved in the organic solvent (C).
  • silver powder (B) and additives as necessary are added, and dispersion is carried out with a double planetary, a dissolver, a planetary stirrer or the like.
  • the conductive paste thus obtained can be filtered if necessary. There is no problem even if the dispersion is performed using other dispersers such as a bead mill, a kneader, and an extruder.
  • the opening as a filter for filtering the conductive paste is not particularly limited, but a filter of 25 ⁇ m or less is preferable, more preferably 20 ⁇ m or less, and most preferably 15 ⁇ m or less.
  • a filter having a mesh size exceeding 25 ⁇ m is used, undispersed conductive powder, coarse particles, foreign matter, etc. cannot be removed, and a short circuit occurs between the fine wires after etching, resulting in poor yield.
  • the opening is preferably 1 ⁇ m or more, and if it is finer than this, depending on the particle diameter of the silver powder, the filtration rate is remarkably lowered, and finally the filtration filter is clogged. As a result, the number of filtration filter replacements increases, and the production efficiency decreases significantly.
  • the material of the filter for filtering the conductive silver paste is not particularly limited, such as stainless steel, nickel, polyester, nylon, PTFE (polytetrafluoroethylene), polypropylene, and other metals, but stainless steel is preferable from the viewpoint of durability. Moreover, there is no restriction
  • the method of filtering the conductive silver paste is not particularly limited, but the method of scraping the paste with its own weight while stirring and rotating a stirring blade made of plastic (for example, polyoxymethylene) with excellent wear resistance is apparatus-like.
  • the manufacturing efficiency is good.
  • the number of rotations of stirring is not limited as long as paste filtration does not impair manufacturing efficiency.
  • PF160A and PF320A manufactured by Protech Co., Ltd. are preferable.
  • the conductive paste of the present invention is formed by applying or printing the conductive paste of the present invention on a substrate to form a coating film, and then evaporating the organic solvent (C) contained in the coating film and drying the coating film. Can be formed.
  • the method for applying or printing the conductive paste on the substrate is not particularly limited, but printing by the screen printing method is simple in the process and the technology that is widely used in the industry for forming an electric circuit using the conductive paste It is preferable from the point.
  • the conductive paste can be applied or printed on a portion slightly wider than the portion of the conductive thin film that is ultimately required as an electric circuit, reducing the load of the laser etching process and improving the efficiency of the electric circuit of the present invention. From the viewpoint of forming, it is preferable.
  • a material excellent in dimensional stability is preferably used.
  • a film made of a material having excellent flexibility such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, or polycarbonate can be used.
  • inorganic materials, such as glass can also be used as a base material.
  • the thickness of the substrate is not particularly limited, but is preferably from 50 to 350 ⁇ m, more preferably from 100 to 250 ⁇ m from the viewpoint of mechanical properties, shape stability, or handleability of the pattern forming material.
  • the adhesion between the conductive thin film and the substrate can be improved.
  • the physical treatment method include a sand blast method, a wet blast method in which a liquid containing fine particles is sprayed, a corona discharge treatment method, a plasma treatment method, an ultraviolet ray or vacuum ultraviolet ray irradiation treatment method, and the like.
  • chemical treatment methods include strong acid treatment methods, strong alkali treatment methods, oxidizing agent treatment methods, and coupling agent treatment methods.
  • the base material may have a transparent conductive layer.
  • the conductive thin film of the present invention can be laminated on the transparent conductive layer.
