WO2016171074A1 - マスクの形成方法、これを利用したプリント配線基板の製造方法、電鋳部品の製造方法およびスクリーン印刷製版の製造方法 - Google Patents

マスクの形成方法、これを利用したプリント配線基板の製造方法、電鋳部品の製造方法およびスクリーン印刷製版の製造方法 Download PDF

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Publication number
WO2016171074A1
WO2016171074A1 PCT/JP2016/062057 JP2016062057W WO2016171074A1 WO 2016171074 A1 WO2016171074 A1 WO 2016171074A1 JP 2016062057 W JP2016062057 W JP 2016062057W WO 2016171074 A1 WO2016171074 A1 WO 2016171074A1
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WIPO (PCT)
Prior art keywords
layer
mask
base material
acid
forming
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PCT/JP2016/062057
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English (en)
French (fr)
Japanese (ja)
Inventor
森家英幸
森家圭一郎
森家洋晃
Original Assignee
株式会社北陸濾化
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Priority to CN201680023007.2A priority Critical patent/CN107533298B/zh
Publication of WO2016171074A1 publication Critical patent/WO2016171074A1/ja

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/02—Local etching
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/10—Moulds; Masks; Masterforms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • 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
    • H05K3/06—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 chemically or electrolytically, e.g. by photo-etch process

Definitions

  • the present invention relates to a mask forming method, a printed wiring board manufacturing method using the mask, an electroformed component manufacturing method, and a screen printing plate making method.
  • a dry film is applied as a photoresist on the surface of a metal foil layer provided on an insulating layer.
  • the surface of the metal foil layer has been mechanically polished before the dry film is attached.
  • problems such as a decrease in the dimensional accuracy of the completed printed circuit board due to mechanical polishing and a troublesome polishing operation.
  • Patent Document 1 discloses that a metal foil layer is treated with an aqueous solution containing hydrogen peroxide, sulfuric acid, 5-amino-1H-tetrazole, and phenylurea so that the surface of the metal foil layer is uniformly roughened. A method for improving the adhesion between the layer and the dry film has been proposed.
  • Patent Document 2 a method of treating the surface of the metal foil layer more precisely with an aqueous solution containing hydrogen peroxide, sulfuric acid, halogen ions, and tetrazoles is proposed.
  • electroformed parts are also manufactured by using a pattern formed of such a photoresist as an electroforming mold (see Patent Document 3 and Patent Document 4).
  • the treatment liquid on the surface is washed with water or dried in the subsequent step, and then the dry film and In this case, an oxide film is formed on the roughened active surface.
  • this oxide film is interposed between the metal foil film and the dry film.
  • the adhesiveness is sufficient to cope with increasing the density, thinning, and thinning of the wiring pattern.
  • the dry film is heated and pressed against the metal foil layer for laminating to improve adhesion, but in this case, the dry film is stretched by heating, so that the film surface is distorted and adhered cleanly. It becomes difficult to do this, and energy and time are required for heating and pressure welding, and a special device is required, which increases the cost.
  • the adhesion of the photoresist is improved by roughening the surface of the metal foil layer, the photoresist solution (photosensitive resin) that has entered the dent may remain undeveloped and remain. This causes inconveniences such as troubles in product characteristics.
  • the present invention has been made in view of such circumstances, and a mask forming method that can be provided by forming a resin layer in a state of being in close contact with a surface of a base material layer such as a metal layer in a simple and reliable manner.
  • Another object of the present invention is to provide a printed wiring board manufacturing method, an electroformed component manufacturing method, and a screen printing plate making method using the same.
  • an acidic aqueous solution containing an undercoat layer forming agent is brought into contact with the surface of the base material layer to oxidize the surface of the base material layer.
  • an acidic aqueous solution is brought into contact with the surface of the base material layer to remove the oxide film on the surface of the base material layer, and the surface of the base material layer is activated.
  • a step of contacting an aqueous solution containing an undercoat layer forming agent with the active surface of the base material layer to form an undercoat layer on the active surface of the base material layer; and on the surface of the undercoat layer, A step of forming a resin layer that is cured by irradiation, laminating the resin layer on the surface of the base material layer via the undercoat layer, and forming a mask layer composed of the undercoat layer and the resin layer.
  • the first mask forming method when forming the undercoat layer on the active surface of the base material layer, forms the undercoat layer all at once using an acidic aqueous solution containing the undercoat layer forming agent.
  • the second mask formation method first, the surface of the base material layer is activated using an acidic aqueous solution not containing an undercoat layer forming agent, and then the active surface of the base material layer is undercoated.
  • the aqueous solution containing the coating layer forming agent is treated by contact.
  • the former forms an undercoat layer on the active surface of the base material layer using a one-component acidic aqueous solution, while the latter is a two-component solution. They differ in that an undercoat layer is formed on the active surface of the substrate layer using a mold solution.
  • an acidic, neutral or alkaline aqueous solution can form a good undercoat layer.
  • contact means that the various aqueous solutions touch the surface of the base material layer formed of a metal or the like, and thus the various aqueous solutions used in the present invention are the base material layer.
  • the contact method is not particularly limited. Specifically, for example, the surface of the base material layer is immersed in the various aqueous solutions, or the various aqueous solutions are applied, sprayed or sprayed (sprayed) on the surface of the base material layer. .
  • the base material layer used is not particularly limited as long as it is a layer formed of a metal, a resin, an inorganic material, or the like used as a base material.
  • copper or an alloy containing copper is used.
  • a layer of metal selected from titanium or an alloy containing titanium, silver or an alloy containing silver, gold or an alloy containing gold or platinum or an alloy containing platinum is preferably used.
