WO2008065976A1 - Procédé de formation de motif conducteur - Google Patents

Procédé de formation de motif conducteur Download PDF

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Publication number
WO2008065976A1
WO2008065976A1 PCT/JP2007/072713 JP2007072713W WO2008065976A1 WO 2008065976 A1 WO2008065976 A1 WO 2008065976A1 JP 2007072713 W JP2007072713 W JP 2007072713W WO 2008065976 A1 WO2008065976 A1 WO 2008065976A1
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WO
WIPO (PCT)
Prior art keywords
emulsion layer
silver halide
substrate
halide emulsion
conductive pattern
Prior art date
Application number
PCT/JP2007/072713
Other languages
English (en)
Japanese (ja)
Inventor
Minoru Ohashi
Yasuo Tsubai
Original Assignee
Mitsubishi Paper Mills Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2007139881A external-priority patent/JP5166772B2/ja
Application filed by Mitsubishi Paper Mills Limited filed Critical Mitsubishi Paper Mills Limited
Publication of WO2008065976A1 publication Critical patent/WO2008065976A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/58—Processes for obtaining metallic images by vapour deposition or physical development
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
    • H05K3/184—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method using masks
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
    • H05K3/106—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam by photographic methods

Definitions

  • the present invention relates to a method of forming a conductive pattern on a substrate such as a film or a glass substrate.
  • Manufacturing methods of a material having a conductive pattern on a substrate are roughly classified into a printing method, a photolithography method, a silver salt method, and other methods.
  • a printing method a method in which conductive metal ink or paste is printed on a substrate by means of screen printing or the like and then fired to impart conductivity (Patent Document 1), and an electroless galvanizing touch on the substrate.
  • Patent Document 2 A method in which a conductive paint is applied by electroless plating after printing a resin paint containing a medium.
  • a photoresist is applied onto a substrate having a uniform conductive metal layer, exposed, developed, and then the conductive metal layer from which the resist has been peeled is removed by etching to obtain a conductive pattern.
  • Subtractive method (Patent Document 3): A resist containing an electroless plating catalyst is coated on a support, exposed and developed, and after removing the unexposed portion of the resist, electroless plating is performed. There is an additive method (Patent Document 4) for obtaining a sex pattern.
  • a conductive image forming layer composed of a silver particle layer is formed on a transparent support by silver plating or the like, and the image forming layer is irradiated with high-density energy light.
  • Patent Document 5 a method of reducing the bonding force between the image forming layer and the support in the irradiated area to obtain a conductive pattern
  • Patent Document 7 As a silver salt method using photosensitive silver halide, a silver salt diffusion transfer method ( Patent Document 6) and those using chemically developed silver (Patent Document 7) have been proposed! Among these silver salt methods, a method using chemically developed silver as shown in Patent Document 7 is a method in which a photosensitive silver halide emulsion layer provided on a support is exposed to light with a developer. In this method, after development, the electroconductive plating is performed by applying electroless plating using chemically developed silver, which is formed by reducing the silver halide in the exposed portion by the developing agent present in the developer.
  • those using the silver salt diffusion transfer system are called physical development nuclei on a support, a physical development nucleus layer for reducing a silver complex to metallic silver by reduction with a developing agent, and a halogen layer on the upper layer.
  • a material provided with a silver halide emulsion layer is used.
  • a compound that dissolves silver halide (silver halide solvent) is added to the developer in addition to the developing agent.
  • the exposed silver halide is converted to chemically developed silver and remains in the silver halide emulsion layer.
  • the silver halide in the unexposed area is dissolved by the silver halide solvent added in the developer and becomes a silver complex that moves and diffuses to the physical development nucleus layer on the support, where it is reduced by the developing agent.
  • conductive metallic silver is deposited.
  • the silver halide emulsion layer containing chemically developed silver at the exposed site is removed by washing off.
  • the physical development nucleus layer still remains on the support, which is a negative factor for ensuring transparency.
  • problems such as complicated manufacturing processes including the application of an extremely thin physical development nucleus layer.