  • the material for the transparent conductive layer is not particularly limited, and examples thereof include an ITO film mainly composed of indium tin oxide and a silver nanowire film composed of nano-sized linear silver.
  • the transparent conductive layer is not limited to the one formed on the entire surface of the base material, but can also be one obtained by removing a part of the transparent conductive layer by etching or the like.
  • the step of evaporating the organic solvent (C) is preferably performed at room temperature and / or under heating.
  • the heating temperature is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 110 ° C. or higher. Further, from the viewpoint of heat resistance of the underlying transparent conductive layer and energy saving in the production process, the heating temperature is preferably 150 ° C. or lower, more preferably 135 ° C. or lower, and further preferably 130 ° C. or lower.
  • the curing reaction proceeds when the step of evaporating the organic solvent (C) is performed under heating.
  • the thickness of the conductive thin film of the present invention may be set to an appropriate thickness according to the application used.
  • the thickness of the conductive thin film is preferably 3 ⁇ m or more and 30 ⁇ m or less, more preferably 4 ⁇ m from the viewpoint that the conductivity of the conductive thin film after drying is good and the suitability for laser etching processing is good. As mentioned above, it is 20 micrometers or less, More preferably, they are 4 micrometers or more and 10 micrometers or less. If the conductive thin film is too thin, there is a possibility that desired conductivity as a circuit cannot be obtained. If the film thickness is too thick, an excessive amount of laser irradiation is required for laser etching, which may damage the substrate.
  • the conductive thin film tends to be etched easily, and a short circuit between lines due to insufficient etching or disconnection due to excessive etching tends to occur. For this reason, it is better that the variation in film thickness is small.
  • the surface roughness Ra of the conductive thin film of the present invention is preferably 0.7 ⁇ m or less, more preferably 0.5 ⁇ m or less. If the surface roughness Ra is too high, the etching end portion of the conductive thin film is likely to be jagged, and there is a possibility that a short circuit between lines or disconnection due to excessive etching is likely to occur. Since the surface roughness Ra is strongly influenced by the paste composition (especially organic component species and silver powder species), paste viscosity, and screen printing conditions, it is necessary to adjust and control them appropriately.
  • the electrical circuit of the present invention removes a part of the conductive layer from the substrate by irradiating at least a part of the conductive thin film formed on the substrate with the conductive paste of the present invention. It is an electric circuit which has the wiring site
  • the pattern formation process can be a dry process, and no waste liquid containing metal components is generated, so there is no need for waste liquid treatment and the environment is friendly. It can be said that it is a process.
  • the process is simple, investment in manufacturing equipment can be suppressed, and maintenance and management of the manufacturing equipment after operation is easy.
  • the method for forming the conductive thin film on the substrate with the conductive paste is not particularly limited, but can be performed by printing or painting.
  • the laser beam irradiation method is not particularly limited, but a laser etching processing apparatus that has been widely used in recent years, or a device that further improves the dimensional accuracy thereof can be used. Since the laser etching processing apparatus can directly use data produced by image processing application software such as CAD for laser processing, it is very easy to switch manufacturing patterns. This can be cited as one of the advantages over the conventional pattern formation by the screen printing method.
  • the conductive thin film of the present invention preferably has strong absorption at the wavelength of the irradiated laser light. Therefore, it is preferable to select a laser species having energy in a wavelength region where any of the components constituting the conductive thin film of the present invention has strong absorption.