  • resin it may be the same as the resin layer, or may be of a different type. Specific examples include polyester, epoxy resin, polyimide resin, phenol resin / polybenzimidazole (PBI) resin, and the like. Moreover, in the case of an inorganic material, ceramics, glass, quartz, etc. are mentioned.
  • undercoat layer forming agent examples include gallic acid, pyrogallol, tannic acid, citric acid, malic acid, lactic acid, tartaric acid, glycolic acid, glyceric acid, oxyvaleric acid, salicylic acid, mandelic acid, oxalic acid, malonic acid, succinic acid. And at least one selected from glutaric acid, adipic acid, maleic acid or phthalic acid, or an alkali metal salt or ammonium salt thereof, or an alkali metal salt or ammonium salt of EDTA.
  • a resin layer used in the present invention a resin layer formed of an irradiation ray curable dry film, or after applying or spraying, spraying or spraying an irradiation ray curable resin solution or resin solution on the surface of the base material layer And those formed by drying.
  • the temperature range is from room temperature to 100 ° C, preferably from room temperature to 55 ° C, particularly preferably from room temperature to 45 ° C.
  • a resin layer that is cured by irradiation rays is provided on the surface of the dried undercoat layer.
  • a mask layer composed of an undercoat layer and a resin layer is formed on the surface of the base material layer through such a process, and the irradiated portion is cured by irradiating a predetermined portion of the mask layer with an irradiation beam. Thereafter, the uncured mask layer is removed with a solvent to form a cured mask layer.
  • the drying method is not particularly limited, and specific examples include natural drying, vacuum drying, heat drying, air drying, hot air drying, and the like.
  • the undercoat layer is a compound formed by the combination of an undercoat layer forming agent and element ions of components constituting the base material formed on the surface of the base material layer, and has a thickness of 0.1. It is estimated that it is in the range of ⁇ 0.01 ⁇ m.
  • examples of the irradiation rays include infrared rays, near infrared rays, ultraviolet rays, electron beams, and lasers.
  • the method for manufacturing a printed wiring board of the present invention for solving the above-described problem is provided on the surface of the metal layer provided on the insulating layer via the metal seed layer, or on the surface of the metal layer provided on the insulating layer.
  • the metal seed layer and metal layer not protected by the mask layer, or the metal layer is removed, and the metal seed layer and metal layer protected by the mask layer; Or after forming a metal layer as a conductor pattern, it is obtained by removing the said hardened
  • the printed wiring board manufacturing method of the present invention for solving the above-mentioned problem is the method of forming the mask layer after forming a cured mask layer on the surface of the metal seed layer provided on the insulating layer by the method described above.
  • a pattern is formed by removing an uncured portion of the layer, and a plating pattern is applied to the pattern portion to form a conductor pattern, and then the mask layer and the metal seed layer protected by the mask layer are removed. Is.
  • the metal seed layer a layer obtained by further laminating a metal layer on the surface of the metal seed layer may be used as necessary.
  • an uncured portion of the mask layer is removed to form a mold part, and this mold
  • the peelability was improved by expansion or contraction of the mask layer and the electroformed parts which were cured by heating or cooling to give a temperature difference.
  • the hardened mask layer and the electroformed part are peeled off.
  • the electroformed part according to the present invention can be produced without particular limitation as long as it is used in a conventional electroformed part. Specifically, for example, a nozzle part of an ink jet head. , Vibration plate parts, various precision machine parts, vapor deposition mask, fine mesh, IC tag, flat coil, wiring board mounting bump, semiconductor wiring board, hologram master, electroformed part manufacturing mold, etc. It can be applied to parts and parts manufacturing technology.
  • the method for producing the screen printing plate making of the present invention for solving the above-mentioned problems is that the base material layer is a mesh sheet for screen printing, the mask layer cured by the above-mentioned method is formed, and then the uncured portion of the mask layer is removed. It is removed to form an opening through which screen printing paste passes.
  • a mask layer composed of an undercoat layer and a resin layer is formed on the surface of the base material layer, and a predetermined portion of the mask layer is irradiated with irradiation radiation.
  • the cured mask layer can be formed by removing the uncured mask layer.
  • the method for forming a mask of the present invention is used, and the undercoat layer is formed in a state of being extremely tightly adhered to the surface of the metal layer. Oxidation of the active surface in the metal layer is prevented, and the resin layer such as the undercoat layer and the dry film has a high affinity between organic substances, and as a result of extremely good adhesion, the dry film and the like
  • the resin layer can be pressure-bonded to the undercoat layer without heating. Therefore, since the resin layer such as a dry film can be pressure-bonded without heating, there is no occurrence of distortion or the like, and the resin layer can be neatly formed on the surface of the undercoat layer. As a result, it is possible to achieve higher density and higher accuracy of the conductor pattern, and to obtain a printed wiring board having a highly reliable fine conductor pattern, and it does not require a heat source. It can be done safely.
  • the printed wiring board provided can be obtained, and the printed wiring board can be manufactured at low cost without using a complicated apparatus.
  • the method for forming a mask according to the present invention is used. After forming a cured mask layer, an uncured portion of the mask layer is removed to remove a mold part. The mold part is subjected to electroforming plating treatment to form an electroformed part. In this case, a fine and highly accurate mold part can be manufactured by forming a hardened mask layer. A highly reliable fine electroformed part can be obtained.
  • an undercoat layer is formed by utilizing the mask forming method of the present invention, and after forming a cured mask layer, an uncured portion of the mask layer In this case, the cured mask layer is firmly adhered to the metal mesh sheet for screen printing by the undercoat layer, and the mask layer finely forms the opening.
