WO2014013899A1 - Conductive paste for laser etching, conductive thin film, and conductive laminate - Google Patents
Conductive paste for laser etching, conductive thin film, and conductive laminate Download PDFInfo
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- WO2014013899A1 WO2014013899A1 PCT/JP2013/068613 JP2013068613W WO2014013899A1 WO 2014013899 A1 WO2014013899 A1 WO 2014013899A1 JP 2013068613 W JP2013068613 W JP 2013068613W WO 2014013899 A1 WO2014013899 A1 WO 2014013899A1
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- Prior art keywords
- conductive
- resin
- thin film
- laser
- laser etching
- Prior art date
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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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
- 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
- H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
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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
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/027—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed by irradiation, e.g. by photons, alpha or beta particles
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/09—Shape and layout
- H05K2201/09209—Shape and layout details of conductors
- H05K2201/0929—Conductive planes
- H05K2201/09363—Conductive planes wherein only contours around conductors are removed for insulation
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
- H05K2203/107—Using laser light
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.
- An object of the present invention is to provide a manufacturing method capable of manufacturing a high-density electrode circuit wiring having an L / S of 50/50 ⁇ m or less, which is difficult to cope with by a screen printing method, at low cost and low environmental load. It is in. Moreover, it is providing the electrically conductive paste which can be used suitably for such a manufacturing method.
- the present inventors formed a layer made of a binder resin and conductive powder on an insulating substrate, and a part of the layer was formed by laser light. It has been found that a high-density electrode circuit wiring having an L / S of 50/50 ⁇ m or less, which is difficult to achieve by the screen printing method, can be produced by removing from the insulating substrate by irradiation. Moreover, the electroconductive paste suitable for forming the layer which consists of binder resin and electroconductive powder suitable for such a manufacturing method was discovered. That is, this invention consists of the following structures.
- a conductive paste for laser etching containing a binder resin (A) made of a thermoplastic resin, a metal powder (B), and an organic solvent (C).
- the binder resin (A) is a thermoplastic resin having a number average molecular weight of 5,000 to 60,000 and a glass transition temperature of 60 to 100 ° C.
- the binder resin (A) is one or a mixture of two or more selected from the group consisting of a polyester resin, a polyurethane resin, an epoxy resin, a vinyl chloride resin, and a fiber derivative resin ( The conductive paste for laser etching according to 1) or (2).
- the binder resin (A) one selected from the group consisting of acid value 50-300 equivalents / 10 6 polyester resin and an acid number of 50 is g ⁇ 300 equivalents / 10 6 g and a polyurethane resin or 2
- the conductive paste for laser etching according to (1) or (2) which is a mixture of seeds or more.
- (6) A conductive thin film formed from the conductive paste for laser etching according to any one of (1) to (5).
- a part of the conductive thin film according to (6) is irradiated with a laser beam selected from a carbon dioxide laser, a YAG laser, a fiber laser, and a semiconductor laser to remove a part of the conductive thin film.
- a touch panel comprising the electric circuit according to any one of (9) to (11) as a constituent member.
- the conductive paste of the present invention is a conductive paste containing a binder resin (A) made of a thermoplastic resin, a metal powder (B) and an organic solvent (C).
- A binder resin
- B metal powder
- C organic solvent
- the conductive paste containing the laser light absorber (D) according to the embodiment of the present invention has higher sensitivity to laser light irradiation than the conductive paste not containing the laser light absorber (D), The laser scanning speed can be improved and the laser output can be reduced.
- FIG. 1 It is a schematic diagram showing the pattern which irradiates a laser beam to the laser etching process aptitude evaluation test piece used by the Example and comparative example of this invention.
- 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.
- the conductive paste for laser etching according to the present invention contains a binder resin (A) made of a thermoplastic resin, a metal powder (B), and an organic solvent (C) as essential components.
- A binder resin
- B metal powder
- C organic solvent
- binder resin (A) is not particularly limited as long as it is a thermoplastic resin.
- Rukoto can be used, and these resins are used alone or as a mixture of two or more.
- Rukoto can. It is preferably one or a mixture of two or more selected from the group consisting of polyester resins, polyurethane resins, epoxy resins, vinyl chloride resins, and fiber derivative resins.
- a polyurethane resin containing a polyester resin and / or a polyester component as a copolymer component (hereinafter sometimes referred to as a polyester polyurethane resin) is preferable as the binder resin (A).
- One of the advantages of using a polyester resin as the binder resin (A) in the present invention is the high degree of freedom in molecular design.
- the dicarboxylic acid and glycol components constituting the polyester resin can be selected and the copolymerization component can be freely changed, and the functional group can be easily added in the molecular chain or at the molecular end. For this reason, the characteristics of the resin such as the glass transition temperature of the polyester resin to be obtained and the affinity with other components blended in the base material and the conductive paste can be appropriately adjusted.
- Dicarboxylic acids such as dicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecane dicarboxylic acid, azelaic acid and the like, dibasic acids having 12 to 28 carbon atoms such as dimer acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 2-methylhexahydrophthalic anhydride, dicarboxyhydrogenated bisphenol A, Dicarboxy hydrogenated bisphenol S, Timer acid, hydrogenated dimer acid, hydrogenated naphthalenedicarboxylic acid, alicyclic dicarboxylic acids such as tricyclodecane acid, hydroxybenzoic 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 / or 5-sulfoisophthalic acid sodium salt, etc., as long as the effects of the invention are not impaired.
- the sulfonic acid metal base-containing dicarboxylic acid may be used as a copolymerization component.
- trivalent or higher polyols such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, polyglycerin and the like may be used in combination as a copolymerization component as long as the effects of the invention are not impaired.
- the polyester resin used as the binder resin (A) in the present invention is an aromatic dicarboxylic acid among all acid components constituting the polyester resin from the viewpoints of durability such as strength, heat resistance, moisture resistance, and thermal shock resistance.
- the acid is preferably copolymerized in an amount of 60 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 98 mol% or more. It is a preferred embodiment that the total acid component consists of an aromatic dicarboxylic acid.
- the glass transition temperature of the resulting polyester resin will be lower than 60 ° C., and the heat and humidity resistance and durability of the resulting conductive thin film will tend to be reduced.
- the polyester resin used as the binder resin (A) in the present invention is a main chain carbon among all polyols constituting the polyester resin from the viewpoint of durability such as strength, heat resistance, moisture resistance, and thermal shock resistance.
- the number of glycols having 4 or less is preferably 60 mol% or more, more preferably 80 mol% or more, and further preferably 95 mol% or more.
- the copolymerization ratio of glycol having 4 or less carbon atoms in the main chain among all polyol components is too low, the glass transition temperature of the resulting polyurethane resin is lower than 60 ° C., and the resulting conductive thin film has heat and heat resistance and durability. Tend to decrease.
- a polyurethane resin as the binder resin (A) in the present invention.
- glass transition can be achieved by selecting appropriate components as copolymer components that make up polyurethane resins, and by adding functional groups in the molecular chain or at the molecular ends. Resin properties such as temperature and affinity with other components blended in the substrate and the conductive paste can be appropriately adjusted.
- the copolymer component of the polyurethane resin is not particularly limited, but is preferably a polyester polyurethane resin using a polyester polyol as a copolymer component from the viewpoint of freedom of design, heat and humidity resistance, and maintenance of durability.
- a polyester polyol what is a polyol among the polyester resins which can be used as binder resin (A) in the above-mentioned this invention can be mentioned.
- the polyurethane resin used as the binder resin (A) in the present invention can be obtained, for example, by a reaction between a polyol and a polyisocyanate.
- the polyisocyanate that can be used as a copolymerization component of the polyurethane resin include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, m-phenylene diisocyanate.
- a compound having a functional group capable of reacting with isocyanate can be copolymerized as necessary.
- the functional group capable of reacting with isocyanate is preferably a hydroxyl group or an amino group, and may have either one or both.
- dimethylolbutanoic acid dimethylolpropionic acid
- 1,2-propylene glycol 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 2,2- Dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,2- Dimethyl-3-hydroxypropyl-2 ′, 2′-dimethyl-3′-hydroxypropanoate, 2-normalbutyl-2-ethyl-1,3-propanediol, 3-ethyl-1,5-pentanediol, 3 -Propyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 3-octyl-1,5-pentanediol, -2 in
- 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 5,000 to 60,000. 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, and more preferably 65 ° C. or higher. If the glass transition temperature is low, the suitability for laser etching may be improved, but there is a risk that the reliability of wet heat environment as a conductive thin film may be reduced, and the manufacturing process and There is a risk that the reliability of the conductive thin film is lowered due to the migration of the paste-containing component to the contact partner side during use.
- the glass transition temperature of the binder resin (A) used in the present invention is preferably 150 ° C. or less, more preferably 120 ° C. or less in consideration of printability, adhesion, solubility, paste viscosity, laser etching processing suitability, and the like. Preferably, 100 degrees C or less is still more preferable.
- the acid value of the binder resin (A) in the present invention is not particularly limited, but the adhesion to the substrate may be remarkably improved by having an acid value in a specific range.
- the temperature around the laser irradiation site may increase and the adhesion between the conductive thin film and the substrate may decrease, but the binder resin (A) has an acid value in a specific range.
- the acid value of the binder resin (A) is preferably 50 to 350 eq / ton, and more preferably 100 to 250 eq / ton.
- the adhesion between the conductive thin film to be formed and the substrate tends to be low.
- the acid value is too high, the water-absorbing property of the formed conductive thin film increases, and the hydrolysis of the binder resin may be promoted by the catalytic action of the carboxyl group. It tends to lead to a decline.