  • Common laser types include excimer laser (fundamental wavelength 193 to 308 nm), YAG laser (fundamental wave wavelength 1064 nm), fiber laser (fundamental wave wavelength 1060 nm), CO2 laser (fundamental wave wavelength) 10600 nm), semiconductor lasers, and the like. Basically, there is no problem even if any system and laser type of any wavelength are used. By selecting a laser species that matches the absorption wavelength region of any constituent of the conductive thin film and that can be irradiated with a wavelength that the substrate does not have strong absorption, the conductive thin film at the laser light irradiation site is selected. Can be efficiently removed, and damage to the substrate can be avoided.
  • the wavelength of the fundamental wave is preferably in the range of 532 to 10700 nm as the laser type to be irradiated.
  • a YAG laser or a fiber laser may be used. Since the base material has no absorption at the wavelength of the fundamental wave, it is particularly preferable in that the base material is not easily damaged.
  • Laser output and frequency are not particularly limited, but are adjusted so that the conductive thin film at the laser beam irradiation site can be removed and the underlying substrate is not damaged.
  • the laser output is preferably adjusted as appropriate within a range of 0.5 to 100 W and a frequency of 10 to 1000 kHz. If the laser output is too low, removal of the conductive thin film tends to be insufficient, but such tendency can be avoided to some extent by reducing the laser scanning speed or increasing the number of scans. If the laser output is too high, the portion where the conductive thin film is peeled off due to the diffusion of heat from the irradiated portion becomes extremely larger than the laser beam diameter, and the line width may be too thin or disconnected. In this respect, the laser output is preferably adjusted appropriately within the range of 0.5 to 20 W and the frequency of 10 to 800 kHz, more preferably 0.5 to 12 W and the frequency of 10 to 600 kHz.
  • the scanning speed of the laser beam is preferably as high as possible from the viewpoint of improving the production efficiency by reducing the tact time. Specifically, it is preferably 1000 mm / s or more, more preferably 1500 mm / s or more, and further preferably 2000 mm / s or more. It is. If the scanning speed is too slow, not only the production efficiency is lowered, but the conductive thin film and the substrate may be damaged by the thermal history. Although the upper limit of the processing speed is not particularly defined, if the scanning speed is too high, the removal of the conductive thin film at the laser light irradiation site may be incomplete and the circuit may be short-circuited.
  • Laser beam scanning may be performed by either moving the laser beam projectile, moving the irradiated object irradiated with the laser beam, or combining both, for example, by using an XY stage. Further, the laser beam can be scanned by changing the irradiation direction of the laser beam using a galvanometer mirror or the like.
  • the energy density per unit area can be increased by using a condensing lens (such as an achromatic lens) at the time of laser light irradiation.
  • a condensing lens such as an achromatic lens
  • the advantage of this method is that the energy density per unit area can be increased compared to the case of using a mask, so laser etching can be performed at a high scanning speed even with a low-power laser oscillator. The point that becomes possible.
  • the focal length must be adjusted according to the film thickness applied to the substrate, but it can be adjusted so that the substrate is not damaged and the predetermined conductive thin film pattern can be removed and removed. preferable.
  • laser beam scanning is repeated a plurality of times in the same pattern. Even if there is an incompletely removed conductive thin film portion in the first scan, or even if the component constituting the removed conductive thin film is attached to the substrate again, the laser light irradiated portion is scanned multiple times. It is possible to completely remove the conductive thin film.