  • Patent Document 1 JP 55-91199 A
  • Patent Document 2 Pamphlet of International Publication No. 04/39138
  • Patent Document 3 Japanese Patent Laid-Open No. 5-16281
  • Patent Document 4 JP-A-11 170421
  • Patent Document 5 JP-A-10-151858
  • Patent Document 6 International Publication No. 04/007810 Pamphlet
  • Patent Document 7 Japanese Unexamined Patent Application Publication No. 2004-221564
  • the present invention has been made in view of power and circumstances, and an object of the present invention is to obtain a highly accurate conductive pattern on a substrate such as a film or a glass substrate in a relatively simple manner. It is to provide a method.
  • the present inventors have focused on a method different from the above-described silver salt diffusion transfer method and chemical development method, that is, the silver salt curing development method, and achieved the object of the present invention.
  • the object of the present invention is achieved by the following method.
  • (4) A) a step of imagewise exposure to a photographic material having at least one type of photosensitive silver halide emulsion layer on the substrate, and (B) a step of curing and developing the photosensitive silver halide emulsion layer. , (C) removing the uncured portion of the photosensitive silver halide emulsion layer, (D) depositing an electroless catalyst on the substrate having the cured emulsion layer, and (E) etching with an enzyme. And (F) a step of performing an electroless plating process, in order.
  • the silver salt curing development method is described in J. Photo. Sci. 1 1 pl, AG Tull (1963) or “The Theory oi the photographic Process t edition, p32 Richi 327”, TH James et al.
  • a developer containing a developing agent such as polyhydroxybenzene.
  • the developing agent reduces the silver halide in the exposed area, the gelatin formed as the binder of the silver halide emulsion layer is cross-linked with the oxidized product generated from the developing agent itself. This is a method of hardening into a film.
  • the conductive pattern in the present invention is a continuous conductive wiring image or a discontinuous conductive isolated wiring image.
  • the former continuous conductive wiring image has mainly shapes such as lattice, hayumu, swirl, radial, circle, straight line, polygon, etc., from any end to the farthest end. Conduction is intended.
  • the latter discontinuous conductive isolated wiring image is an isolated wiring image mainly having a shape such as a circle, a straight line, a polygon, and a star.
  • a conductive pattern having high accuracy and excellent conductivity can be obtained on a substrate such as a film or a glass substrate by a relatively simple method.
  • FIG. 1 is a schematic diagram showing one embodiment of a method for forming a conductive pattern of the present invention
  • FIGS. 2, 3, 4, and 6 are schematic diagrams showing another embodiment of the present invention. is there.
  • FIG. 1 (I) shows a photographic light-sensitive material in which a photosensitive silver halide emulsion layer (2) is laminated on a substrate (la).
  • the photographic photosensitive material is imagewise exposed through a mask film (4), cured and developed, and then the uncured portion of the photosensitive silver halide emulsion layer is removed.
  • the substantially non-conductive cured emulsion layer (2a) obtained by imagewise exposure remains on the substrate (FIG. 1 (111)).
  • the image-like exposure method it is acceptable to use a direct exposure method using a laser beam or the like without using a mask film (4).
  • an electroless plating catalyst (5) is attached to a substrate having a hardened emulsion layer (2a) obtained in a pattern (Fig. 3 (IV)), and then the hardened emulsion layer is removed. To do. As shown in Fig. 3, the electroless plating catalyst (5) is attached to the entire surface of the cured emulsion layer and the other substrate surface. Therefore, by removing the cured emulsion layer, it is the same as the mask film pattern. A catalyst pattern is obtained (Fig. 3 (V)). Conductive metal plating patterns can be easily formed by applying ordinary electroless plating to the substrate with the electroless plating catalyst attached in the pattern obtained in Fig. 3 (V).
  • an electroless catalyst (5) is attached to a substrate (FIG. 4 (III)) having a hardened emulsion layer (2a) obtained in a pattern (see FIG. 4).
  • the electroless plating catalyst (5) is removed from the surface of the hardened emulsion layer (2a) by enzymatic etching.
  • the substrate which also has a hardened emulsion layer (2a)
  • the electroless plating catalyst attached in the pattern obtained in Fig. 4 (V) the conductive metal layer can be easily obtained. A pattern can be formed.
  • the hardened emulsion layer (2a) is removed.
  • the substrate according to the present invention does not require translucency, it can be used in the form shown in FIG. 4 (VI).
  • the enzymatic etching treatment is intended to selectively remove the electroless plating catalyst (5) present in the vicinity of the surface of the cured emulsion layer (2a).