- the metal powder (B) used in the present invention is plated with noble metal powder such as silver powder, gold powder, platinum powder and palladium powder, base metal powder such as copper powder, nickel powder, aluminum powder and brass powder, or noble metal such as silver. Examples include alloyed base metal powders. These metal powders may be used alone or in combination. Among these, considering the conductivity, stability, cost, etc., the silver powder alone or the one mainly composed of silver powder is preferable.
- the shape of the metal powder (B) used in the present invention is not particularly limited.
- Examples of conventionally known metal powder shapes include flakes (flakes), spheres, dendrites (dendrites), and spherical primary particles described in JP-A-9-306240.
- the center diameter (D50) of the metal powder (B) used in the present invention is preferably 4 ⁇ m or less.
- the metal 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.
- a metal 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 metal powder (B) is not particularly limited, but it is preferable that the center diameter is 80 nm or more because it tends to agglomerate when the particle diameter becomes fine and dispersion becomes difficult as a result.
- the center diameter is smaller than 80 nm, the cohesive force of the metal powder increases, the laser etching processing suitability deteriorates, and it is not preferable from the viewpoint of cost.
- the central diameter (D50) is a particle diameter ( ⁇ m) at which the cumulative value becomes 50% in the cumulative distribution curve (volume) obtained by some measurement method.
- the cumulative distribution curve is measured by a laser diffraction / scattering particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., MICROTRAC). Measured in total reflection mode using HRA).
- the content of the metal powder (B) is preferably 400 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin (A) from the viewpoint that the conductivity of the formed conductive thin film is good. The above is more preferable. 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 substrate. 230 parts by mass or less is more preferable.
- the 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 a thermoplastic resin (A), a metal powder (B), an organic solvent (C) and other components as necessary with a three-roll mill or the like.
- thermoplastic resin (A) is soluble and a metal powder (B) can be disperse
- distributed favorably is preferable.
- EDGAC ethyl diglycol acetate
- BMGAC butyl glycol acetate
- BDGAC butyl diglycol acetate
- 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.
- thermoplastic resins From the viewpoints of excellent solubility of the compounding component A), moderate solvent volatility during continuous printing, and good suitability for printing by a screen printing method, etc., EDGAC, BMGAC, BDGAC, and mixtures thereof Solvents are preferred.
- 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. For example, when a YAG laser having a fundamental wavelength of 1064 nm is used as the light source, the wavelength is 1064 nm. Dyes and / or pigments having strong absorption 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 resin (A) due to heat generation is promoted, and as a result, suitability for laser etching processing. 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 can be 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 metal 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; various oxidations such as titanium oxide (titania), calcium oxide, magnesium oxide, zinc oxide, copper oxide, aluminum oxide, silica and colloidal silica Products: various titanate compounds such as calcium titanate, magnesium titanate, strontium titanate; sulfides such as molybdenum disulfide; various fluorides such as magnesium fluoride and carbon fluoride; aluminum stearate
- silica is preferable from the viewpoint of imparting durability, printability, particularly screen printability.
- 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 resin (A) of the present invention is not limited, but an isocyanate compound is particularly preferable from the viewpoint of adhesion, flex resistance, curability, and the like. Furthermore, it is preferable to use those having an isocyanate group blocked as these isocyanate compounds because 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, epoxy resins, 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 resin (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.
- 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 mass part is a mass part of components other than the solvent, and includes all of the conductive powder, the binder resin, and other curing agents and additives. If the F value is too low, a conductive thin film showing good conductivity cannot be obtained.
- the conductive powder refers to both the metal powder (B) and the conductive powder made of a nonmetal.
- the conductive paste of the present invention can be prepared by dispersing the thermoplastic resin (A), the metal powder (B), the organic solvent (C), and other components as necessary with a three roll or the like. it can.
- the thermoplastic resin (A) is first dissolved in the organic solvent (C).
- the metal powder (B) and additives as necessary are added, and preliminary dispersion is carried out with a double planetary, a dissolver, a planetary stirrer or the like. Then, it disperses
- 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 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 of the transparent conductive layer is not particularly limited, and examples thereof include an ITO film containing indium tin oxide as a main component.
- 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 5 ⁇ 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. 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 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 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 base material a polyester film, a transparent conductive laminate in which an ITO layer is formed on a polyester film, or a laminate in which an ITO layer is formed on a polyester film and a part thereof is removed by etching
- a YAG laser or a fiber laser because the base material has no absorption at the wavelength of the fundamental wave and is difficult to damage the base material.
- the laser output and the Q modulation frequency are not particularly limited, but are adjusted so that the conductive thin film at the laser light 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 Q modulation frequency of 10 to 400 kHz. If the laser output is too low, removal of the conductive thin film tends to be insufficient, but such a tendency can be avoided to some extent by reducing the scanning speed of the laser 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.
- 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 or the physical properties of the coating film may be deteriorated by receiving heat history multiple times. 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, 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
- Acid value 0.2 g of sample resin was precisely weighed and dissolved in 20 ml of chloroform. Subsequently, titration was performed with 0.01 N potassium hydroxide (ethanol solution) using a phenolphthalein solution as an indicator. The unit of the acid value was eq / ton, that is, the equivalent per 1 ton of the sample.
- Resin Composition The sample resin was dissolved in chloroform-d, and the resin composition was determined by 1 H-NMR analysis using a Varian 400 MHz-NMR apparatus.
- Paste viscosity Viscosity is measured at a sample temperature of 25 ° C using a BH viscometer (manufactured by Toki Sangyo Co., Measurements were performed at 20 rpm.
- conductive laminate test piece A 200-mesh polyester screen was used for each of a PET film (Lumirror S manufactured by Toray Industries, Inc.) and an ITO film (KH300 manufactured by Oike Kogyo Co., Ltd.) that had been annealed to a thickness of 100 ⁇ m.
- a conductive paste was printed by a screen printing method to form a solid coating pattern having a width of 25 mm and a length of 450 mm, and then heated at 120 ° C. for 30 minutes in a hot air circulation drying oven to obtain a conductive laminate test piece. .
- the coating thickness at the time of printing was adjusted so that the dry film thickness was 6 to 10 ⁇ m.
- the sheet resistance and film thickness of the conductive laminate test piece 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 or less ( ⁇ ⁇ cm), and a specific resistance of 1 ⁇ 10 ⁇ 2 ( ⁇ ⁇ cm) or more is outside the measurement limit.
- Pencil Hardness The conductive laminate test piece was placed on a 2 mm thick SUS304 plate, and the pencil hardness was measured according to JIS K 5600-5-4: 1999.
- Moisture and heat resistance test The conductive laminate test piece was 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 T400 stainless mesh emulsion thickness 10 ⁇ m, wire diameter 23 ⁇ m (manufactured by Tokyo Process Service) was used as a screen plate, and printing was performed at a squeegee speed of 150 mm / s. After the printing application, drying was performed at 120 ° 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 12 ⁇ m.
- laser etching processing was performed on the conductive thin film prepared by the above method to prepare a pattern having four straight portions with a length of 50 mm shown in FIG. 1 and used as a test piece for evaluating the suitability for laser etching processing.
- the laser etching process between the straight line portions was performed by scanning a laser beam having a beam diameter of 30 ⁇ m twice at a pitch of 60 ⁇ m.
- a fiber laser was used as the laser light source, and the Q modulation frequency was 200 kHz, the output was 10 W, and the scanning speed was 2700 mm / s.
- Evaluation items and measurement conditions are as follows.
- the line width of the portion where the conductive thin film was removed 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 process suitability evaluation test piece (1) Conductivity between both ends of fine wire
- the evaluation was made based on whether or not conduction between both ends of the thin wires 1b, 2b, 3b, and 4b was secured. Specifically, the presence or absence of continuity is confirmed by applying a tester between each of terminals 1a and 1c, between terminals 2a and 2c, between terminals 3a and 3c, and between terminals 4a and 4c. Judged by.
- ⁇ 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 1a-terminal 2a, the terminals 2a-terminal 3a, and the terminals 3a-terminal 4a to confirm the presence or absence of conduction, and the following evaluation criteria were used.
- ⁇ All adjacent fine wires are insulated
- Some adjacent fine wires are insulated
- All adjacent fine wires are not insulated
- Example of Resin Production Example of Polyester Resin P-1 In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 700 parts of terephthalic acid, 700 parts of isophthalic acid, 16.9 parts of trimellitic anhydride, 983 parts of ethylene glycol, 2 -154 parts of methyl-1,3-propanediol were charged, and the temperature was raised from 160 ° C to 230 ° C over 3 hours under a pressure of 2 atmospheres in a nitrogen atmosphere to carry out an esterification reaction.
- Polyester resins P-2 to P-11 were produced by changing the type and blending ratio of the monomers in the production example of polyester resin P-1.
- the compositions and physical properties of the obtained copolyester resins are shown in Tables 1 and 2.
- BPE-20F Ethylene oxide adduct of bisphenol A (manufactured by Sanyo Chemical Industries)
- BPX-11 Propylene oxide adduct of bisphenol A (Asahi Denka)
- Example of production of polyurethane resin U-1 In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 1000 parts of polyester resin P-7, 80 parts of neopentyl glycol (NPG) and 90 parts of dimethylolbutanoic acid (DMBA) are charged. Then, 1087 parts of ethyl diglycol acetate (EDGAC) was charged and dissolved at 85 ° C. Thereafter, 460 parts of 4,4′-diphenylmethane diisocyanate (MDI) was added and reacted at 85 ° C. for 2 hours, and then 0.5 part of dibutyltin dilaurate was added as a catalyst and reacted at 85 ° C.