  • the upper limit of the number of scans is not particularly limited. However, care must be taken because the periphery of the processed part may be damaged and discolored by being subjected to heat history a plurality of times, and the physical properties of the coating film may deteriorate. Of course, the smaller the number of scans, the better from the viewpoint of production efficiency.
  • laser beam scanning is not repeated a plurality of times in the same pattern. As long as the number of scans is small, the production efficiency is naturally excellent as long as the properties of the obtained conductive thin film, conductive laminate and electric circuit are not adversely affected.
  • the conductive thin film of the present invention contains expensive conductive powder at a high concentration, it is included in the conductive thin film removed from the base material in view of the total cost required for manufacturing the electric circuit to be manufactured. It is important to collect and reuse the conductive powder.
  • a highly profitable processing method can be obtained by providing a high-performance dust collector near the laser beam irradiation site and constructing a system for efficiently collecting the conductive powder.
  • the conductive thin film, conductive laminate and / or electric circuit of the present invention can be used as a constituent member of a touch panel.
  • the touch panel may be a resistive film type or a capacitive type. Although it can be applied to any touch panel, the paste is suitable for forming a thin line, and therefore can be particularly suitably used for electrode wiring of a capacitive touch panel.
  • a base material which comprises the said touch panel it is preferable to use the base material which has transparent conductive layers, such as an ITO film
  • the sample resin was dissolved in tetrahydrofuran so that the resin concentration was about 0.5% by weight and filtered through a polytetrafluoroethylene membrane filter having a pore size of 0.5 ⁇ m to obtain a GPC measurement sample.
  • GPC measurement of a resin sample using tetrahydrofuran as a mobile phase, a gel permeation chromatograph (GPC) Prominence manufactured by Shimadzu Corporation, and a differential refractometer (RI meter) as a detector at a column temperature of 30 ° C. and a flow rate of 1 ml / min. was done.
  • the number average molecular weight was a standard polystyrene equivalent value, and was calculated by omitting a portion corresponding to a molecular weight of less than 1000.
  • GPC column shodex KF-802, 804L and 806L manufactured by Showa Denko KK were used.
  • Glass transition temperature (Tg) 5 mg of sample resin is put in an aluminum sample pan, sealed, and measured with a differential scanning calorimeter (DSC) DSC-220 manufactured by Seiko Instruments Inc. up to 200 ° C. at a heating rate of 20 ° C./min. And the temperature at the intersection of the base line extension below the glass transition temperature and the tangent indicating the maximum slope at the transition.
  • DSC differential scanning calorimeter
  • Paste viscosity Viscosity was measured at 20 rpm using a BH viscometer (manufactured by Toki Sangyo Co., Ltd.) at a sample temperature of 25 ° C.
  • Conductive Laminate Test Piece 1 A 400 ⁇ m thick PET film (Lumirror S manufactured by Toray Industries, Inc.), ITO film (manufactured by Oike Industry Co., Ltd., KH300), and Ag nanowire base material each having a thickness of 100 ⁇ m.
  • a conductive paste was printed by using a stainless steel screen by a screen printing method to form a solid coating pattern with a width of 25 mm and a length of 450 mm, and then heated at 130 ° C. for 30 minutes in a hot-air circulating drying oven. A laminate test piece was obtained. The coating thickness at the time of printing was adjusted so that the dry film thickness was 5 to 10 ⁇ m. 5.
  • Conductive Laminate Test Piece 2 A conductive paste is applied to each of the ITO film (Koh300, manufactured by Oike Kogyo Co., Ltd.) and the Ag nanowire substrate by screen printing using a 400 mesh stainless screen as shown in FIG.
  • the conductive laminate test piece 2 was printed as described above and then heated at 130 ° C. for 30 minutes in a hot-air circulating drying oven. The coating thickness at the time of printing was adjusted so that the dry film thickness was 5 to 10 ⁇ m.