  • the cured mask layer is firmly adhered to the metal mesh sheet for screen printing by the undercoat layer, and the mask layer finely forms the opening.
  • FIG. 1 (a) to (f) are process diagrams showing each process of a mask forming method according to the present invention.
  • FIG. 2 (a) to (h) are process diagrams showing respective steps of a method for manufacturing a printed wiring board by a subtractive method according to the present invention.
  • FIG. 3 (a) to (h) are process diagrams showing respective steps of a method for manufacturing a printed wiring board by a semi-additive method according to the present invention.
  • FIG. 4 (a) to (h) are process diagrams showing each process of the method for manufacturing an electroformed component according to the present invention.
  • FIG. 5 (a) to (f) are process diagrams showing each process of the method for producing a screen printing plate making according to the present invention.
  • FIG. 1 is a schematic view of a method for forming a mask 10
  • FIGS. 2 and 3 are schematic views showing a manufacturing process of a printed wiring board 4 using the method for forming a mask 10 shown in FIG. It is the schematic which shows the manufacturing process of the electroformed component 5 using the formation method of the mask 10 shown in FIG.
  • the surface of the base material layer 2 is brought into contact with the acidic aqueous solution 30 containing the undercoat layer forming agent, and the oxide film 2a on the surface of the base material layer 2 is removed.
  • a step of forming the undercoat layer 3 derived from the undercoat layer forming agent on the exposed active surface of the base layer 2 (FIGS. 1A to 1D), and the surface of the undercoat layer 3
  • a dry film as a resin layer 1 that is cured by irradiation radiation is provided by pressure bonding at room temperature, and the resin layer 1 is adhered to the surface of the base material layer 2 via an undercoat layer 3.
  • the step of forming an ultraviolet curable mask layer 31 composed of 3 and the resin layer 1, and the irradiated portion is cured by irradiating the mask layer 31 with irradiation radiation, and then the uncured mask layer 31 is removed.
  • the It is to form a mask 10 has been turned into (FIG. 1 (e) and FIG. 1 (f)).
  • the base material layer 2 copper or an alloy containing copper, iron or an alloy containing iron, nickel or an alloy containing nickel, aluminum or an alloy containing aluminum, zinc or an alloy containing zinc, an alloy containing lead or lead
  • Preferred is a layer of metal selected from cobalt or alloys containing cobalt, tin or alloys containing tin, titanium or alloys containing titanium, silver or alloys containing silver, gold or alloys containing gold or platinum or alloys containing platinum Used for.
  • resin it may be the same as the resin layer, or may be of a different type. Specific examples include polyester, epoxy resin, polyimide resin, phenol resin / polybenzimidazole (PBI) resin, and the like.
  • PBI polybenzimidazole
  • the aluminum alloy is not particularly limited as long as it is an alloy containing aluminum, but in particular, an ACL (Al—Co—Ge—La) alloy, an ACL (Al—Ni—B) alloy, an aluminum-neodymium (Al -Nd) alloy, aluminum-zirconium (Al-Zr) alloy, aluminum-copper (Al-Cu) alloy, aluminum-silicon (Al-Si) alloy, aluminum-silicon-copper (Al-Si-Cu) alloy, etc. Can be mentioned.
  • the iron alloy is not particularly limited as long as it is an alloy containing iron (Fe).
  • iron (Fe) is a main component, and depending on the purpose, Ni, Cr, W, Cu, Co, What contains 1 or 2 or more types of components, such as C, Si, Mn, or Mo, is desirable.
  • ferritic stainless steel, martensitic stainless steel, austenitic stainless steel, or carbon steel is used. Examples include products formed as materials.
  • the acidic aqueous solution 30 containing the undercoat layer 3 forming agent preferably contains nitric acid or sulfuric acid.
  • the ratio of nitric acid to the acidic aqueous solution 30 as a whole is adjusted to a range of 0.5 to 9.9% by weight, and the ratio of sulfuric acid is adjusted to a range of 0.5 to 9.9% by weight. desirable.
  • the concentration of nitric acid or sulfuric acid is less than 0.5% by weight with respect to the entire acidic aqueous solution 30, the required effect cannot be obtained and the concentration of nitric acid or sulfuric acid is not sufficient.
  • blending ratio of phosphoric acid is the effect, safety
  • the acidic aqueous solution 30 is preferably a three-component system containing nitric acid, sulfuric acid and phosphoric acid.
  • the mixing ratio of nitric acid in the entire acidic aqueous solution 30 is in the range of 0.5 to 9.9 wt%. It is desirable that the blending ratio of sulfuric acid is in the range of 0.5 to 9.9% by weight and the blending ratio of phosphoric acid is in the range of 0.05 to 40% by weight. Among them, the total amount of nitric acid and sulfuric acid is the entire acidic aqueous solution 30.
  • the acidic aqueous solution 30 is no longer subject to the so-called poisonous and deleterious substances control law, and various legal regulations are imposed on transportation and storage. It can be handled easily without receiving it.
  • hydrochloric acid to the acidic aqueous solution 30.
  • at least one selected from nitric acid or sulfuric acid is added with hydrochloric acid to form a two-component system or a three-component system.
  • a base material layer made of an alloy containing nickel such as austenitic stainless steel by adding phosphoric acid to the acidic aqueous solution to form a ternary or quaternary acidic aqueous solution 30 2 is also preferable because the oxide film on the surface of the base material layer 2 can be suitably removed.