- MDI 4,4′-diphenylmethane diisocyanate
- the solution was diluted with 1940 parts of EDGAC to obtain a solution of polyurethane resin U-1.
- the solid content concentration of the obtained polyurethane resin solution was 35% by mass.
- 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 3 shows the evaluation results of various resin properties, using the dry resin thin film on the left as a sample resin of polyurethane resin U-1.
- Polyurethane resins U-2 to U-8 are polyurethanes except that polyester polyols, compounds having groups that react with isocyanates, and polyisocyanates are replaced with those shown in Table 3.
- the resin U-1 was produced by the same method as in the production example.
- the evaluation results of the resin physical properties of the polyurethane resins U-2 to U-8 are shown in Table 3.
- DMBA dimethylol butanoic acid
- NPG neopentyl glycol
- DMH 2-butyl-2-ethyl-1,3-propanediol
- MDI 4,4′-diphenylmethane diisocyanate
- IPDI isophorone diisocyanate
- Example 1 2860 parts (1000 parts in terms of solid part) of polyester resin P-1 dissolved in EDGAC so that the solid content concentration is 35% by mass, 7,888 parts of flaky silver powder 1, and Kyoeisha Chemical Co., Ltd. as a leveling agent 71 parts of MK Conk made, 30 parts of Disperbyk 130 made by Big Chemie Japan Co., Ltd. as a dispersant and 300 parts of EDGAC as a solvent were blended and dispersed by passing 3 times through a chilled three-roll kneader. Thereafter, the obtained conductive paste was printed in a predetermined pattern and then dried at 120 ° 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. Table 4 shows the evaluation results of the paste, paste coating film, and laser etching processability.
- Examples 2 to 13 Examples 2 to 17 were carried out by changing the resin and formulation of the conductive paste.
- the formulation and evaluation results of the conductive paste are shown in Tables 4 to 6.
- good film properties could be obtained by heating at a relatively low temperature of 120 ° C. for 30 minutes in an oven at a relatively low temperature.
- the adhesion to the ITO film and the adhesion after the wet heat environment test were good.
- Silver powder 1 flaky silver powder (D50: 2 ⁇ m)
- Silver powder 2 Spherical silver powder (D50: 1 ⁇ m)
- Carbon black Tokai Carbon Co., Ltd.
- Ketjen Black Ketjen ECP600JD made by Lion Corporation
- Graphite powder Graphite BF manufactured by Chuetsu Graphite Co., Ltd.
- Curing agent MF-K60X manufactured by Asahi Kasei Chemicals Corporation Curing catalyst: Kyodo Pharmaceutical Co., Ltd. KS1260 Leveling agent: Kyoeisha Chemical Co., Ltd. MK Conk Dispersant 1: Disperbyk130 manufactured by Big Chemie Japan Co., Ltd. Dispersant 2: Disperbyk 2155 manufactured by Big Chemie Japan Co., Ltd. Dispersant 3: Disperbyk180 manufactured by Big Chemie Japan Co., Ltd. Additive 1: Silica R972 manufactured by Nippon Aerosil Co., Ltd.
- Additive 2 NIR-AM1 manufactured by Nagase ChemteX Corporation
- Additive 3 Light acrylate PE-3A (pentaerythritol triacrylate) manufactured by Kyoeisha Chemical Co., Ltd.
- EDGAC Ethyl diglycol acetate manufactured by Daicel Corp.
- BMGAC Butyl glycol acetate manufactured by Daicel Corp.
- BDGAC Butyl diglycol acetate manufactured by Daicel Corp.
- TPOL Terpineol manufactured by Nippon Terpene Chemical Co., Ltd.
- the obtained silver powder 3 had a particle diameter of about 10 nm from a transmission electron micrograph.
- the solid content concentration of the conductive paste was 35% by mass.
- a conductive laminate test piece and a laser etching processability evaluation test piece were prepared in the same manner as in the example, and the evaluation was performed in the same manner as in the example.
- the evaluation results are shown in Table 7.
- This electroconductive silver paste composition was remarkably inferior in initial coating film properties, in particular, poor in adhesion, and could not withstand practical use.
- This conductive silver paste composition was remarkably inferior in initial coating film properties, in particular, poor adhesion, and could not withstand practical use.
- the coating film with a width much wider than the width of the laser beam irradiated in a wider range than the irradiated site was peeled off, and the predetermined line width could not be processed.
- the adhesion of the thin wire portion after etching and the heat and humidity resistance were also poor.
- 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 touch panel mounted on a mobile phone, a notebook computer, an electronic book, or the like.
- 1a, 2a, 3a, 4a Terminals 1a, 2a, 3a, 4a 1b, 2b, 3b, 4b: Fine wires 1b, 2b, 3b, 4b 1c, 2c, 3c, 4c: Terminals 1c, 2c, 3c, 4c 5: Pattern formed on test piece for evaluating laser etching process suitability
Abstract
Description
(1) 熱可塑性樹脂からなるバインダ樹脂(A)、金属粉(B)および有機溶剤(C)を含有するレーザーエッチング加工用導電性ペースト。
(2) 前記バインダ樹脂(A)が、数平均分子量が5,000~60,000であり、なおかつ、ガラス転移温度が60~100℃である熱可塑性樹脂であることを特徴とする、(1)に記載のレーザーエッチング加工用導電性ペースト。
(3) 前記バインダ樹脂(A)が、ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂、塩化ビニル樹脂、繊維素誘導体樹脂からなる群から選ばれる1種又は2種以上の混合物であることを特徴とする(1)または(2)に記載のレーザーエッチング加工用導電性ペースト。
(4) 前記バインダ樹脂(A)が、酸価50~300当量/106gであるポリエステル樹脂および酸価50~300当量/106gであるポリウレタン樹脂からなる群から選ばれる1種又は2種以上の混合物であることを特徴とする(1)または(2)に記載のレーザーエッチング加工用導電性ペースト。
(5) 更にレーザー光吸収剤(D)を含有することを特徴とする(1)~(4)のいずれかに記載の導電性レーザーエッチング加工用導電性ペースト。
(6) (1)~(5)のいずれかに記載のレーザーエッチング加工用導電性ペーストから形成された導電性薄膜。
(7) (6)に記載の導電性薄膜と基材とが積層されている導電性積層体。
(8) 前記基材が透明導電性層を有することを特徴とする(7)に記載の導電性積
層体。
(9) (6)に記載の導電性薄膜、または、(7)または(8)に記載の導電性積層体、を用いてなる電気回路。
(10) (6)に記載の導電性薄膜の一部に、炭酸ガスレーザー、YAGレーザー、ファイバーレーザーおよび半導体レーザーから選ばれるレーザー光を照射して、前記導電性薄膜の一部を除去することによって形成された配線部位を有する電気回路。
(11) 前記導電性薄膜が透明導電性層上に形成されていることを特徴とする(9)に記載の電気回路。
(12) (9)~(11)のいずれかに記載の電気回路を構成部材として含むタッチパネル。 As a result of intensive studies on a manufacturing method for arranging electrode circuit wiring at a high density in a planar direction, the present inventors formed a layer made of a binder resin and conductive powder on an insulating substrate, and a part of the layer was formed by laser light. It has been found that a high-density electrode circuit wiring having an L / S of 50/50 μm or less, which is difficult to achieve by the screen printing method, can be produced by removing from the insulating substrate by irradiation. Moreover, the electroconductive paste suitable for forming the layer which consists of binder resin and electroconductive powder suitable for such a manufacturing method was discovered. That is, this invention consists of the following structures.
(1) A conductive paste for laser etching containing a binder resin (A) made of a thermoplastic resin, a metal powder (B), and an organic solvent (C).
(2) The binder resin (A) is a thermoplastic resin having a number average molecular weight of 5,000 to 60,000 and a glass transition temperature of 60 to 100 ° C. The conductive paste for laser etching processing as described in).
(3) The binder resin (A) is one or a mixture of two or more selected from the group consisting of a polyester resin, a polyurethane resin, an epoxy resin, a vinyl chloride resin, and a fiber derivative resin ( The conductive paste for laser etching according to 1) or (2).
(4) the binder resin (A), one selected from the group consisting of acid value 50-300 equivalents / 10 6 polyester resin and an acid number of 50 is g ~ 300 equivalents / 10 6 g and a polyurethane resin or 2 The conductive paste for laser etching according to (1) or (2), which is a mixture of seeds or more.
(5) The conductive paste for conductive laser etching according to any one of (1) to (4), further comprising a laser light absorber (D).
(6) A conductive thin film formed from the conductive paste for laser etching according to any one of (1) to (5).
(7) A conductive laminate in which the conductive thin film according to (6) and a substrate are laminated.
(8) The conductive laminate according to (7), wherein the substrate has a transparent conductive layer.
(9) An electric circuit using the conductive thin film according to (6) or the conductive laminate according to (7) or (8).
(10) A part of the conductive thin film according to (6) is irradiated with a laser beam selected from a carbon dioxide laser, a YAG laser, a fiber laser, and a semiconductor laser to remove a part of the conductive thin film. The electric circuit which has the wiring site | part formed by.
(11) The electric circuit according to (9), wherein the conductive thin film is formed on a transparent conductive layer.
(12) A touch panel comprising the electric circuit according to any one of (9) to (11) as a constituent member.
本発明におけるレーザーエッチング加工用導電性ペーストは、熱可塑性樹脂からなるバインダ樹脂(A)、金属粉(B)および有機溶剤(C)を必須成分として含有する。 << Components constituting the conductive paste of the present invention >>
The conductive paste for laser etching according to the present invention contains a binder resin (A) made of a thermoplastic resin, a metal powder (B), and an organic solvent (C) as essential components.