  • the electroless plating catalyst (5) on the substrate (la) is removed by appropriately changing the treatment conditions of the method using a protease such as protease exemplified in the removal method of 2a). It is possible to selectively remove the electroless plating catalyst (5) existing in the vicinity of the surface of the hardened emulsion layer (2a).
  • the hardened emulsion layer (2a) can be decomposed and removed by dipping for 90 seconds or longer.
  • a method using a protease such as a protease for the purpose of etching with an enzyme is immersed in a protease-containing solution at 10 to 80 ° C for less than 60 seconds, preferably less than 50 seconds.
  • the pattern having sufficient conductivity can be easily obtained.
  • electrolytic plating is further performed. That power S.
  • the electroplating method generally used in the industry can be applied mutatis mutandis.
  • FIG. 5 is a schematic diagram when electroplating is applied.
  • electrolysis plating is applied to the electroless plating area (3)
  • the force due to the thickness increases, and at the same time, the line width of continuous conductive wiring images or discontinuous conductive isolated wiring images is also increased. It tends to get fat (Fig. 5 (1)).
  • an electroless plating part (3) is provided by electroless plating without removing the hardened emulsion layer (2a), and an electrolytic plating part (6) is further provided.
  • a hardened emulsion layer (2a ) Makes it possible to easily form a high-definition conductive metal plating pattern without increasing the line width. Thereafter, the hardened emulsion layer (2a) is removed.
  • the substrate according to the present invention does not require translucency, it can be used in the form of FIG. 6 (VI).
  • the photographic light-sensitive material used in the method for forming a conductive pattern of the present invention has at least one kind of light-sensitive silver halide emulsion layer on a substrate.
  • the photographic light-sensitive material of the present invention has a hydrophilic colloid layer having a hydrophilic polymer as a binder, if necessary, between the substrate and the photosensitive silver halide emulsion layer or on the photosensitive silver halide emulsion layer. May be.
  • the photographic light-sensitive material in the present invention can be produced by coating a photosensitive silver halide emulsion layer on a substrate by a known method.
  • the light-sensitive silver halide emulsion layer in the present invention contains a silver halide crystal and a silver halide emulsion binder.
  • the silver halide crystals contained in the photosensitive silver halide emulsion layer include silver chloride, silver bromide, silver chlorobromide, and silver iodide alone or in combination thereof. A silver crystal etc. are mentioned.
  • the silver halide crystals, rhodium salts, iridium salts, palladium salts, ruthenium salts, nickel salts, good tool its content also contain heavy metal salts such as platinum salt per mol of silver halide 1 X 10- 8 ⁇ 1 X 10- 3 mole are preferred.
  • the crystal form of silver halide is not particularly limited, and may be cubic to tetradecahedral grains, or core chenole type or tabular grains.
  • the silver halide crystal may be a monodispersed crystal or a polydispersed crystal.
  • the average grain size is preferably in the range of 0.05 to 0.88 m.
  • One preferred example is a monodispersed or polydispersed crystal containing 80 mol% or more of silver chloride containing a rhodium salt or an iridium salt.
  • a resin-coated paper, a film, or a glass substrate in which both surfaces of a base paper are coated with a polyethylene resin or the like can be used.
  • a film material known in the art such as a synthetic or semi-synthetic polymer film, for example, a polyester film such as PET, a polycarbonate film, a polyimide film, or a cellulose triacetate film can be used.
  • glass substrate glass materials known in the art can be used. For example, soda lime glass such as soda lime and white crown, low expansion glass such as borosilicate, alkali-free, alumino acid, synthetic quartz glass, etc. Etc.
  • the substrate to be used can be selected depending on the application and required performance.
  • the surface of the substrate is used.
  • the surface may be subjected to corona discharge treatment and / or coated with a very small amount of resin or gelatin.
  • the binder of the silver halide emulsion layer according to the present invention contains water-soluble gelatin as an essential component.
  • the binder of the silver halide emulsion layer may be water-soluble gelatin alone, or may be combined with water-soluble gelatin and casein, dextrin, gum arabic, polybulal alcohol, starch or the like.
  • Examples of the water-soluble gelatin include acid-treated gelatin, alkali-treated gelatin, gelatin derivatives, grafted gelatin, and the like.