  • the concentration of hydrochloric acid to be added is preferably in the range of 0.1 to 9.9 wt% with respect to the entire acidic aqueous solution 30, and the concentration of hydrochloric acid is relative to the entire acidic aqueous solution 30. If the concentration is less than 0.1% by weight, the required effect cannot be obtained because the amount is too small. On the other hand, if the concentration of hydrochloric acid exceeds 9.9% by weight with respect to the entire acidic aqueous solution 30, the meaning of blending is significant. In addition to the absence, there are too many, and the safety and handling properties and the working environment are deteriorated.
  • the acidic aqueous solution 30 is more preferable because it is not subject to poisonous and deleterious substances control laws and can be handled easily without being subject to various regulations regarding transportation and storage.
  • the acidic aqueous solution 30 is mixed with an undercoat layer forming agent.
  • the undercoat layer forming agent As the undercoat layer forming agent, the oxide film 2a on the surface of the base material layer 2 is dissolved and removed with the acidic aqueous solution 30, and the acidic aqueous solution 30 is dissolved.
  • the surface of the base material layer 2 is activated, the element ions of the components constituting the base material layer 2 formed on the active surface are combined with the undercoat layer forming agent, and the undercoat layer 3 is formed on the surface of the base material layer 2.
  • the substance is not particularly limited as long as it is a substance for forming.
  • carbolsyl that can be easily combined with element ions of components constituting the base material layer 2 formed on the active surface of the base material layer 2.
  • Examples thereof include those having a functional group such as a group and an organic group having good adhesion between the resin layer 1 formed on the active surface of the base material layer 2.
  • undercoat layer forming agent examples include gallic acid, pyrogallol, tannic acid, citric acid, malic acid, lactic acid, tartaric acid, glycolic acid, glyceric acid, oxyvaleric acid, salicylic acid, mandelic acid, and oxalic acid.
  • At least one selected from malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid or phthalic acid or an alkali metal salt or ammonium salt thereof, or an alkali metal salt or ammonium salt of EDTA Can be mentioned.
  • the functional group mainly binds to the element ions of the components constituting the base material layer 2 to form a compound, while the organic group is on the active surface of the base material layer 2. Since it faces outward, the adhesion between the undercoat layer 3 formed on the active surface of the base material layer 2 and the resin layer 1 is further improved.
  • the undercoat layer 3 may be formed using a one-component acidic aqueous solution 30 containing an undercoat layer forming agent.
  • the layer 2 may be treated with an acidic aqueous solution that does not contain an undercoat layer forming agent, and then with a two-component aqueous solution that is treated with an aqueous solution containing an undercoat layer forming agent.
  • the surface of the base material layer 2 is brought into contact with the first acidic aqueous solution containing the above-mentioned inorganic acid to remove the oxide film 2a on the surface of the base material layer 2.
  • the surface of the base material layer 2 is activated.
  • a second aqueous solution containing an undercoat layer forming agent is brought into contact with the active surface of the obtained base material layer 2 to form the undercoat layer 3 on the active surface of the base material layer 2.
  • any acidic, neutral or alkaline aqueous solution can be used.
  • the acidic aqueous solution (including the first acidic aqueous solution; the same shall apply hereinafter) or the second aqueous solution may optionally contain other components, for example, an organic acid or a surfactant. It is.
  • the “organic acid” is not particularly limited as long as it is mainly for preventing the surface of the base material layer 2 from being excessively dissolved, but is generally a carboxyl group (—COOH).
  • Specific examples include organic acids having a polyoxymonocarboxylic acid, gluconic acid, formic acid, acetic acid, propionic acid, butyric acid, and the like.
  • the amount of these organic acids to be added is appropriately determined depending on the material of the base material layer 2 that is the object and the composition of the inorganic acid, and is not particularly limited.
  • the range is preferably 0.01 to 20.0% by weight, more preferably about 0.1 to 10% by weight, based on the entire acidic aqueous solution.
  • the addition amount of the organic acid is less than 0.01% by weight based on the entire acidic aqueous solution, the action of suppressing the reaction of the base material layer 2 is insufficient, and a required suppressing effect cannot be obtained. If the added amount exceeds 20.0% by weight with respect to the entire acidic aqueous solution, the effect is limited, meaning that not only is meaningless, but also the balance and adjustment with other components become worse, and it becomes uneconomical. It is not preferable.
  • organic acids may be added by mixing not only one type but also two or more types as appropriate.
  • the “surfactant” is mainly added to infiltrate and adapt the acidic aqueous solution over the details of the surface of the base material layer 2 to achieve uniform treatment or to give gloss. Any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or a nonionic surfactant can be used.
  • the anionic surfactants include fatty acid salt type, alkylbenzene sulfonate type, alkyl sulfate ester type, linear secondary sulfonate type, dialkyl sulfosuccinate type, POE alkyl or alkylphenyl ether.
  • examples thereof include a sulfate ester salt type and a POE alkyl or alkylphenyl ether phosphate ester salt type.
  • examples of the cationic surfactant include an alkylpicolinium chloride type, an alkyltriethylammonium chloride type, and other quaternary ammonium salt types.
  • Nonionic surfactants include POE alkylphenyl ether type nonions, POE alkyl ether type nonions, POE polyoxypropylene block polymer type nonions, POE glycol alkyl ester type nonions, sorbitan fatty acid ester type nonions, and sucrose fatty acid ester type nonions. Etc.
  • amphoteric surfactants include alkylcarboxybetaine type, alkylaminocarboxylic acid type, and alkylimidazoline type.
  • nonionic surfactant examples include POE alkyl ether, POE alkyl phenyl ether, sucrose fatty acid ester, ethylene glycol, and glycerin.