バインダ樹脂(A)の種類は熱可塑性樹脂であれば特に限定されないが、ポリエステル樹脂、エポキシ樹脂、フェノキシ樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、フェノール樹脂、アクリル樹脂、ポリスチレン、スチレンーアクリル樹脂、スチレンーブタジエン共重合体、フェノール樹脂、ポリエチレン系樹脂、ポリカーボネート系樹脂、フェノール樹脂、アルキッド樹脂、スチレンーアクリル樹脂、スチレンーブタジエン共重合樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、塩化ビニル-酢酸ビニル共重合樹脂、エチレン-酢酸ビニル共重合、ポリスチレン、シリコーン樹脂、フッ素系樹脂等を挙げることができ、これらの樹脂は単独で、あるいは2種以上の混合物として、使用することができる。ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂、塩化ビニル樹脂、繊維素誘導体樹脂からなる群から選ばれる1種又は2種以上の混合物であることが好ましい。また、これらの樹脂の中でも、ポリエステル樹脂および/またはポリエステル成分を共重合成分として含有するポリウレタン樹脂(以下ポリエステルポリウレタン樹脂と呼ぶ場合がある)が、バインダ樹脂(A)として好ましい。 <Binder resin (A)>
The type of binder resin (A) is not particularly limited as long as it is a thermoplastic resin. However, 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. can be used, and these resins are used alone or as a mixture of two or more. Rukoto can. It is preferably one or a mixture of two or more selected from the group consisting of polyester resins, polyurethane resins, epoxy resins, vinyl chloride resins, and fiber derivative resins. Among these resins, a polyurethane resin containing a polyester resin and / or a polyester component as a copolymer component (hereinafter sometimes referred to as a polyester polyurethane resin) is preferable as the binder resin (A).
ロールエタン、トリメチロールプロパン、グリセリン、ペンタエリスリトール、ポリグリセリン等の1分子中に3個以上の水酸基を有するアルコール、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等の1分子に1個以上の水酸基とアミノ基を有するアミノアルコール、エチレンジアミン、1,6-ヘキサンジアミン、1,8-オクタンジアミン、1,9-ノナンジアミン、1,10-デカンジアミン、1,11-ウンデカンジアミン、1,12-ドデカンジアミンなどの脂肪族ジアミンやメタキシレンジアミン、4,4’-ジアミノジフェニルメタン、3,4’-ジアミノジフェニルエーテル、4,4’-ジアミノジフェニルエーテル等の芳香族ジアミンなどの1分子中に2個のアミノ基を有する化合物が挙げられる。上記の数平均分子量1,000未満の1分子に2個以上のイソシアネートと反応し得る官能基を有する化合物は単独で用いてもよいし複数を併用しても何ら問題はない。 In the polyurethane resin used as the binder resin (A) in the present invention, a compound having a functional group capable of reacting with isocyanate can be copolymerized as necessary. The functional group capable of reacting with isocyanate is preferably a hydroxyl group or an amino group, and may have either one or both. Specific examples thereof include dimethylolbutanoic acid, dimethylolpropionic acid, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 2,2- Dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,2- Dimethyl-3-hydroxypropyl-2 ′, 2′-dimethyl-3′-hydroxypropanoate, 2-normalbutyl-2-ethyl-1,3-propanediol, 3-ethyl-1,5-pentanediol, 3 -Propyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 3-octyl-1,5-pentanediol, -2 in one molecule such as phenyl-1,5-pentanediol, 2,5-dimethyl-3-sodium sulfo-2,5-hexanediol, dimer diol (eg, PRIPOOL-2033 manufactured by Unikema International) One molecule such as a compound having three or more hydroxyl groups in one molecule such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, polyglycerin, etc., monoethanolamine, diethanolamine, triethanolamine Amino alcohols having one or more hydroxyl groups and amino groups, ethylenediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1 , 12-Dodecandia 2 amino groups in one molecule such as aliphatic diamine such as meta-xylene diamine, aromatic diamine such as 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenyl ether, and 4,4′-diaminodiphenyl ether The compound which has is mentioned. The above-mentioned compound having a functional group capable of reacting with two or more isocyanates per molecule having a number average molecular weight of less than 1,000 may be used alone or in combination with a plurality of compounds without any problem.
本発明に用いられる金属粉(B)としては、銀粉、金粉、白金粉、パラジウム粉等の貴金属粉、銅粉、ニッケル粉、アルミ粉、真鍮粉等の卑金属粉、銀等の貴金属でめっき又は合金化した卑金属粉等を挙げることができる。これらの金属粉は、単独で用いてもよく、また、併用してもよい。これらの中でも導電性、安定性、コスト等を考慮すると銀粉単独又は銀粉を主体とするものが好ましい。 <Metal powder (B)>
The metal powder (B) used in the present invention is plated with noble metal powder such as silver powder, gold powder, platinum powder and palladium powder, base metal powder such as copper powder, nickel powder, aluminum powder and brass powder, or noble metal such as silver. Examples include alloyed base metal powders. These metal powders may be used alone or in combination. Among these, considering the conductivity, stability, cost, etc., the silver powder alone or the one mainly composed of silver powder is preferable.
HRA)を用い全反射モードで測定することとする。 The central diameter (D50) is a particle diameter (μm) at which the cumulative value becomes 50% in the cumulative distribution curve (volume) obtained by some measurement method. In the present invention, the cumulative distribution curve is measured by a laser diffraction / scattering particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., MICROTRAC).
Measured in total reflection mode using HRA).
であるという観点から、熱可塑性樹脂(A)100質量部に対して、1,900質量部以下が好ましく、1,230質量部以下がより好ましい。 The content of the metal powder (B) is preferably 400 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin (A) from the viewpoint that the conductivity of the formed conductive thin film is good. The above is more preferable. 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 substrate. 230 parts by mass or less is more preferable.
本発明に用いることのできる有機溶剤(C)は、とくに限定されないが、有機溶剤の揮発速度を適切な範囲に保つ観点から、沸点が100℃以上、300℃未満であることが好ましく、より好ましくは沸点が150℃以上、280℃未満である。本発明の導電性ペーストは、典型的には熱可塑性樹脂(A)、金属粉(B)、有機溶剤(C)および必要に応じてその他の成分を三本ロールミル等で分散して作製するが、その際に有機溶剤の沸点が低すぎると、分散中に溶剤が揮発し、導電性ペーストを構成する成分比が変化する懸念がある。一方で、有機溶剤の沸点が高すぎると、乾燥条件によっては溶剤が塗膜中に多量に残存する可能性があり、塗膜の信頼性低下を引き起こす懸念がある。 <Organic solvent (C)>
The 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 a thermoplastic resin (A), a metal powder (B), an organic solvent (C) and other components as necessary with a three-roll mill or the like. In this case, if the boiling point of the organic solvent is too low, the solvent volatilizes during dispersion, and there is a concern that the ratio of components constituting the conductive paste changes. On the other hand, if 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.
ベッソ100,150,200、プロピレングリコールモノメチルエーテルアセテート、アジピン酸、こはく酸およびグルタル酸のジメチルエステルの混合物(例えば、デュポン(株)社製DBE)、ターピオネール等が挙げられるが、これらの中で、熱可塑性樹脂(A)の配合成分の溶解性に優れ、連続印刷時の溶剤揮発性が適度でありスクリーン印刷法等による印刷に対する適性が良好であるという観点から、EDGAC、BMGAC、BDGACおよびそれらの混合溶剤が好ましい。 Moreover, as an organic solvent (C) which can be used for this invention, the thing in which a thermoplastic resin (A) is soluble and a metal powder (B) can be disperse | distributed favorably is preferable. Specific examples include ethyl diglycol acetate (EDGAC), butyl glycol acetate (BMGAC), butyl diglycol acetate (BDGAC), cyclohexanone, toluene, isophorone, γ-butyrolactone, benzyl alcohol, Exson Chemical's
本発明の導電ペーストには、レーザー光吸収剤(D)を配合しても良い。ここでレーザー光吸収剤(D)とは、レーザー光の波長に強い吸収を有する添加剤のことであり、レーザー光吸収剤(D)自身は導電性であっても非導電性であってもよい。例えば、基本波の波長が1064nmであるYAGレーザーを光源として用いる場合には、波長1064nm
に強い吸収を有する染料および/又は顔料を、レーザー光吸収剤(D)として用いることができる。レーザー光吸収剤(D)を配合するとにより、本発明の導電性薄膜はレーザー光を高効率に吸収し、発熱によるバインダ樹脂(A)の揮散や熱分解が促進され、その結果レーザーエッチング加工適性が向上する。 <Laser light absorber (D)>
You may mix | blend a laser beam absorber (D) with the electrically conductive paste of this invention. Here, 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. For example, when a YAG laser having a fundamental wavelength of 1064 nm is used as the light source, the wavelength is 1064 nm.
Dyes and / or pigments having strong absorption can be used as the laser light absorber (D). By blending 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 resin (A) due to heat generation is promoted, and as a result, suitability for laser etching processing. Will improve.
本発明の導電性ペーストには、バインダ樹脂(A)と反応し得る硬化剤を、本発明の効果を損なわない程度に配合してもよい。硬化剤を配合することにより、硬化温度が高くなり、生産工程の負荷が増す可能性はあるが、塗膜乾燥時あるいはレーザーエッチング時に発生する熱による架橋で塗膜の耐湿熱性の向上が期待できる。 <Curing agent (E)>
You may mix | blend the hardening | curing agent which can react with binder resin (A) in the electrically conductive paste of this invention to such an extent that the effect of this invention is not impaired. By adding a curing agent, there is a possibility that the curing temperature becomes high and the load of the production process may increase. However, it is expected that 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. .