  • the water-soluble gelatin according to the present invention is preferably low molecular weight gelatin having an average molecular weight of about 50,000 or less.
  • Low molecular weight gelatin is described in, for example, JP-A-1-158426, JP-A-4-340539, JP-A-8-110641 and the like.
  • the method for producing low molecular weight gelatin according to the present invention can be produced by the method described in the aforementioned patent, for example, preferably by enzymatic degradation.
  • the average molecular weight of the low molecular weight gelatin is preferably about 50,000 or less, more preferably about 20,000 or less, particularly preferably about 3,000 to about 20,000.
  • the low molecular weight gelatin according to the present invention is contained in a silver halide emulsion layer or / and a hydrophilic colloid layer having an optionally provided hydrophilic polymer as a binder.
  • the layer containing the low molecular weight gelatin may be only one layer or a plurality of layers.
  • the amount of low molecular weight gelatin added according to the present invention varies depending on the molecular weight and the kind of binder in the layer to be added, etc., and it is as small as about 1% by mass to 100% by mass with respect to the amount of binder constituting the layer. Can be extensive.
  • the amount of low molecular weight gelatin added is preferably 30% by mass or more, more preferably 50% by mass with respect to the total amount of binder constituting the silver halide emulsion layer. % Or more is good.
  • the silver halide emulsion layer can be sensitized by various methods when it is produced or coated, if necessary. For example, sodium thiosulfate, alkylthiourea Or by a gold compound such as rhodium gold, gold chloride, or a combination of both, and chemically sensitized by methods well known in the art.
  • the silver halide emulsion layer can also be sensitized or desensitized both positively and negatively by dyes such as cyanine and merocyanine.
  • dyes such as cyanine and merocyanine.
  • dyes and pigments used in usual silver halide photographic emulsion layers are added as needed to cope with image deterioration due to irradiation or halation. can do.
  • dyes and pigments contained in the silver halide emulsion layer and / or optionally provided hydrophilic colloid layer used in the present invention those well known to those skilled in the art can be used alone or in combination. Because the terms dye and pigment have unique definitions for each industry used, there is no general standard to clearly distinguish them from each other, but as used herein, dyes are in water.
  • the dye preferably contains a plurality of water-soluble groups such as sulfonic acid groups or carboxylic acid groups in the molecule in order to enhance solubility in water.
  • additives known in the art can be added to the silver halide emulsion layer of the present invention, if necessary.
  • Various surfactants such as anion, cation, betaine, and nonionic, thickeners such as carboxymethylcellulose, coating aids such as antifoaming agents, chelating agents such as ethylenediaminetetraacetate, polyquinones such as hydroquinone, catechol, and pyrogallol Developers such as hydroxybenzenes and 3-virazolidinones may be included. It is also possible to add stabilizers such as azaindenes and heterocyclic mercapto compounds, and fogging inhibitors.
  • the hardened development process is a process in which the exposed photosensitive silver halide emulsion layer on the support is developed with a hardened developer containing a developing agent, and the developing agent reduces the silver halide in the exposed area.
  • gelatin which is a binder of a silver halide emulsion
  • an oxidant generated from the developing agent itself to form an image-like film.
  • the cured developer used in the main curing development process contains polyhydroxybenzenes (for example, pyrogallol, catechol, hydroquinone) as a developing agent.
  • the main developing developer further comprises an auxiliary developing agent such as 3-virazolidinones; for example, alkaline substances such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, lithium hydroxide, sodium triphosphate, and amine compounds; For example, preservatives such as sodium sulfite; thickeners such as carboxymethyl cellulose; anti-fogging agents such as potassium bromide; development regulators such as polyoxyalkylene compounds; eg thiosulfates, thiocyanates, cyclic Additives such as silver halide solvents such as imide, thiosalicylic acid, and mesoionic compounds can be included.
  • the pH of the developer is usually preferably 10 or more and 14 or less.
  • the step of removing the uncured portion is a step of removing the silver halide emulsion layer in the uncured portion (non-image portion) after the curing and developing treatment to expose the substrate surface.
  • the processing solution used in this step contains water as a main component, but may contain a pH buffer component.
  • the treatment liquid used in this step can contain a preservative for the purpose of preventing the removed gelatin from being spoiled.