  • the sheet resistance and film thickness of the conductive laminate test piece 1 were measured, and the specific resistance was calculated.
  • a gauge stand ST-022 manufactured by Ono Sokki Co., Ltd.
  • the sheet resistance was measured for four test pieces using MILLIOHMMETER 4338B (manufactured by HEWLETT PACKARD), and the average value was used.
  • the range that can be detected by this milliohm meter is 1 ⁇ 10 ⁇ 2 ( ⁇ ⁇ cm) or less, and a specific resistance of 1 ⁇ 10 ⁇ 2 ( ⁇ ⁇ cm) or more is outside the measurement limit.
  • Pencil Hardness The conductive laminate test piece 1 was placed on a 2 mm thick SUS304 plate, and the pencil hardness was measured according to JIS K 5600-5-4: 1999. 9. Contact resistance The resistance values between 1a-2a, 2a-3a, and 1a-3a of the conductive laminate test piece 2 were measured, and the contact resistance value was calculated from the following equation.
  • Contact resistance value ((resistance value between 1a and 2a) + (resistance value between 2a and 3a)-(resistance value between 1a and 3a)) / 2 ⁇ Initial value> ⁇ : Contact resistance ⁇ 50 ⁇ ⁇ : Contact resistance value> 50 ⁇ ⁇ After wet heat resistance test> ⁇ : Contact resistance value after wet heat resistance test / initial contact resistance value ⁇ 1.2 ⁇ : Contact resistance value after room thermal resistance test / initial contact resistance value> 1.2 12 Surface Roughness In the conductive laminate test piece 1, the surface roughness Ra was measured using a surface roughness meter (Handy Surf E-35B, Tokyo Seimitsu Co., Ltd., calculated based on JIS-1994).
  • Moisture and heat resistance test The conductive laminate test pieces 1 and 2 were heated at 80 ° C. for 300 hours, then heated at 85 ° C. and 85% RH (relative humidity) for 300 hours, and then allowed to stand at room temperature for 24 hours, after which various evaluations were performed. .
  • a conductive paste was printed and applied in a 2.5 ⁇ 10 cm rectangle on a polyester base material (Lumirror S (thickness: 100 ⁇ m) manufactured by Toray Industries, Inc.) by a screen printing method.
  • a 400 stainless mesh emulsion thickness 10 ⁇ m, wire diameter 18 ⁇ m (manufactured by Murakami Co., Ltd.), calendaring was used as a screen plate, and printing was performed at a squeegee speed of 50 mm / s. After the printing application, drying was performed at 130 ° C. for 30 minutes in a hot air circulation drying oven to obtain a conductive thin film.
  • the paste was diluted and adjusted so that the film thickness was 5 to 7 ⁇ m.
  • laser etching was performed on the conductive thin film prepared by the above method to produce a pattern having four straight portions with a length of 50 mm as shown in FIG.
  • a YAG laser (wavelength: 1064 nm) was used as the laser light source, and the frequency was 200 kHz, the output was 11 W, and the scanning speed was 3000 mm / s.
  • Evaluation items and measurement conditions are as follows.
  • the line width of the silver coating film after laser etching was measured. The measurement was performed using a laser microscope (Keyence VHX-1000), and judged according to the following evaluation criteria.
  • ⁇ The line width of the portion where the conductive thin film is removed is 28 to 32 ⁇ m.
  • ⁇ The line width of the portion where the conductive thin film is removed is 24 to 27 ⁇ m or 33 to 36 ⁇ m.
  • X The line width of the portion where the conductive thin film has been removed is 23 ⁇ m or less, or 37 ⁇ m or more
  • Laser etching processing suitability evaluation 1 Conductivity between both ends of fine wire
  • the evaluation was made based on whether or not conduction between both ends of the thin wire was ensured. Specifically, a tester is applied to each terminal A1-terminal B1, between terminal A2-terminal B2, between terminal A3-terminal B3, and between terminal A4-terminal B4 to confirm the presence or absence of conduction. Judged.
  • ⁇ Conduction between both ends of the fine wire for all four fine wires
  • ⁇ Conductivity between both ends of the thin wire for one to three of the four thin wires
  • ⁇ Fine wire for all four thin wires No conduction between both ends (Laser etching process suitability evaluation 2 Insulation between adjacent thin wires)