本発明の導電性ペーストは前述したように熱可塑性樹脂(A)、金属粉(B)、有機溶剤(C)および必要に応じてその他の成分を三本ロール等で分散して作製することができる。ここで、より具合的な作製手順の例を示す。熱可塑性樹脂(A)をまずは有機溶剤(C)に溶解する。その後、金属粉(B)ならびに、必要に応じて添加剤を添加し、ダブルプラネタリーやディゾルバー、遊星式の攪拌機等で予備分散を実施する。その後、三本ロールミルで分散して、導電性ペーストを得る。このようにして得られた導電性ペーストは必要に応じて濾過することができる。その他の分散機、例えばビーズミル、ニーダー、エクストルーダーなどを用いて分散しても何ら問題はない。 << Method for Producing Conductive Paste of the Present Invention >>
As described above, the conductive paste of the present invention can be prepared by dispersing the thermoplastic resin (A), the metal powder (B), the organic solvent (C), and other components as necessary with a three roll or the like. it can. Here, an example of a more specific production procedure is shown. The thermoplastic resin (A) is first dissolved in the organic solvent (C). Thereafter, the metal powder (B) and additives as necessary are added, and preliminary dispersion is carried out with a double planetary, a dissolver, a planetary stirrer or the like. Then, it disperses | distributes with a 3 roll mill, and obtains an electrically conductive paste. 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.
本発明の導電性ペーストを基材上に塗布または印刷して塗膜を形成し、次いで塗膜に含まれる有機溶剤(C)を揮散させ塗膜を乾燥させることにより、本発明の導電性薄膜を形成することができる。導電性ペーストを基材上に塗布または印刷する方法はとくに限定されないが、スクリーン印刷法により印刷することが工程の簡便さおよび導電性ペーストを用いて電気回路を形成する業界で普及している技術である点から好ましい。また、導電性ペーストは、最終的に電気回路として必要とされる導電性薄膜部位よりも幾分広い部位に塗布または印刷することが、レーザーエッチング工程の負荷を下げ効率よく本発明の電気回路を形成するとの観点から、好ましい。 << Conductive Thin Film, Conductive Laminate and Production Method of the Present Invention >>
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. In addition, 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.
られ、基本的にはどのような方式、どのような波長のレーザー種を用いても何ら問題はない。導電性薄膜のいずれかの構成成分の吸収波長領域と一致し、なおかつ基材が強い吸収を有さない波長を照射することのできるレーザー種を選択することにより、レーザー光照射部位の導電性薄膜の除去を効率的に行い、なおかつ基材のダメージを避けることができる。このような観点から、照射するレーザー種としては、基本波の波長が、532~10700nmの範囲が好ましい。例えば、ポリエステルフィルム、ポリエステルフィルム上にITO層を形成した透明導電性積層体、または、ポリエステルフィルム上にITO層を形成しその一部をエッチングにより除去された積層体を基材として用いる場合には、YAGレーザーまたはファイバーレーザーを使用することが、基本波の波長に基材が吸収を有さないので基材にダメージを与えにくい点で特に好ましい。 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. From such a viewpoint, the wavelength of the fundamental wave is preferably in the range of 532 to 10700 nm as the laser type to be irradiated. For example, when using as a base material a polyester film, a transparent conductive laminate in which an ITO layer is formed on a polyester film, or a laminate in which an ITO layer is formed on a polyester film and a part thereof is removed by etching It is particularly preferable to use a YAG laser or a fiber laser because the base material has no absorption at the wavelength of the fundamental wave and is difficult to damage the base material.
本発明の導電性薄膜、導電性積層体および/または電気回路はタッチパネルの構成部材としてを用いることができる。前記タッチパネルは、抵抗膜方式であっても静電容量方式であってもよい。いずれのタッチパネルにも適用が可能であるが、本ペーストは、細線形成に好適であるため、静電容量方式のタッチパネルの電極配線用に特に好適に用いることができる。尚、前記タッチパネルを構成する基材としては、ITO膜等の透明導電性層を有している基材、もしくはそれらがエッチングによって一部除去された基材を用いることが好ましい。 << Touch Panel of the Present Invention >>
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. In addition, as 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 | membrane, or the base material from which they were partially removed by the etching.
試料樹脂を、樹脂濃度が0.5重量%程度となるようにテトラヒドロフランに溶解し、孔径0.5μmのポリ四フッ化エチレン製メンブランフィルターで濾過し、GPC測定試料とした。テトラヒドロフランを移動相とし、島津製作所社製のゲル浸透クロマトグラフ(GPC)Prominenceを用い、示差屈折計(RI計)を検出器として、カラム温度30℃、流量1ml/分にて樹脂試料のGPC測定を行なった。尚、数平均分子量は標準ポリスチレン換算値とし、分子量1000未満に相当する部分を省いて算出した。GPCカラムは昭和電工(株)製のshodex KF-802、804L、806Lを用いた。 1. Number average molecular weight 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 μm 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. As the GPC column, shodex KF-802, 804L and 806L manufactured by Showa Denko KK were used.
試料樹脂5mgをアルミニウム製サンプルパンに入れて密封し、セイコーインスツルメンツ(株)製の示差走査熱量分析計(DSC)DSC-220を用いて、200℃まで、昇温速度20℃/分にて測定し、ガラス転移温度以下のベースラインの延長線と遷移部における最大傾斜を示す接線との交点の温度で求めた。 2. 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.
試料樹脂0.2gを精秤し20mlのクロロホルムに溶解した。ついで、指示薬にフェノールフタレイン溶液を用い、0.01Nの水酸化カリウム(エタノール溶液)で滴定を行った。酸価の単位はeq/ton、すなわち試料1トン当たりの当量とした。 3. Acid value 0.2 g of sample resin was precisely weighed and dissolved in 20 ml of chloroform. Subsequently, titration was performed with 0.01 N potassium hydroxide (ethanol solution) using a phenolphthalein solution as an indicator. The unit of the acid value was eq / ton, that is, the equivalent per 1 ton of the sample.
クロロホルム-dに試料樹脂を溶解し、VARIAN製400MHz-NMR装置を用い、1H-NMR分析により樹脂組成を求めた。 4). Resin Composition The sample resin was dissolved in chloroform-d, and the resin composition was determined by 1 H-NMR analysis using a Varian 400 MHz-NMR apparatus.
粘度の測定はサンプル温度25℃において、BH型粘度計(東機産業社製,)を用い、
20rpmにおいて測定を実施した。 5. Paste viscosity Viscosity is measured at a sample temperature of 25 ° C using a BH viscometer (manufactured by Toki Sangyo Co.,
Measurements were performed at 20 rpm.
導電性ペーストをポリ容器に入れ、密栓したものを40℃で1ヶ月貯蔵した。貯蔵後に粘度測定及び上記5.導電性積層体テストピースにより作製したテストピースの評価を行った。
○:著しい粘度変化はなく、初期の比抵抗、鉛筆硬度および密着性を維持している。
×:著しい粘度上昇(初期粘度の2倍以上)または著しい粘度低下(初期粘度の1/2以
下)、および/または、比抵抗、鉛筆硬度および/または密着性の低下、のいずれかが認められる。 6). Storage stability of conductive paste The conductive paste was placed in a plastic container and sealed and stored at 40 ° C. for 1 month. 4. Viscosity measurement after storage and above 5. The test piece produced by the conductive laminate test piece was evaluated.
◯: There is no significant change in viscosity, and the initial specific resistance, pencil hardness and adhesion are maintained.
X: Either a significant increase in viscosity (more than twice the initial viscosity) or a significant decrease in viscosity (1/2 or less of the initial viscosity) and / or a decrease in specific resistance, pencil hardness and / or adhesion are observed. .
厚み100μmのアニール処理をしたPETフィルム(東レ社製ルミラーS)およびITO膜(尾池工業(株)製、KH300)のそれぞれに、200メッシュのポリエステルスクリーンを用いてスクリーン印刷法により導電性ペーストを印刷し、幅25mm、長さ450mmのべた塗りパターンを形成し、次いで熱風循環式乾燥炉にて120℃で30分加熱したものを導電性積層体テストピースとした。なお、乾燥膜厚が6~10μmになるように印刷時の塗布厚を調整した。 7). Preparation of conductive laminate test piece A 200-mesh polyester screen was used for each of a PET film (Lumirror S manufactured by Toray Industries, Inc.) and an ITO film (KH300 manufactured by Oike Kogyo Co., Ltd.) that had been annealed to a thickness of 100 μm. A conductive paste was printed by a screen printing method to form a solid coating pattern having a width of 25 mm and a length of 450 mm, and then heated at 120 ° C. for 30 minutes in a hot air circulation drying oven to obtain a conductive laminate test piece. . The coating thickness at the time of printing was adjusted so that the dry film thickness was 6 to 10 μm.
前記導電性積層体テストピースを用いてJIS K-5400-5-6:1990に従って、セロテープ(登録商標)(ニチバン(株)製)を用い、剥離試験により評価した。但し、格子パターンの各方向のカット数は11個、カット間隔は1mmとした。100/100は剥離がなく密着性が良好なことを示し、0/100は全て剥離してしまったことを表す。 8). Adhesiveness Using the conductive laminate test piece, according to JIS K-5400-5-6: 1990, evaluation was performed by a peel test using cello tape (registered trademark) (manufactured by Nichiban Co., Ltd.). However, the number of cuts in each direction of the lattice pattern was 11, and the cut interval was 1 mm. 100/100 indicates that there is no peeling and good adhesion, and 0/100 indicates that all are peeled off.