  • the silver halide emulsion layer in the uncured part can be removed by rubbing with a sponge or the like, by peeling off by sliding the roller against the film surface, or by wrapping the roller in contact with the film surface. There are methods.
  • the step of removing the silver halide emulsion layer by physical contact is substantially not included.
  • Preferred method for removing the unhardened silver halide emulsion layer in the present invention the uncured silver halide emulsion layer may be removed by applying a treatment liquid stream to the surface of the silver halide emulsion layer.
  • a treatment liquid stream to the silver halide emulsion layer surface
  • a shower method, a slit method, or the like can be used alone or in combination.
  • a plurality of showers and slits can be provided to increase the removal efficiency.
  • Electroless plating is a method in which a substrate is immersed in an aqueous solution (electroless plating process solution) containing a metal salt to be deposited and a reducing agent to deposit metal on the surface of the substrate.
  • a catalyst addition step for adsorbing a catalyst metal referred to as an electroless plating catalyst in the present specification; generally using a radium-tin complex
  • electroless plating is performed.
  • the reducing agent in the electroless plating process solution reduces the metal ions by the electrons released when oxidized on the surface of the catalytically active palladium, and the metal deposits. It is believed that a film is formed.
  • electroless plating solution is used depends on the application of the conductive material to be manufactured, but the electroless plating solution for gold, silver, copper, zinc or nickel can be used / separated.
  • the uncured portion (non-image portion) of the silver or silver halide emulsion layer is removed to expose the substrate surface, and then the patterned Electroless plating is applied to the substrate having the hardened emulsion layer (2a).
  • the hardened emulsion layer (2a) which is substantially non-conductive, is relatively free from the surface of the substrate from which the uncured emulsion layer where electroless plating hardly progresses is removed. Since electroless plating progresses quickly, the exposed substrate surface can be selectively subjected to electroless plating.
  • the uncured portion (non-image portion) of the silver halide emulsion layer is removed to expose the substrate surface, and then the patterned cured emulsion layer is formed.
  • An electroless plating catalyst is attached to the substrate having (2a).
  • the step of attaching the electroless plating catalyst to the substrate having the cured emulsion layer there is a force such as a method of immersing the substrate in a solution having the catalyst or a method of applying the catalyst solution to the substrate surface.
  • the catalyst can be easily attached also by this method.
  • Substrate surface with patterned hardened emulsion layer there are various methods for removing the hardened emulsion layer to which the electroless plating catalyst is adhered, but it is effective to remove the hardened emulsion layer and to remain on the substrate. In order to retain the catalytic activity, it is particularly effective to use a protease such as a protease. Etching with an enzyme intended to selectively remove the electroless plating catalyst (5) present in the vicinity of the surface of the hardened emulsion layer (2a) is also proteolytic as described above. It is preferred to use an enzyme.
  • Electrolytic plating is a method of immersing the treated product as the cathode (-) and the same metal as the plating as the anode (+) in an aqueous solution (electrolytic plating bath) in which the metal is dissolved and ionized. By passing an electric current between the two electrodes, the metal ions in the electrolysis bath move to the cathode, exchange electrons on the surface of the processed material, and return to the original metal to form a plating layer. is there.
  • electrolytic plating in the present invention known plating methods such as electrolytic copper plating, electrolytic nickel plating, electrolytic zinc plating, and electrolytic tin plating can be used.
  • plating Technology Guidebook (Tokyo ⁇ Gold Material Cooperative Technical Committee, 1987) can be used. Which plating method is used depends on the application of the conductive material to be manufactured. When plating is performed to further increase conductivity, copper plating or nickel plating is preferred. Preferred methods for the copper plating method include a copper sulfate bath plating method and a copper pyrophosphate bath plating method. Preferable nickel plating methods include the Watt bath plating method and the black plating method.
  • silver bromide 65.5 mol 0/0, silver chloride 34, 0 mole 0/0, having a composition of silver iodide 0.5 mole 0/0, light sensitive silver having an iodine silver chlorobromide crystals A silver halide emulsion was prepared by the neutral single jet method. The average grain size of the silver iodochlorobromide crystal was 0.45 m. Subsequently, gelatin was added to the light-sensitive silver halide emulsion and then sodium thiosulfate was added for chemical sensitization.
  • a stabilizer and a surfactant After adding a stabilizer and a surfactant, this was applied to a photographic polyester film and dried to prepare a photographic light-sensitive material having a light-sensitive silver halide emulsion layer.