  • the amount of these surfactants to be added is appropriately determined depending on the material of the base material layer 2 as the object and the concentration of the inorganic acid, and is not particularly limited.
  • the amount is preferably about 0.005 to 7.5% by weight, more preferably about 0.05 to 5% by weight, and particularly preferably about 0.1 to 3% by weight with respect to the entire acidic aqueous solution.
  • the addition amount of the surfactant is less than 0.005% by weight with respect to the whole acidic aqueous solution, the addition amount of the surfactant is too small to obtain the required addition effect, whereas 7.5% by weight Exceeding this is not preferable because the effect is limited, and not only is this meaningless, but when the wastewater treatment of this acidic aqueous solution is performed, the waste liquid foams, making it difficult to treat and adjust, and is not preferable.
  • the surfactant may be added as a mixture of not only one type but also two or more types.
  • the acidic aqueous solution 30 is brought into contact with the surface of the base material layer 2 to remove the oxide film 2a formed on the surface of the base material layer 2.
  • the base material layer 2 may be contacted by being immersed in the acidic aqueous solution 30, or the acidic aqueous solution is contacted by any method such as coating, spraying, spraying, roll coating or pouring. Is also good.
  • the oxide film 2a on the surface of the base material layer 2 is removed and the surface of the base material layer 2 is activated, element ions of the components constituting the base material layer 2 formed on the active surface,
  • the undercoat layer 3 is formed on the surface of the base material layer 2 by combining with the coat layer forming agent.
  • the drying temperature is controlled to 100 ° C. or lower, preferably from room temperature to 55 ° C., particularly preferably from room temperature to 45 ° C., It is preferable to dry by a method such as natural drying, vacuum drying, heat drying, air drying or hot air drying.
  • the resin layer 1 is laminated via the coat layer 3, and an ultraviolet curable mask layer 31 composed of the undercoat layer 3 and the resin layer 2 is formed.
  • the undercoat layer 3 is formed in close contact with the surface of the base material layer 2, and the undercoat layer 3 has good compatibility with the resin layer 1 and remarkably adheres to the resin layer 1. It will improve.
  • an ultraviolet curable mask layer 31 is formed by bringing an ultraviolet curable resin solution or an ultraviolet curable resin solution into contact with the undercoat layer 3 on the surface of the base material layer 2 and drying it.
  • the ultraviolet curable mask layer 31 may be formed by pressure-bonding an ultraviolet curable dry film (resin layer 1) at room temperature or while heating as necessary. Since the undercoat layer 3 is already formed on the surface of the base material layer 2 when the dry film (resin layer 1) is bonded, the bondability with the dry film (resin layer 1) is good.
  • the mask layer 31 can be formed by affixing the dry film (resin layer 1) effectively even in a safe temperature range at the factory, that is, at room temperature or at a relatively low temperature (20 to 45 ° C.). When the mask layer 31 is formed at a relatively low temperature as described above, the mask layer 10 having a fine and precise pattern can be formed in a later step as will be described later.
  • ultraviolet rays are irradiated onto a predetermined portion from above to form a mask layer 10 by curing the irradiated portion.
  • the treatment with ultraviolet rays may be performed by providing a pattern sheet on the surface of the mask layer 31 on which a pattern composed of ultraviolet irradiation portions and non-irradiation portions is formed, and irradiating the ultraviolet rays from the pattern sheet. Then, a predetermined portion of the mask layer 31 may be irradiated with ultraviolet rays according to a pre-programmed pattern and cured according to the pattern.
  • the uncured portion of the mask layer 31 is removed with a dedicated solvent, and the mask layer 10 cured according to a predetermined pattern is formed.
  • the mask layer 31 is formed at a relatively low temperature as described above, there are no wrinkles or floats of the resin layer 1, further elongation or distortion, and no gaps. Therefore, the mask layer 31 is fine, precise, and reliable.
  • a high-pattern mask 10 can be formed.
  • FIG. 2 shows a manufacturing process of the printed wiring board 4 by the subtractive method.
  • the printed wiring board 4 is manufactured by forming an underlayer on the surface of a metal layer (base material layer) 22 provided on the insulating layer 40 via a metal seed layer (base material layer) 21.
  • the undercoat layer 3 is formed by the above-described method, and the ultraviolet curable resin layer 1 is provided on the undercoat layer 3 to thereby form the ultraviolet curable mask layer.
  • 31 is formed (FIGS. 2A to 2E).
  • a predetermined part (mask layer 10) where the mask layer 31 is cured and other uncured parts are formed by irradiating a predetermined part from above the mask layer 31 with ultraviolet rays.
  • the exposed metal seed layer 21 and the metal layer 22 are removed with a solvent.
  • the mask layer 10 is removed.
  • the printed wiring board 4 is obtained. The manufacturing method of the printed wiring board 4 will be described in more detail.
  • the metal seed layer 21 is provided on the insulating layer 40.
  • the insulating layer 40 include a paper phenol substrate, a paper epoxy substrate, a glass composite substrate, a glass epoxy substrate, a rigid substrate such as a fluororesin and a ceramic substrate, a flexible substrate made of a film such as polyimide or polyester, or a composite substrate thereof. Either may be sufficient.
  • the metal seed layer 21 is provided on the surface of the insulating layer 40 in order to improve the adhesion between the insulating layer 40 and the metal layer 22 when the metal layer 22 is formed on the surface of the insulating layer 40.
  • the metal seed layer 21 is made of Ni, Ni—Cr, Cu, or the like.
  • the metal seed layer 21 is provided by physical vapor deposition, chemical vapor deposition, sputtering, or the like.