前記導電性積層体テストピースのシート抵抗と膜厚を測定し、比抵抗を算出した。膜厚はゲージスタンドST-022(小野測器社製)を用い、PETフィルムの厚みをゼロ点として硬化塗膜の厚みを5点測定し、その平均値を用いた。シート抵抗はMILLIOHMMETER4338B(HEWLETT PACKARD社製)を用いてテストピース4枚について測定し、その平均値を用いた。尚、本ミリオームメーターで検出できる範囲は1×10-2以下(Ω・cm)であり、1×10-2(Ω・cm)以上の比抵抗は測定限界外となる。 9. Specific Resistance The sheet resistance and film thickness of the conductive laminate test piece were measured, and the specific resistance was calculated. For the film thickness, a gauge stand ST-022 (manufactured by Ono Sokki Co., Ltd.) was used, and the thickness of the cured coating film was measured at 5 points using the thickness of the PET film as a zero point, and the average value was used. 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 or less (Ω · cm), and a specific resistance of 1 × 10 −2 (Ω · cm) or more is outside the measurement limit.
導電性積層体テストピースを厚さ2mmのSUS304板上に置き、JIS K 5600-5-4:1999に従って鉛筆硬度を測定した。 10. Pencil Hardness The conductive laminate test piece was placed on a 2 mm thick SUS304 plate, and the pencil hardness was measured according to JIS K 5600-5-4: 1999.
導電性積層体テストピースを、80℃で300時間加熱し、次いで85℃、85%RH(相対湿度)で300時間加熱し、その後24時間常温で放置した後、各種評価を行った。 11. Moisture and heat resistance test:
The conductive laminate test piece was 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.
スクリーン印刷法により、ポリエステル基材(東レ社製ルミラーS(厚み100μm))上に、導電性ペーストを2.5×10cmの長方形に印刷塗布した。スクリーン版としてT400ステンレスメッシュ(乳剤厚10μm、線径23μm(東京プロセスサービス社製))を用い、スキージ速度150mm/sで印刷した。印刷塗布後、熱風循環式乾燥炉にて120℃で30分間の乾燥を行って導電性薄膜を得た。尚、膜厚は5~12μmとなるようにペーストを希釈調整した。次いで、上記方法にて作成した導電性薄膜にレーザーエッチング加工を行い、図1に示す長さ50mmの4本の直線部分を有するパターンを作製し、レーザーエッチング加工適性評価試験片とした。上記直線部分の線間のレーザーエッチング加工は、ビーム径30μmのレーザー光を60μmピッチで各2回走査することに
よって行った。レーザー光源にはファイバーレーザーを用い、Q変調周波数200kHz、出力10W、走査速度2700mm/sとした。 12 Evaluation of laser etching process suitability A conductive paste was printed and applied in a 2.5 × 10 cm rectangle on a polyester base material (Lumirror S (thickness: 100 μm) manufactured by Toray Industries, Inc.) by a screen printing method. A T400 stainless mesh (
前記レーザーエッチング加工適性評価試験片において、導電性薄膜が除去された部位の線幅を測定した。測定は、レーザー顕微鏡(キーエンスVHX-1000)を用いて行い、下記の評価判断基準で判定した。
○;導電性薄膜が除去された部位のライン幅が28~32μm
△;導電性薄膜が除去された部位のライン幅が24~27μmもしくは33~36μm
×;導電性薄膜が除去された部位のライン幅が23μm以下、もしくは37μm以上 (Laser etching processing width evaluation)
In the laser etching process suitability evaluation test piece, the line width of the portion where the conductive thin film was removed 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 μm.
Δ: The line width of the portion where the conductive thin film is removed is 24 to 27 μm or 33 to 36 μm.
X: The line width of the portion where the conductive thin film has been removed is 23 μm or less, or 37 μm or more
前記レーザーエッチング加工適性評価試験片において、細線1b、2b、3b、4bの両端の間の導通が確保されているかにより評価した。具体的には、端子1a-端子1c間、端子2a-端子2c間、端子3a-端子3c間、端子4a-端子4c間、のそれぞれについてテスターを当てて導通の有無を確認し、下記評価基準で判定した。
○;4本の細線の全てについて細線の両端間に導通がある
△;4本の細線のうち、1~3本について細線の両端間に導通がない
×;4本の細線の全てについて細線の両端間に導通がない
(レーザーエッチング加工適性評価(2)隣接細線間絶縁性)
前記レーザーエッチング加工適性評価試験片において、隣接する細線の間の絶縁が確保されているかにより評価した。具体的には、端子1a-端子2a間、端子2a-端子3a間、端子3a-端子4a間、のそれぞれについてテスターを当てて導通の有無を確認し、下記評価基準で判定した。
○;すべての隣接細線間が絶縁されている
△;一部の隣接細線間が絶縁されている
×;すべての隣接細線間が絶縁されていない (Laser etching process suitability evaluation (1) Conductivity between both ends of fine wire)
In the laser etching process suitability evaluation test piece, the evaluation was made based on whether or not conduction between both ends of the
○: Conduction between both ends of the fine wire for all four fine wires Δ: 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
○: All adjacent fine wires are insulated △: Some adjacent fine wires are insulated ×: All adjacent fine wires are not insulated
前記レーザーエッチング加工適性評価試験片において、導電性薄膜が除去された部位をレーザー顕微鏡で観察し、残渣の付着有無を下記評価基準により判定した。
○:導電性薄膜が除去された部位に残渣がない。
△:導電性薄膜が除去された部位に残渣が多少ある。
×:導電性薄膜が除去された部位に残渣が多く見られる。 (Evaluation of residue at the site where the conductive thin film has been removed)
In the laser etching process suitability evaluation test piece, the site from which the conductive thin film was removed was observed with a laser microscope, and the presence or absence of residue was determined according to the following evaluation criteria.
○: There is no residue at the site where the conductive thin film has been removed.
Δ: There is some residue at the site where the conductive thin film has been removed.
X: Many residues are observed at the site where the conductive thin film has been removed.
前記レーザーエッチング加工適性評価試験片における導電性薄膜が除去された部位に挟まれている導電性薄膜が残存している部位の、基材に対する密着性を、セロテープ(登録商標)(ニチバン(株)製)を用いたテープ剥離テストにより、評価した。この評価は、試験片作成の24時間後直後(初期)とその後さらに85℃、85%RH(相対湿度)の湿熱環境下に120時間静置しさらに24時間常温で静置した後(耐湿熱試験後)に行った。
○:剥離がない。 △:一部剥離する。×:全て剥離する。 (Evaluation of adhesion between conductive thin film and substrate after laser etching)
The adhesiveness to the substrate of the portion where the conductive thin film is sandwiched between the portions where the conductive thin film has been removed in the laser etching processing suitability evaluation test piece is measured with Cellotape (registered trademark) (Nichiban Co., Ltd.) The product was evaluated by a tape peeling test using This evaluation was performed immediately after 24 hours (initial stage) after the test piece was prepared, and after that, after further standing in a moist heat environment of 85 ° C. and 85% RH (relative humidity) for 120 hours and then at room temperature for 24 hours (moisture heat resistance After the test).
○: No peeling. Δ: Partially peeled off. X: All peel.
ポリエステル樹脂P-1の製造例
攪拌機、コンデンサー、及び温度計を具備した反応容器にテレフタル酸700部、イソフタル酸700部、無水トリメリット酸16.9部、エチレングリコール983部、2-メチル-1,3-プロパンジオール154部を仕込み、窒素雰囲気2気圧加圧下、160℃から230℃まで3時間かけて昇温し、エステル化反応を行った。放圧後、テトラブチルチタネート0.92部を仕込み、次いで系内を徐々に減圧していき、20分かけて5mmHgまで減圧し、さらに0.3mmHg以下の真空下、260℃にて40分間重縮合反応を行った。次いで、窒素気流下、220℃まで冷却し、無水トリメリット酸を50.6部投入し、30分間反応を行いポリエステル樹脂を得た。得られた共重合ポリエステル樹脂P-1の組成及び物性を表1に示した。 Example of Resin Production Example of Polyester Resin P-1 In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 700 parts of terephthalic acid, 700 parts of isophthalic acid, 16.9 parts of trimellitic anhydride, 983 parts of ethylene glycol, 2 -154 parts of methyl-1,3-propanediol were charged, and the temperature was raised from 160 ° C to 230 ° C over 3 hours under a pressure of 2 atmospheres in a nitrogen atmosphere to carry out an esterification reaction. After releasing the pressure, 0.92 part of tetrabutyl titanate was added, and then the pressure inside the system was gradually reduced to 5 mmHg over 20 minutes, and then the pressure was reduced to 260 ° C. for 40 minutes under a vacuum of 0.3 mmHg or less. A condensation reaction was performed. Subsequently, it cooled to 220 degreeC under nitrogen stream, 50.6 parts of trimellitic anhydride was thrown in, and it reacted for 30 minutes, and obtained the polyester resin. The composition and physical properties of the obtained copolyester resin P-1 are shown in Table 1.
ポリエステル樹脂P-1の製造例においてモノマーの種類と配合比率を変更し、ポリエステル樹脂P-2~P-11を製造した。得られた共重合ポリエステル樹脂の組成及び樹脂物性を表1~2に示した。 Production Examples of Polyester Resins P-2 to P-11 Polyester resins P-2 to P-11 were produced by changing the type and blending ratio of the monomers in the production example of polyester resin P-1. The compositions and physical properties of the obtained copolyester resins are shown in Tables 1 and 2.