  • the coating amount of photosensitive silver halide emulsion in terms of silver nitrate
  • the coating amount of high molecular weight gelatin with an average molecular weight of about 300,000 and the coating amount of low molecular weight gelatin with an average molecular weight of about 10,000 or less are shown in Table 1 below.
  • the coating solution was adjusted so that photographic photosensitive material samples A to E were obtained.
  • the obtained samples 1A to 1E all have excellent adhesion and a dense copper plating uniformly formed on the surface of the polyester film, and the surface resistivity of the lOmmX 10mm square solid copper plating part. All indicated 1. ⁇ / mouth or less.
  • Sample 1A- treated with electroless copper plating obtained in Example 1 above; IE was soaked in a solution of 0.3% biobrase (protease manufactured by Nagase Chemtex Corporation) at 50 ° C for 5 minutes. After decomposing the hardened emulsion layer, the hardened emulsion layer was removed by lightly rubbing with a sponge, washed and dried in a 35 ° C hot water shower to obtain samples 2A to 2E. In each of the obtained samples 2A to 2E, a 10 ⁇ m / 200 ⁇ m line-and-space image and a lOmm ⁇ 10 mm square conductive pattern image similar to those of the mask film remain. Formed a transparent film surface. Of Samples 2A to 2E, Sample 2B and Sample 2D were particularly excellent in the removal of the cured part when lightly rubbed with a sponge!
  • the obtained samples 3A to 3E all have excellent adhesion and a dense nickel-plated surface uniformly formed on the surface of the polyester film.
  • the surface is inherent to the surface of the 1 Omm x 10mm square solid nickel plating.
  • the resistance values were all 1.5 ⁇ / mouth or less.
  • each of the nickel-plated samples 3A to 3E obtained in Example 3 was treated with 0.2% bioplase (protease manufactured by Nagase Chemtex Co., Ltd.) at 50 °. After soaking in a solution of C for 5 minutes to decompose the hardened emulsion layer, the hardened emulsion layer is removed by rubbing gently with a sponge, washed and dried in a 35 ° C hot water shower, and samples 4A to 4E are removed. Obtained. In each of the obtained samples 4A to 4E, the same 10 ⁇ 111 / 200 ⁇ m line-and-space image and 10mm XI Omm square conductive pattern image remained as in the mask Finolem. Formed a transparent film surface. Of Samples 4A to 4E, Sample 4B and Sample 4D were particularly excellent in removal of the cured portion when lightly rubbed with a sponge.
  • Example 1 each of the above samples (A to E) subjected to imagewise exposure, curing and developing treatment, and removal of the uncured portion was subjected to a Meltex metal plate containing an electroless metal catalyst.
  • the pretreatment liquid was subjected to immersion treatment under the following conditions.
  • the cured emulsion layer was separated by immersing in a 40% C solution of 0.5% bioplase (protease manufactured by Nagase Chemtex Co., Ltd.) for 3 minutes. I understood. Thereafter, by washing with a hot water shower at about 35 ° C., the cured emulsion layer could be easily removed while the electroless catalyst was supported on the substrate.
  • bioplase prote manufactured by Nagase Chemtex Co., Ltd.
  • a substrate having a conductive copper pattern was prepared by immersing in an electroless copper plating solution manufactured by Meltex Co., Ltd., and Samples 5A to 5E were obtained.
  • samples 5A to 5E are all 10 111/200 m
  • An in-and-space image and a 10 mm XI Omm square conductive pattern image force S were formed, and the non-image area formed a transparent film surface.
  • samples 5A to 5E all have excellent adhesion and a dense copper plating is uniformly formed on the surface of the polyester film. What is the surface resistivity value of the 10mm x 10mm square solid copper plating? Also showed less than 1.0 ⁇ / mouth.
  • Samples 6A to 6E were prepared in the same manner as in Example 5, except that a polycarbonate film was used instead of the polyester film used in Example 5.
  • Each of the obtained samples 6A to 6E has a 10 ⁇ m / 200 ⁇ m line and space image and a l Omm ⁇ 10 mm square conductive pattern image similar to those of the mask film.
  • the image portion formed a transparent film surface.