  • a metal layer 22 is provided on the surface of the metal seed layer 21. Since this metal layer 22 later becomes the conductor pattern A, a conventionally known metal, specifically, for example, copper, copper alloy, nickel, aluminum, zinc, tin, stainless steel, titanium, silver, gold, or an alloy thereof, etc. Made of metal.
  • the metal layer 22 is formed by a known method such as electrolytic plating.
  • the undercoat layer 3 is formed using an acidic aqueous solution 30 containing an undercoat layer forming agent, and then washed with water. After drying, as shown in FIG. 2E, an ultraviolet curable resin layer 1 is provided on the undercoat layer 3 to form an ultraviolet curable mask layer 31. In this case, the adhesion between the metal layer 22 and the mask layer 31 is extremely good via the undercoat layer 3.
  • the predetermined portion of the mask layer 31 is irradiated with ultraviolet rays to cure the predetermined portion, and the uncured portion is removed with a solvent to form a cured mask layer 10.
  • the treatment with ultraviolet rays may be performed by providing a photographic original plate on which the conductor pattern A is formed on the mask layer 31 and irradiating the ultraviolet rays to cure only the portion through which the ultraviolet rays are transmitted, or by pre-programmed conductors.
  • the conductor pattern A may be formed by irradiating ultraviolet rays in accordance with the pattern A.
  • the metal layer 22 is formed via the undercoat layer 3 formed on the metal seed layer 21, and the resin layer 1 is not spaced on the metal layer 22.
  • the printed wiring has a highly reliable fine conductor pattern that is capable of achieving higher density and higher accuracy of the conductor pattern because it does not cause any expansion, shrinkage or distortion. The substrate can be easily obtained.
  • the printed wiring board 4 is described as a single-sided board in which the conductor pattern A is formed on one side, but it may be a double-sided board.
  • FIG. 3 shows a manufacturing process of the printed wiring board 4 by the semi-additive method.
  • the method for manufacturing the printed wiring board 4 uses an acidic aqueous solution 30 containing an undercoat layer forming agent on the surface of the metal seed layer 21 provided on the insulating layer 40, and passes the undercoat layer 3 by the method described above. Then, an ultraviolet curable resin layer 1 is provided to form an ultraviolet curable mask layer 31 (FIGS. 3A to 3D).
  • the predetermined part (mask layer 10) where the mask layer 31 is cured and the other uncured part 11 are formed.
  • the uncured portion 11 of the mask layer 31 is removed with a solvent to expose the metal seed layer 21 (FIG. 3E), and then the exposed metal seed layer 21 is plated to form a conductor pattern.
  • the printed mask 4 is obtained by removing the hardened mask layer 10 and the metal seed layer 21 thereunder to form a conductor pattern A (FIG. 3 ( g) and FIG. 3 (h)).
  • the metal seed layer 21 used in the present invention may be a single layer metal layer or a two layer metal layer.
  • the acidic aqueous solution 30 containing the undercoat layer forming agent used for this semi-additive method can be the same as that used for the above-mentioned subtractive method.
  • the resin layer 1 does not have a gap through the undercoat layer 3 on the metal seed layer 21 as in the case of the above-described subtractive method, and the resin layer 1 expands and contracts and is further distorted. As a result, the printed circuit board having a highly reliable fine conductive pattern can be easily obtained. .
  • the pattern 11 formed by the mask layer 10 is subjected to a plating process.
  • the mask 10 peels off and causes defective products.
  • the method of the present invention such defective products can be prevented from being generated and the yield of products can be improved.
  • the printed wiring board 4 is a single-sided board in which the conductor pattern A is formed on one side, but may be a double-sided board.
  • FIG. 4 shows a manufacturing process of the electroformed component 5.
  • the undercoat layer 3 is formed on the surface of the base material layer 2 using the acidic aqueous solution 30 containing the undercoat layer forming agent by the above-described method.
  • An ultraviolet curable mask layer 31 is formed by providing the ultraviolet curable resin layer 1 on the substrate (FIGS. 4A to 4D).
  • examples of the base material layer 2 include those formed of conventionally known metals, resins, or inorganic materials.
  • the mask layer 31 is irradiated with ultraviolet rays from above the mask layer 31 to form a predetermined portion (mask layer 10) where the mask layer 31 is cured and other uncured portions, and then the mask layer The uncured portion 31 is removed with a solvent to expose the base material layer 2, and the mold part 12 is formed (FIG. 4E).
  • the mold part 12 is subjected to an electroforming plating process to manufacture the electroformed part 5.
  • this is heated or cooled, and the peelability is improved by expansion or contraction of the mask layer 10 and the electroformed part 5 which are cured by giving a temperature difference from immediately after the electroformed part 5 is produced.
  • the cured mask layer 10 and the electroformed component 5 are peeled off to obtain the electroformed component 5 (FIG. 4 (h)).
  • the heating temperature is preferably in the range of 50 to 250 ° C.
  • the cooling temperature is preferably in the range of minus 5 ° C. to minus 200 ° C.
  • liquid nitrogen may be used.
  • it is desirable to control so that the temperature difference from immediately after the electroformed part 5 is manufactured is about 150 to 250 ° C.
  • the electroformed part 5 is manufactured.
  • the ultraviolet curable resin layer 1 is firmly formed on the base material layer 2 via the undercoat layer 3 with no gap. Formed in close contact.
  • the resin layer 1 is not closely stretched, contracted, or distorted, and is firmly adhered to the undercoat layer 3.
  • the resin layer 1 has a high density, high accuracy, and high reliability. Can be easily obtained.