BPX-11 :ビスフェノールAのプロピレンオキサイド付加物(旭電化社製) BPE-20F: Ethylene oxide adduct of bisphenol A (manufactured by Sanyo Chemical Industries)
BPX-11: Propylene oxide adduct of bisphenol A (Asahi Denka)
攪拌機、コンデンサー、温度計を具備した反応容器にポリエステル樹脂P-7を1000部、ネオペンチルグリコール(NPG)を80部、ジメチロールブタン酸(DMBA)を90部投入した後、エチルジグリコールアセテート(EDGAC)1087部仕込み、85℃において溶解した。その後、4,4’-ジフェニルメタンジイソシアネート(MDI)を460部加え、85℃、2時間反応を行った後、触媒としてジブチルチンジラウレートを0.5部添加し、85℃でさらに4時間反応させた。ついで、EDGAC1940部で溶液を希釈し、ポリウレタン樹脂U-1の溶液を得た。得られたポリウレタン樹脂溶液の固形分濃度は35質量%であった。このようにして得た樹脂溶液をポリプロピレンフィルム上に滴下し、ステンレス鋼製のアプリケーターを用いて延展し、樹脂溶液の薄膜を得た。これを120℃に調整した熱風乾燥機内に3時間静置して溶剤を揮散させ、次いでポリプロピレンフィルムから樹脂薄膜を剥がし、フィルム状の乾燥樹脂薄膜を得た。乾燥樹脂薄膜の厚みは約30μmであった。左記乾燥樹脂薄膜をポリウレタン樹脂U-1の試料樹脂として、各種樹脂物性の評価結果を表3に示した。 Example of production of polyurethane resin U-1 In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 1000 parts of polyester resin P-7, 80 parts of neopentyl glycol (NPG) and 90 parts of dimethylolbutanoic acid (DMBA) are charged. Then, 1087 parts of ethyl diglycol acetate (EDGAC) was charged and dissolved at 85 ° C. Thereafter, 460 parts of 4,4′-diphenylmethane diisocyanate (MDI) was added and reacted at 85 ° C. for 2 hours, and then 0.5 part of dibutyltin dilaurate was added as a catalyst and reacted at 85 ° C. for another 4 hours. . Next, the solution was diluted with 1940 parts of EDGAC to obtain a solution of polyurethane resin U-1. The solid content concentration of the obtained polyurethane resin solution was 35% by mass. 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 μm. Table 3 shows the evaluation results of various resin properties, using the dry resin thin film on the left as a sample resin of polyurethane resin U-1.
ポリウレタン樹脂U-2~U-8は、ポリエステルポリオール、イソシアネートと反応する基を有する化合物及びポリイソシアネートを表3に示すものに代えた以外は、ポリウレタン樹脂U-1の製造例と同様の方法にて製造した。ポリウレタン樹脂U-2~U-8の樹脂物性の評価結果を表3に示した。 Production Examples of Polyurethane Resins U-2 to U-8 Polyurethane resins U-2 to U-8 are polyurethanes except that polyester polyols, compounds having groups that react with isocyanates, and polyisocyanates are replaced with those shown in Table 3. The resin U-1 was produced by the same method as in the production example. The evaluation results of the resin physical properties of the polyurethane resins U-2 to U-8 are shown in Table 3.
NPG:ネオペンチルグリコール
DMH:2-ブチル-2-エチル-1,3-プロパンジオール
MDI:4,4’-ジフェニルメタンジイイソシアネート
IPDI:イソホロンジイソシアネート DMBA: dimethylol butanoic acid NPG: neopentyl glycol DMH: 2-butyl-2-ethyl-1,3-propanediol MDI: 4,4′-diphenylmethane diisocyanate IPDI: isophorone diisocyanate
ポリエステル樹脂P-1を固形分濃度が35質量%となるようにEDGACに溶解した溶液2860部(固形部換算1000部)、フレーク状銀粉1を7,888部、レベリング剤として共栄社化学(株)製のMKコンクを71部、分散剤としてビックケミー・ジャパン(株)製のDisperbyk130を30部、溶剤としてEDGACを300部を配合し、チルド三本ロール混練り機に3回通して分散した。その後、得られた導電性ペーストを所定のパターンに印刷後、120℃×30分間乾燥し、導電性薄膜を得た。本導電性薄膜を用いて基本物性を測定し、次いで、レーザーエッチング加工の検討を行った。ペーストおよびペースト塗膜、レーザーエッチング加工性の評価結果を表4に示した。 Example 1
2860 parts (1000 parts in terms of solid part) of polyester resin P-1 dissolved in EDGAC so that the solid content concentration is 35% by mass, 7,888 parts of flaky silver powder 1, and Kyoeisha Chemical Co., Ltd. as a leveling agent 71 parts of MK Conk made, 30 parts of Disperbyk 130 made by Big Chemie Japan Co., Ltd. as a dispersant and 300 parts of EDGAC as a solvent were blended and dispersed by passing 3 times through a chilled three-roll kneader. Thereafter, the obtained conductive paste was printed in a predetermined pattern and then dried at 120 ° 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. Table 4 shows the evaluation results of the paste, paste coating film, and laser etching processability.
導電性ペーストの樹脂および配合を変えて実施例2~17を実施した。導電性ペーストの配合および評価結果を表4~表6に示した。実施例においてはオーブン120℃×30分という比較的低温かつ短時間の加熱により良好な塗膜物性を得ることができた。またITO膜への密着性、湿熱環境試験後の密着性も良好であった。 Examples 2 to 13
Examples 2 to 17 were carried out by changing the resin and formulation of the conductive paste. The formulation and evaluation results of the conductive paste are shown in Tables 4 to 6. In the examples, good film properties could be obtained by heating at a relatively low temperature of 120 ° C. for 30 minutes in an oven at a relatively low temperature. Also, the adhesion to the ITO film and the adhesion after the wet heat environment test were good.
バインダ樹脂PH-1:InChem製PKKH(フェノキシ樹脂、数平均分子量14000、Tg=71℃)
銀粉1:フレーク状銀粉(D50:2μm)
銀粉2:球状銀粉(D50:1μm)
カーボンブラック:東海カーボン(株)製♯4400
ケッチェンブラック:ライオン(株)製ケッチェンECP600JD
グラファイト粉:(株)中越黒鉛工業所製のグラファイトBF
硬化剤:旭化成ケミカルズ(株)製MF-K60X
硬化触媒:共同薬品(株)製KS1260
レベリング剤:共栄社化学(株)MKコンク
分散剤1:ビックケミー・ジャパン(株)社製のDisperbyk130
分散剤2:ビックケミー・ジャパン(株)社製Disperbyk2155
分散剤3:ビックケミー・ジャパン(株)社製のDisperbyk180
添加剤1:日本アエロジル(株)製シリカR972
添加剤2:ナガセケムテックス(株)製 NIR-AM1
添加剤3:共栄社化学(株)製 ライトアクリレートPE-3A(ペンタエリスリトールトリアクリレート)
EDGAC:(株)ダイセル製エチルジグリコールアセテート
BMGAC:(株)ダイセル製ブチルグリコールアセテート
BDGAC:(株)ダイセル製ブチルジグリコールアセテート
TPOL :日本テルペン化学(株)製ターピネオール In Tables 4 to 7, the following binder resin, conductive powder, additive and solvent were used.
Binder resin PH-1: PKKH manufactured by InChem (phenoxy resin, number average molecular weight 14000, Tg = 71 ° C.)
Silver powder 1: flaky silver powder (D50: 2 μm)
Silver powder 2: Spherical silver powder (D50: 1 μm)
Carbon black: Tokai Carbon Co., Ltd. # 4400
Ketjen Black: Ketjen ECP600JD made by Lion Corporation
Graphite powder: Graphite BF manufactured by Chuetsu Graphite Co., Ltd.
Curing agent: MF-K60X manufactured by Asahi Kasei Chemicals Corporation
Curing catalyst: Kyodo Pharmaceutical Co., Ltd. KS1260
Leveling agent: Kyoeisha Chemical Co., Ltd. MK Conk Dispersant 1: Disperbyk130 manufactured by Big Chemie Japan Co., Ltd.
Dispersant 2: Disperbyk 2155 manufactured by Big Chemie Japan Co., Ltd.
Dispersant 3: Disperbyk180 manufactured by Big Chemie Japan Co., Ltd.
Additive 1: Silica R972 manufactured by Nippon Aerosil Co., Ltd.
Additive 2: NIR-AM1 manufactured by Nagase ChemteX Corporation
Additive 3: Light acrylate PE-3A (pentaerythritol triacrylate) manufactured by Kyoeisha Chemical Co., Ltd.
EDGAC: Ethyl diglycol acetate manufactured by Daicel Corp. BMGAC: Butyl glycol acetate manufactured by Daicel Corp. BDGAC: Butyl diglycol acetate manufactured by Daicel Corp. TPOL: Terpineol manufactured by Nippon Terpene Chemical Co., Ltd.