  • the laser etching process suitability evaluation test piece was evaluated based on whether insulation between adjacent thin wires was ensured. Specifically, a tester was applied to each of the terminals A1 to A2, between the terminals A2 and A3, and between the terminals A3 and A4 to confirm the presence or absence of conduction, and the determination was made according to the following evaluation criteria.
  • ⁇ All adjacent fine wires are insulated
  • Some adjacent fine wires are insulated
  • All adjacent fine wires are not insulated
  • Example 1 2857 parts of phenoxy resin PH-1 dissolved in EDGAC so that the solid content concentration is 35% by mass (1000 parts in terms of solid part), 8361 parts of flaky silver powder 1, 100 parts of curing agent 1, and a leveling agent 59 parts, 34 parts of additive 1 and 164 parts of EDGAC as a solvent were blended and dispersed by passing twice through a chilled three-roll kneader. Next, a 500 mesh (stainless mesh filter (line diameter 25 ⁇ m, opening 30 ⁇ m)) was attached to a paste filter (Protech PF320A), and the paste was filtered. After printing in a predetermined pattern, the film was dried at 130 ° C. for 30 minutes to obtain a conductive thin film, the basic physical properties were measured using this conductive thin film, and then laser etching processing was examined. The evaluation results of the coating film and laser etching processability are shown in Table 1.
  • Examples 2 to 11 Example 2 to 12 were carried out by changing the resin and the composition of the conductive paste.
  • Table 1 shows the formulation and evaluation results of the conductive paste.
  • good coating film physical properties could be obtained by heating at a relatively low temperature of 130 ° C. for 30 minutes in an oven. Also, the adhesion to the ITO film and the adhesion after the wet heat environment test were good.
  • Binder component PH-6 YP-70 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • Silver powder 1 Agglomerated powder (D50: 0.5 ⁇ m)
  • Silver powder 2 Flake silver powder (D50: 1 ⁇ m)
  • Ketjen Black Ketjen ECP600JD made by Lion Corporation Hardener 1: MF-K60X manufactured by Asahi Kasei Chemicals Corporation Hardener 2: Baksenden BI-7960 Curing catalyst: Kyodo Pharmaceutical Co., Ltd.
  • KS1260 Leveling agent Kyoeisha Chemical Co., Ltd.
  • MK Conk Dispersant 1 Disperbyk 2155 manufactured by Big Chemie Japan Co., Ltd.
  • Additive 1 Silica R972 manufactured by Nippon Aerosil Co., Ltd.
  • Additive 2 Dimethylol butanoic acid dissolved in EDGAC at a solid content of 20% (manufactured by Nippon Kasei Co., Ltd.)
  • Additive 3 BYK-410 manufactured by Big Chemie Japan EDGAC: Ethyl diglycol acetate manufactured by Daicel Corp.
  • BMGAC Butyl glycol acetate manufactured by Daicel Corp.
  • DBE Mixture of adipic acid, succinic acid and dimethyl ester of glutaric acid manufactured by DuPont Co., Ltd.
  • the resin solution thus obtained was dropped on a polypropylene film and spread using a stainless steel applicator to obtain a resin solution thin film. This was left in a hot air dryer adjusted to 120 ° C. for 3 hours to volatilize the solvent, and then the resin thin film was peeled off from the polypropylene film to obtain a film-like dry resin thin film.
  • the thickness of the dry resin thin film was about 30 ⁇ m.
  • Table 1 shows the evaluation results of various resin properties, using the dry resin thin film on the left as a sample resin of phenoxy resin PH-3.
  • the conductive paste for laser etching processing of the present invention provides a conductive thin film that is excellent in wet heat environment reliability while maintaining the suitability of laser etching processing and can maintain the durability of the coating film as a conductive thin film.
  • it is useful as a conductive paste used for a mobile phone, a notebook personal computer, an electronic book or the like equipped with a touch panel.
PCT/JP2015/051521 2014-01-22 2015-01-21 レーザーエッチング加工用導電性ペースト、導電性薄膜、導電性積層体 WO2015111615A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201580005656.5A CN105993050B (zh) 2014-01-22 2015-01-21 激光蚀刻加工用导电浆料、导电性薄膜、导电性层叠体
KR1020167021704A KR102312236B1 (ko) 2014-01-22 2015-01-21 레이저 에칭 가공용 도전성 페이스트, 도전성 박막, 도전성 적층체
JP2015518694A JP6582982B2 (ja) 2014-01-22 2015-01-21 レーザーエッチング加工用導電性ペースト、導電性薄膜、導電性積層体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014009320 2014-01-22
JP2014-009320 2014-01-22