  • the method of the present invention as described above, since the base material layer 2 and the mask 10 are firmly adhered, the generation of defective products can be prevented and the product yield can be improved.
  • FIG. 5 shows a manufacturing process of the screen printing plate making 6.
  • the method for producing the screen printing plate making 6 uses the acidic aqueous solution 30 containing the undercoat layer forming agent on the surface of the mesh sheet 60 for screen printing provided on the insulating layer 40, and the undercoat layer by the above-described method. 3 is formed, and an ultraviolet curable mask layer 31 is formed by providing the ultraviolet curable resin layer 1 on the undercoat layer 3 (FIGS. 5A to 5D).
  • examples of the mesh sheet 60 include those formed of conventionally known metals and resins.
  • the mask layer 31 is irradiated with ultraviolet rays from above the mask layer 31 to form a predetermined portion (mask layer 10) where the mask layer 31 is cured and other uncured portions, and then the mask layer The uncured portion 31 is removed with a solvent to expose the mesh sheet 60 to form an opening 61 through which a paste (not shown) passes (FIG. 5E).
  • the screen printing plate making 6 is completed if the mesh sheet 60 is peeled off from the insulating layer 40 and turned upside down.
  • the screen printing plate making 6 is produced.
  • the UV curable resin layer 1 is firmly adhered to the mesh sheet 60 via the undercoat layer 3 with no gap. It is formed in the state. In this case, the resin layer 1 is not closely stretched, shrunk, or distorted, and is firmly adhered to the undercoat layer 3.
  • the screen layer 6 has high density, high accuracy, and high reliability. Can be easily obtained.
  • the mesh sheet 60 and the mask 10 are firmly in contact with each other, so that the generation of defective products can be prevented and the product yield can be improved. Embodiments according to the present invention will be described below.
  • Example 1 As acidic aqueous solution 30 containing an undercoat layer forming agent, sulfuric acid 4.5% by weight, hydrochloric acid 2.0% by weight, tartaric acid 1.1% by weight, pyrogallol 0.9% by weight, polyoxyethylene styrenated phenyl ether An acidic aqueous solution 30 consisting of 2% by weight and 91.3% by weight of water was prepared.
  • SUS304 50 mm ⁇ 50 mm ⁇ t1 mm, average Ra 0.05, Rz JIS 0.175: measured by Mitutoyo Corp. Sakai Surf Test SJ-301) was used as a test substrate (substrate layer 2).
  • test base material base material layer 2
  • an acidic aqueous solution 30 containing the undercoat layer forming agent at a temperature of 25 ° C. for 3 minutes, and then shower-washed with pure water at a temperature of 25 ⁇ 2 ° C.
  • the undercoat layer 3 was formed by air blow drying.
  • an ultraviolet curable dry film (photocast manufactured by Hitachi Chemical Co., Ltd.) is formed on the surface of the undercoat layer 3 on the surface of the test substrate with the undercoat layer 3 (base material layer 2).
  • HM-4075 was bonded to each temperature condition shown in Table 1.
  • test base material base material layer 2
  • dry film test base material (base material layer 2).
  • Layer 1) was laminated.
  • a stainless steel plate heated to each predetermined temperature was overlaid on the dry film (resin layer 1), and the weight was held for 5 minutes.
  • the used stainless steel plate was the same as the test base material (base material layer 2), and its weight was 18.3 g.
  • an ultraviolet curable mask layer 31 is formed by laminating an ultraviolet curable dry film (resin layer 1) on the surface of the test substrate (base material layer 2) via the undercoat layer 3. did.
  • the entire surface of the ultraviolet curable mask layer 31 was exposed and cured with ultraviolet rays for 5 minutes to form the cured mask layer 10 on the entire surface, thereby obtaining a test piece.
  • the mask layer 10 of the test piece thus obtained was cut at intervals of 5 mm in length and width to form a total of 25 squares in 5 rows and columns. Then, cellophane tape (manufactured by Nichiban Co., Ltd .: trade name cello tape CT1535) is applied to the surface of each square, and after rubbing with a nail several times, the test substrate (base material layer 2) and the tape are 90 degrees. An adhesion evaluation test by T-peeling was performed at a peel strength of 3N so as to be at an angle. The results are shown in Table 1. The adhesion evaluation criteria are as follows.
  • the adhesion evaluation test using the cellophane tape was performed twice, and the average value was shown as a result.
  • the hot plate temperature was 20 degrees, 30 degrees, 40 degrees, 50 degrees, 60 degrees, 70 degrees, 80 degrees, 90 degrees, and 100 degrees, respectively.
  • the results are shown in Table 1.
  • Example 2 A tin plate having a thickness of 1 mm was used as the test substrate (base material layer 2), and the acidic aqueous solution 30 containing the undercoat layer forming agent was replaced with the one used in Example 1, and 4.5 wt. %, Hydrochloric acid 1.0% by weight, tartaric acid 1.1% by weight, pyrogallol 0.9% by weight, polyoxyethylene styrenated phenyl ether 0.2% by weight and water 92.3% by weight, Test pieces were prepared in the same manner as in Example 1, and the same adhesion evaluation test as in Example 1 was performed. The results are shown in Table 1.
  • Example 1 instead of the acidic aqueous solution 30 containing the undercoat layer forming agent used in Example 1, 4.5 wt% sulfuric acid, 2.0 wt% hydrochloric acid, 0.2 wt% polyoxyethylene styrenated phenyl ether and water 93 A test piece was prepared in the same manner as in Example 1 except that a 3% by weight mixed acid aqueous solution was used, and the adhesion evaluation test was performed in the same manner as in Example 1. That is, this test piece was prepared by directly laminating the dry film (resin layer 1) on the surface of the base material layer 2. Therefore, the adhesion evaluation was performed by the base material layer 2 and the dry film (resin layer). This is for evaluating the adhesion to 1). The results are shown in Table 1.