ラウリルカルボン酸銀(1000g)とブチルアミン(480g)とをトルエン(10L)に溶解させた。次いで、蟻酸(150g)を滴下し、そのまま室温で1.5時間攪拌した。大量のメタノールを加えると銀ナノ粒子の凝集物が沈殿するのでこれをデカンテーションした。デカンテーションを3回繰り返したのち、沈殿物を減圧下で乾燥させた。次いで、得られた沈殿物1000g(うち920g銀、カルボン酸銀アミン錯体80g)をターピネオール1860g中へ再分散させ、銀ナノ粒子(銀粉3)を含んだ導電性ペーストを得た。得られた銀粉3は透過型電子顕微鏡写真より粒子径が約10nmであった。導電性ペーストの固形分濃度は35質量%であった。得られた導電性ペーストを用いて実施例と同様に導電性積層体テストピースおよびレーザーエッチング加工適性評価試験片を作成し、実施例と同様に評価を行った。評価結果を表7に示した。本導電性銀ペースト組成物は初期塗膜物性が顕著に劣り、特には密着性に乏しく、実用には耐えないものであった。 Comparative Example 1
Silver lauryl carboxylate (1000 g) and butylamine (480 g) were dissolved in toluene (10 L). Next, formic acid (150 g) was added dropwise, and the mixture was stirred at room temperature for 1.5 hours. When a large amount of methanol was added, an aggregate of silver nanoparticles precipitated and was decanted. After repeating the decantation three times, the precipitate was dried under reduced pressure. Next, 1000 g of the resulting precipitate (of which 920 g silver, 80 g silver carboxylate amine complex) was redispersed in 1860 g terpineol to obtain a conductive paste containing silver nanoparticles (silver powder 3). The obtained silver powder 3 had a particle diameter of about 10 nm from a transmission electron micrograph. The solid content concentration of the conductive paste was 35% by mass. Using the obtained conductive paste, a conductive laminate test piece and a laser etching processability evaluation test piece were prepared in the same manner as in the example, and the evaluation was performed in the same manner as in the example. The evaluation results are shown in Table 7. This electroconductive silver paste composition was remarkably inferior in initial coating film properties, in particular, poor in adhesion, and could not withstand practical use.
ターピネオールにドデシルアミンを溶解し、固形分濃度12重量%の溶液とした。この溶液1000部(固形120重量部)に、銀粉4(球状銀粉(D50=1μm)を8083部、さらに平均粒径1.5μmとなるようにビーズミルで粉砕したガラスフリット((酸化ビスマス(Bi2O3)を主成分するガラス粉末(酸化ビスマス含有量80.0~99.9%)を
250部加えて混合を継続し、均一となってから、この溶液を三本ロールミルで分散し、ガラスフリット含有導電性ペーストを作製した。得られた導電性ペーストを用いて実施例と同様に導電性積層体テストピースおよびレーザーエッチング加工適性評価試験片を作成し、実施例と同様に評価を行った。評価結果を表7に示した。本導電性銀ペースト組成物は初期塗膜物性が顕著に劣り、特には密着性に乏しく、実用には耐えないものであった。また、レーザーエッチング加工性が顕著に劣り、照射部位よりも広い範囲で照射したレーザービームの幅よりも大幅に広い巾の塗膜が剥離されてしまい、所定の線幅を加工することはできなかった。また、レーザーエッチング加工後の細線部分の密着性および耐湿熱性にも乏しかった。 Comparative Example 2
Dodecylamine was dissolved in terpineol to obtain a solution having a solid content of 12% by weight. To 1000 parts of this solution (solid 120 parts by weight), silver powder 4 (spherical silver powder (D50 = 1 μm) 8083 parts, and further a glass frit (bismuth oxide (Bi 2 Add 250 parts of O 3 ) glass powder (bismuth oxide content: 80.0-99.9%) and continue mixing. After the mixture is uniform, disperse this solution with a three-roll mill. Using the obtained conductive paste, a conductive laminate test piece and a laser etching processability evaluation test piece were prepared in the same manner as in the example, and evaluated in the same manner as in the example. It was shown in Table 7. This conductive silver paste composition was remarkably inferior in initial coating film properties, in particular, poor adhesion, and could not withstand practical use. The coating film with a width much wider than the width of the laser beam irradiated in a wider range than the irradiated site was peeled off, and the predetermined line width could not be processed. The adhesion of the thin wire portion after etching and the heat and humidity resistance were also poor.
1b、2b、3b、4b : 細線1b、2b、3b、4b
1c、2c、3c、4c : 端子1c、2c、3c、4c
5 : レーザーエッチング加工適性評価試験片上に形成されるパターン 1a, 2a, 3a, 4a:
1b, 2b, 3b, 4b:
1c, 2c, 3c, 4c:
5: Pattern formed on test piece for evaluating laser etching process suitability
Claims (12)
- 熱可塑性樹脂からなるバインダ樹脂(A)、金属粉(B)および有機溶剤(C)を含有するレーザーエッチング加工用導電性ペースト。 A conductive paste for laser etching containing a binder resin (A) made of a thermoplastic resin, a metal powder (B) and an organic solvent (C).
- 前記バインダ樹脂(A)が、数平均分子量が5,000~60,000であり、なおかつ、ガラス転移温度が60~100℃である熱可塑性樹脂であることを特徴とする、請求項1に記載のレーザーエッチング加工用導電性ペースト。 2. The binder resin (A) according to claim 1, wherein the binder resin (A) is a thermoplastic resin having a number average molecular weight of 5,000 to 60,000 and a glass transition temperature of 60 to 100 ° C. Conductive paste for laser etching.
- 前記バインダ樹脂(A)が、ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂、塩化ビニル樹脂、繊維素誘導体樹脂からなる群から選ばれる1種又は2種以上の混合物であることを特徴とする請求項1または2に記載のレーザーエッチング加工用導電性ペースト。 The binder resin (A) is one or a mixture of two or more selected from the group consisting of a polyester resin, a polyurethane resin, an epoxy resin, a vinyl chloride resin, and a fiber derivative resin. The conductive paste for laser etching according to 2.
- 前記バインダ樹脂(A)が、酸価50~300当量/106gであるポリエステル樹脂および酸価50~300当量/106gであるポリウレタン樹脂からなる群から選ばれる1種又は2種以上の混合物であることを特徴とする請求項1または2に記載のレーザーエッチング加工用導電性ペースト。 The binder resin (A) is an acid value 50-300 from the group consisting of polyurethane resins one or more selected is equivalent / 10 6 g polyester resin is and an acid number of 50-300 equivalents / 10 6 g The conductive paste for laser etching according to claim 1 or 2, which is a mixture.
- 更にレーザー光吸収剤(D)を含有することを特徴とする請求項1~4のいずれかに記載の導電性レーザーエッチング加工用導電性ペースト。 The conductive paste for conductive laser etching according to any one of claims 1 to 4, further comprising a laser light absorber (D).
- 請求項1~5のいずれかに記載のレーザーエッチング加工用導電性ペーストから形成された導電性薄膜。 A conductive thin film formed from the conductive paste for laser etching according to any one of claims 1 to 5.
- 請求項6に記載の導電性薄膜と基材とが積層されている導電性積層体。 A conductive laminate in which the conductive thin film according to claim 6 and a substrate are laminated.
- 前記基材が透明導電性層を有することを特徴とする請求項7に記載の導電性積層体。 The conductive laminate according to claim 7, wherein the substrate has a transparent conductive layer.
- 請求項6に記載の導電性薄膜、または、請求項7または8に記載の導電性積層体、を用いてなる電気回路。 An electric circuit using the conductive thin film according to claim 6 or the conductive laminate according to claim 7 or 8.
- 請求項6に記載の導電性薄膜の一部に、炭酸ガスレーザー、YAGレーザー、ファイバーレーザーおよび半導体レーザーから選ばれるレーザー光を照射して、前記導電性薄膜の一部を除去することによって形成された配線部位を有する電気回路。 It is formed by irradiating a part of the conductive thin film according to claim 6 with a laser beam selected from a carbon dioxide laser, a YAG laser, a fiber laser and a semiconductor laser to remove a part of the conductive thin film. An electric circuit having a wiring part.
- 前記導電性薄膜が透明導電性層上に形成されていることを特徴とする請求項9に記載の電気回路。 10. The electric circuit according to claim 9, wherein the conductive thin film is formed on a transparent conductive layer.
- 請求項9~11のいずれかに記載の電気回路を構成部材として含むタッチパネル。 A touch panel comprising the electric circuit according to any one of claims 9 to 11 as a constituent member.
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JP2013532388A JP5773292B2 (en) | 2012-07-20 | 2013-07-08 | Conductive paste, conductive thin film and conductive laminate for laser etching |
CN201380038679.7A CN104488040B (en) | 2012-07-20 | 2013-07-08 | Use circuit wiring, circuit and touch panel made of laser ablation processing conductive paste |
KR1020187007912A KR102007129B1 (en) | 2012-07-20 | 2013-07-08 | Conductive paste for laser etching, conductive thin film, and conductive laminate |
KR20157001614A KR20150037861A (en) | 2012-07-20 | 2013-07-08 | Conductive paste for laser etching, conductive thin film, and conductive laminate |
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Also Published As
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JP2015135817A (en) | 2015-07-27 |
JP2020053393A (en) | 2020-04-02 |
JP2017126771A (en) | 2017-07-20 |
TW201515022A (en) | 2015-04-16 |
JP2015181207A (en) | 2015-10-15 |
CN104488040A (en) | 2015-04-01 |
JP6363048B2 (en) | 2018-07-25 |
JPWO2014013899A1 (en) | 2016-06-30 |
JP5773298B2 (en) | 2015-09-02 |
CN104488040B (en) | 2018-08-03 |
JP5987930B2 (en) | 2016-09-07 |
KR20150037861A (en) | 2015-04-08 |
KR20180031820A (en) | 2018-03-28 |
KR102007129B1 (en) | 2019-08-02 |
JP2014225709A (en) | 2014-12-04 |
JP5987878B2 (en) | 2016-09-07 |
JP7059240B2 (en) | 2022-04-25 |
JP2015026618A (en) | 2015-02-05 |
JP5773292B2 (en) | 2015-09-02 |
JP2018067548A (en) | 2018-04-26 |
JP6458820B2 (en) | 2019-01-30 |
TWI620202B (en) | 2018-04-01 |
JP2015127958A (en) | 2015-07-09 |
TW201409489A (en) | 2014-03-01 |
JP5880650B2 (en) | 2016-03-09 |
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