Publications (1)

Publication Number Publication Date
WO2015111615A1 true WO2015111615A1 (ja) 2015-07-30

Family

ID=53681417

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/051521 WO2015111615A1 (ja) 2014-01-22 2015-01-21 レーザーエッチング加工用導電性ペースト、導電性薄膜、導電性積層体

Country Status (5)

Country Link
JP (1) JP6582982B2 (zh)
KR (1) KR102312236B1 (zh)
CN (1) CN105993050B (zh)
TW (1) TWI657098B (zh)
WO (1) WO2015111615A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017159381A1 (ja) * 2016-03-17 2017-09-21 東洋紡株式会社 導電性皮膜およびレーザーエッチング加工用導電性ペースト
WO2018092762A1 (ja) * 2016-11-21 2018-05-24 東洋紡株式会社 導電性ペースト、導電性膜、導電性膜の製造方法、導電性微細配線、導電性微細配線の製造方法。

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106971789A (zh) * 2017-03-18 2017-07-21 苏州思创源博电子科技有限公司 一种透明金属导电薄膜的制备方法
CN107086083A (zh) * 2017-04-24 2017-08-22 苏州思创源博电子科技有限公司 一种具有柔性衬底的金属导电薄膜的制备方法
JPWO2019038860A1 (ja) * 2017-08-23 2019-11-07 三菱電機株式会社 レーザ加工方法およびレーザ加工装置
JP6521138B1 (ja) * 2018-04-19 2019-05-29 東洋インキＳｃホールディングス株式会社 成形フィルム用導電性組成物、成形フィルム、成形体およびその製造方法
KR102152841B1 (ko) * 2018-11-30 2020-09-07 엘에스니꼬동제련 주식회사 경시 점도변화가 적은 도전성 페이스트의 제조방법
CN110853795B (zh) * 2019-11-22 2021-08-31 广州精卓化工有限公司 一种镭射蚀刻型导电银浆及其制备方法和应用
CN113053560B (zh) * 2021-06-01 2021-09-03 西安宏星电子浆料科技股份有限公司 一种高性能厚膜电阻器用电阻浆料

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005353784A (ja) * 2004-06-10 2005-12-22 Mitsubishi Plastics Ind Ltd 多層配線基板用導電性ペースト組成物
JP2008013809A (ja) * 2006-07-05 2008-01-24 Az Electronic Materials Kk レーザーアブレーションによる機能膜の製造法およびそれに用いるレーザーアブレーション加工用組成物
JP2010044968A (ja) * 2008-08-13 2010-02-25 Nissha Printing Co Ltd 導電性パターン被覆体の製造方法および導電性パターン被覆体
JP2014002992A (ja) * 2012-06-14 2014-01-09 Pelnox Ltd レーザーエッチング用導電性ペースト組成物
WO2014013899A1 (ja) * 2012-07-20 2014-01-23 東洋紡株式会社 レーザーエッチング加工用導電性ペースト、導電性薄膜および導電性積層体
JP2014107533A (ja) * 2012-11-29 2014-06-09 Pelnox Ltd レーザーエッチング用導電性ペースト組成物

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4396126B2 (ja) * 2003-04-16 2010-01-13 藤倉化成株式会社 導電性銅ペースト組成物
JP4687042B2 (ja) * 2004-09-09 2011-05-25 住友電気工業株式会社 導電性ペーストの製造方法
JP2007297608A (ja) * 2006-04-07 2007-11-15 Sumitomo Metal Mining Co Ltd 透光性導電塗料及び透光性導電膜並びに分散型エレクトロルミネッセンス素子
JP2009059574A (ja) * 2007-08-31 2009-03-19 Sony Chemical & Information Device Corp 導電ペースト及びこれを用いた多層配線基板
JP5236557B2 (ja) 2009-03-31 2013-07-17 太陽ホールディングス株式会社 レーザーを用いたパターン形成方法
ES2438745T3 (es) * 2009-09-04 2014-01-20 Basf Se Composición para la impresión de circuitos impresos así como un procedimiento para la fabricación de células solares
JP4968410B2 (ja) * 2009-10-15 2012-07-04 東洋紡績株式会社 導電性ペースト、導電性膜、タッチパネル、及び導電性薄膜の製造方法
JP4702499B1 (ja) * 2010-02-05 2011-06-15 東洋インキＳｃホールディングス株式会社 導電性インキ、および導電パターン付き積層体とその製造方法
JP2011181338A (ja) 2010-03-01 2011-09-15 Taiyo Holdings Co Ltd レーザーを用いた導電パターン形成方法及びその方法に用いる組成物
JP5051553B2 (ja) * 2010-04-19 2012-10-17 住友金属鉱山株式会社 導電性ペーストの製造方法
JP6016328B2 (ja) 2011-02-07 2016-10-26 株式会社三共 遊技用システム
JP5651625B2 (ja) * 2012-03-21 2015-01-14 京都エレックス株式会社 加熱硬化型導電性ペースト組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005353784A (ja) * 2004-06-10 2005-12-22 Mitsubishi Plastics Ind Ltd 多層配線基板用導電性ペースト組成物
JP2008013809A (ja) * 2006-07-05 2008-01-24 Az Electronic Materials Kk レーザーアブレーションによる機能膜の製造法およびそれに用いるレーザーアブレーション加工用組成物
JP2010044968A (ja) * 2008-08-13 2010-02-25 Nissha Printing Co Ltd 導電性パターン被覆体の製造方法および導電性パターン被覆体
JP2014002992A (ja) * 2012-06-14 2014-01-09 Pelnox Ltd レーザーエッチング用導電性ペースト組成物
WO2014013899A1 (ja) * 2012-07-20 2014-01-23 東洋紡株式会社 レーザーエッチング加工用導電性ペースト、導電性薄膜および導電性積層体
JP2014107533A (ja) * 2012-11-29 2014-06-09 Pelnox Ltd レーザーエッチング用導電性ペースト組成物