  • it has excellent adhesion and a dense copper plating is uniformly formed on the surface of the polycarbonate film.
  • the surface resistivity of the square solid copper plating of lOmm x 10mm is 1.0 ⁇ / mouth or less. Was showing.
  • Sample 7A was prepared in the same manner as in Example 5 except that the electroless copper plating process in Example 5 was replaced by electroless nickel plating with a nickel plating solution manufactured by Meltex. ⁇ 7E created.
  • Each of the obtained samples 7A to 7E has a 10 m / 200 ⁇ m line and space image and a 10 mm XI Omm square conductive pattern image similar to those of the mask film.
  • the part formed a transparent film surface.
  • a fine nickel plating with excellent adhesion is uniformly formed on the surface of the polyester film, and the surface specific resistance value of the 10 mm x 10 mm square solid nickel plating part is 1.5 ⁇ / The mouth was showing.
  • Example 8 [0065] In Example 1, each of the samples A to E that had been subjected to imagewise exposure, curing and developing treatment, and removal of the uncured part, was melted containing an electroless plating catalyst as in Example 5.
  • Etching was performed by lightly rubbing with a to remove the electroless catalyst (noradium-tin complex) on the surface of the hardened emulsion layer, followed by washing and drying in a 35 ° C hot water shower. Thereafter, electroless copper plating was performed in the same manner as in Example 5, and the cured emulsion layer was decomposed by immersing in a 40% C solution of 0.5% bioplase (protease manufactured by Nagase Chemtex Co., Ltd.) for 3 minutes. Then, it wash
  • bioplase protease manufactured by Nagase Chemtex Co., Ltd.
  • each of the obtained samples 8A to 8E is formed with a 10 m / 200 m line and space image and a 10 mm XI Omm square conductive pattern image force S similar to those of the mask film.
  • the non-image area formed a transparent film surface.
  • samples 8A to 8E all have excellent adhesion and a dense copper plating is uniformly formed on the surface of the polyester film. What is the surface resistivity of the solid copper plating of 10 mm x 10 mm? Also showed less than 1.0 ⁇ / mouth.
  • Samples 5A to 5E obtained in Example 5 were further plated with electrolytic copper by the following method to obtain Samples 9A to 9E.
  • the film thickness of the copper plating part was set to 3 m.
  • Samples 10A to 10E were obtained in the same manner as in Example 8, except that after electroless copper plating was performed in Example 8, electrolytic copper plating described in Example 9 was subsequently performed.
  • Each of Samples 10A to 10E has a 10 mm x 10 mm square conductive pattern image, and the surface resistivity value of the lOmm x 10 mm square solid copper fitting is 0.5. Shown below ⁇ / mouth.
  • the line widths of the sample 9A to 9E samples obtained in Example 9 were approximately 14 to 16 m (positive fine line) and 4 to 6 m (negative fine line).
  • the line width of the 10E line and space image obtained by applying electrolytic plating was almost 10 ⁇ m for both positive and negative thin lines.
  • the substrate may be transparent or opaque. Therefore, as described in Examples and the like, a substrate having a wide range of conductive patterns is manufactured. It can be used.
  • FIG. 1 is a schematic diagram showing one embodiment of a conductive pattern forming process of the present invention.
  • FIG. 2 is a schematic view showing another embodiment of the conductive pattern forming process of the present invention.
  • FIG. 3 is a schematic view showing another embodiment of the conductive pattern forming process of the present invention.
  • FIG. 4 is a schematic view showing another embodiment of the conductive pattern forming process of the present invention.
  • FIG. 5 is a schematic diagram when electrolytic plating is applied.
  • FIG. 6 is a schematic view showing another embodiment of the conductive pattern formation process of the present invention. It is.

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Abstract

L'invention concerne un procédé de formation d'un motif conducteur caractérisé par la réalisation séquentielle des étapes suivantes : (A) une étape d'exposition d'image sur un matériel photosensible photographique ayant au moins une couche d'émulsion d'halogénure d'argent photosensible sur un substrat ; (B) une étape pour durcir et développer la couche d'émulsion d'halogénure d'argent photosensible ; (C) une étape pour retirer la partie non durcie de la couche d'émulsion d'halogénure d'argent photosensible ; et (D) une étape pour un plaquage anélectrolytique du substrat ayant la couche d'émulsion durcie. Ce procédé permet de former un motif conducteur de haute précision sur un substrat tel qu'un film ou un substrat de verre par un procédé relativement simple.
PCT/JP2007/072713 2006-11-27 2007-11-26 Procédé de formation de motif conducteur WO2008065976A1 (fr)

Applications Claiming Priority (6)

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JP2006-319298 2006-11-27
JP2006319298 2006-11-27
JP2007042111 2007-02-22
JP2007-042111 2007-02-22
JP2007-139881 2007-05-28
JP2007139881A JP5166772B2 (ja) 2006-11-27 2007-05-28 導電性パターンの形成方法

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Publication number Priority date Publication date Assignee Title
JP2012503370A (ja) * 2008-09-18 2012-02-02 ビジュアルソニックス インコーポレイテッド 超音波変換器および他の構成要素の製造方法
US9173047B2 (en) 2008-09-18 2015-10-27 Fujifilm Sonosite, Inc. Methods for manufacturing ultrasound transducers and other components
US9184369B2 (en) 2008-09-18 2015-11-10 Fujifilm Sonosite, Inc. Methods for manufacturing ultrasound transducers and other components
US12029131B2 (en) 2021-07-15 2024-07-02 Fujifilm Sonosite, Inc. Methods for patterning electrodes of ultrasound transducers and other components

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Publication number Priority date Publication date Assignee Title
JPH07202382A (ja) * 1994-01-07 1995-08-04 Sumitomo Metal Ind Ltd 導体層パターンの形成方法
JPH0864934A (ja) * 1994-08-25 1996-03-08 Matsushita Electric Works Ltd プリント配線板の製造方法
JPH09307216A (ja) * 1996-05-13 1997-11-28 Ngk Spark Plug Co Ltd 配線基板の製造方法及び配線基板
JP2003315957A (ja) * 2002-04-19 2003-11-06 Mitsubishi Paper Mills Ltd 露光用マスク材料
JP2004221564A (ja) * 2002-12-27 2004-08-05 Fuji Photo Film Co Ltd 透光性電磁波シールド膜の製造方法及び透光性電磁波シールド膜

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JPH07202382A (ja) * 1994-01-07 1995-08-04 Sumitomo Metal Ind Ltd 導体層パターンの形成方法
JPH0864934A (ja) * 1994-08-25 1996-03-08 Matsushita Electric Works Ltd プリント配線板の製造方法
JPH09307216A (ja) * 1996-05-13 1997-11-28 Ngk Spark Plug Co Ltd 配線基板の製造方法及び配線基板
JP2003315957A (ja) * 2002-04-19 2003-11-06 Mitsubishi Paper Mills Ltd 露光用マスク材料
JP2004221564A (ja) * 2002-12-27 2004-08-05 Fuji Photo Film Co Ltd 透光性電磁波シールド膜の製造方法及び透光性電磁波シールド膜

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012503370A (ja) * 2008-09-18 2012-02-02 ビジュアルソニックス インコーポレイテッド 超音波変換器および他の構成要素の製造方法
US9173047B2 (en) 2008-09-18 2015-10-27 Fujifilm Sonosite, Inc. Methods for manufacturing ultrasound transducers and other components
US9184369B2 (en) 2008-09-18 2015-11-10 Fujifilm Sonosite, Inc. Methods for manufacturing ultrasound transducers and other components
US9555443B2 (en) 2008-09-18 2017-01-31 Fujifilm Sonosite, Inc. Methods for manufacturing ultrasound transducers and other components
US9935254B2 (en) 2008-09-18 2018-04-03 Fujifilm Sonosite, Inc. Methods for manufacturing ultrasound transducers and other components
US10596597B2 (en) 2008-09-18 2020-03-24 Fujifilm Sonosite, Inc. Methods for manufacturing ultrasound transducers and other components
US11094875B2 (en) 2008-09-18 2021-08-17 Fujifilm Sonosite, Inc. Methods for manufacturing ultrasound transducers and other components
US11845108B2 (en) 2008-09-18 2023-12-19 Fujifilm Sonosite, Inc. Methods for manufacturing ultrasound transducers and other components
US12029131B2 (en) 2021-07-15 2024-07-02 Fujifilm Sonosite, Inc. Methods for patterning electrodes of ultrasound transducers and other components

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