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017159381A1 (ja) * 2016-03-17 2017-09-21 東洋紡株式会社 導電性皮膜およびレーザーエッチング加工用導電性ペースト
KR20180121522A (ko) * 2016-03-17 2018-11-07 도요보 가부시키가이샤 도전성 피막 및 레이저 에칭 가공용 도전성 페이스트
CN108781505A (zh) * 2016-03-17 2018-11-09 东洋纺株式会社 导电性覆膜以及激光蚀刻加工用导电性浆料
JPWO2017159381A1 (ja) * 2016-03-17 2019-01-24 東洋紡株式会社 導電性皮膜およびレーザーエッチング加工用導電性ペースト
TWI710041B (zh) * 2016-03-17 2020-11-11 日商東洋紡股份有限公司 導電性皮膜及雷射蝕刻加工用導電性糊劑
CN108781505B (zh) * 2016-03-17 2021-08-06 东洋纺株式会社 导电性覆膜以及激光蚀刻加工用导电性浆料
KR102353074B1 (ko) * 2016-03-17 2022-01-19 도요보 가부시키가이샤 도전성 피막 및 레이저 에칭 가공용 도전성 페이스트
JP7056552B2 (ja) 2016-03-17 2022-04-19 東洋紡株式会社 導電性皮膜およびレーザーエッチング加工用導電性ペースト
WO2018092762A1 (ja) * 2016-11-21 2018-05-24 東洋紡株式会社 導電性ペースト、導電性膜、導電性膜の製造方法、導電性微細配線、導電性微細配線の製造方法。
JPWO2018092762A1 (ja) * 2016-11-21 2019-10-17 東洋紡株式会社 導電性ペースト、導電性膜、導電性膜の製造方法、導電性微細配線、導電性微細配線の製造方法。
JP7024724B2 (ja) 2016-11-21 2022-02-24 東洋紡株式会社 導電性ペースト、導電性膜、導電性膜の製造方法、導電性微細配線、導電性微細配線の製造方法。

Also Published As

Publication number Publication date
TW201533091A (zh) 2015-09-01
KR102312236B1 (ko) 2021-10-14
KR20160111944A (ko) 2016-09-27
JP6582982B2 (ja) 2019-10-02
JPWO2015111615A1 (ja) 2017-03-23
CN105993050A (zh) 2016-10-05
TWI657098B (zh) 2019-04-21
CN105993050B (zh) 2018-09-25

Similar Documents

Publication Publication Date Title
JP7059240B2 (ja) レーザーエッチング加工用導電性ペースト、導電性薄膜および導電性積層体
JP6582982B2 (ja) レーザーエッチング加工用導電性ペースト、導電性薄膜、導電性積層体
KR102324621B1 (ko) 레이저 에칭 가공용 도전성 페이스트, 도전성 박막, 도전성 적층체
KR102353074B1 (ko) 도전성 피막 및 레이저 에칭 가공용 도전성 페이스트
WO2018092762A1 (ja) 導電性ペースト、導電性膜、導電性膜の製造方法、導電性微細配線、導電性微細配線の製造方法。
JP6673215B2 (ja) レーザーエッチング加工用導電性ペースト、導電性薄膜、導電性積層体

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2015518694

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15739797

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20167021704

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 15739797

Country of ref document: EP

Kind code of ref document: A1