  • Example 2 instead of the acidic aqueous solution 30 containing the undercoat layer forming agent used in Example 1, 1.7% by weight of hydrochloric acid, 1.6% by weight of iron chloride, 0.2% by weight of polyoxyethylene styrenated phenyl ether and water A test piece was prepared in the same manner as in Example 1 except that a 96.5 wt% hydrochloric acid mixed solution was used, and the adhesion evaluation test was performed in the same manner as in Example 1. That is, this test piece was also prepared by directly laminating the dry film (resin layer 1) on the surface of the base material layer 2. Therefore, the adhesion evaluation was performed by the base material layer 2 and the dry film (resin layer). This is for evaluating the adhesion to 1). The results are shown in Table 1.
  • Example 3 instead of the acidic aqueous solution 30 containing the undercoat layer forming agent used in Example 1, 13.0 wt% nitric acid, 15.8 wt% ferric nitrate, 0.2 wt% polyoxyethylene styrenated phenyl ether A test piece was prepared in the same manner as in Example 1 except that a nitric acid mixed solution composed of 71.0% by weight of water was used, and the adhesion evaluation test was performed in the same manner as in Example 1. That is, this test piece was also prepared by directly laminating the dry film (resin layer 1) on the surface of the base material layer 2. Therefore, this adhesion evaluation was performed by the metal layer 2 and the dry film (resin layer 1). ) For evaluating the adhesiveness to the adhesive. The results are shown in Table 1.
  • Example 4 instead of the acidic aqueous solution 30 containing the undercoat layer forming agent used in Example 1, hydrogen peroxide 2.0%, sulfuric acid 9.0%, polyoxyethylene styrenated phenyl ether 0.2% by weight and water 88 A test piece was prepared in the same manner as in Example 1 except that a 8% hydrogen peroxide mixed acidic aqueous solution was used, and the adhesion evaluation test was performed in the same manner as in Example 1. That is, this test piece was also prepared by directly laminating the dry film (resin layer 1) on the surface of the base material layer 2. Therefore, the adhesion evaluation was performed by the base material layer 2 and the dry film (resin layer). This is for evaluating the adhesion to 1). The results are shown in Table 1.
  • Example 3 The undercoat layer 3 is formed on the surface of the base material layer 2 in the same manner as in Example 1, and immediately after the formation of the undercoat layer 3, after 1 hour, 20 hours, and 24 hours, respectively, at room temperature (20 ° C.) The test was conducted in the same manner as in Example 1 except that the film was allowed to stand for 72 hours and then the dry film was bonded at a hot plate temperature of 20 degrees (not heated, room temperature). This adhesion evaluation test is for evaluating the stability of the undercoat layer 3 and for evaluating how long the oxidation of the active surface in the base material layer 2 can be prevented. The results are shown in Table 2.
  • Example 4 The undercoat layer 3 is formed on the surface of the base material layer 2 in the same manner as in Example 2. Immediately after the formation of the undercoat layer 3, after 1 hour, 20 hours, and 24 hours, respectively, at room temperature (20 ° C.) The test was conducted in the same manner as in Example 1 except that the film was allowed to stand for 72 hours and then the dry film was bonded at a hot plate temperature of 20 degrees (not heated, room temperature). This adhesion evaluation test is for evaluating the stability of the undercoat layer 3 and for evaluating how long the oxidation of the active surface in the base material layer 2 can be prevented. The results are shown in Table 2.
  • the undercoat layer 3 was formed on the surface of the stainless steel substrate (base material layer 2), and three days or more passed immediately after the formation of the undercoat layer 3. Even if it exists, it is recognized that it can adhere
  • Example 5 or Example 6 the base material layer 2 used in Example 1 or Example 2 corresponds to Example 1 or Example 2, respectively, and the copper plate ( 50 mm ⁇ 50 mm ⁇ t 1 mm, average Ra 0.07, Rz JIS 0.35: measured by Surftest SJ-301 manufactured by Mitutoyo Corporation), and as an acidic aqueous solution, Example 5 is the same as Example 1.
  • Example 6 a test piece was prepared in the same manner as in Example 1 except that the same one as in Example 2 was used, and an adhesion evaluation test similar to that in Example 1 was performed. The results are shown in Table 3.
  • Comparative Examples 9 to 12 the substrate layers 2 respectively used in Comparative Examples 1 to 4 correspond to the Comparative Examples 1 to 4, respectively, and copper plates (50 mm ⁇ 50 mm ⁇ t1 mm, average), which are test substrates, respectively.
  • Comparative Example 9 was Comparative Example 1
  • Comparative Example 10 was Comparative Example 2
  • Comparative Example A test piece was prepared in the same manner as in Comparative Example 1 except that 11 was used in Comparative Example 3 and Comparative Example 12 was used in Comparative Example 4, and the same adhesion evaluation test as in Comparative Example 1 was performed. went. The results are shown in Table 3.
  • Example 7 or Example 8 the base material layer 2 used in Example 3 or Example 4 corresponds to Example 3 or Example 4, respectively, and a copper plate ( 50 mm ⁇ 50 mm ⁇ t 1 mm, average Ra 0.07, Rz JIS 0.35: measured by Surftest SJ-301 manufactured by Mitutoyo Corporation), and as an acidic aqueous solution
  • Example 7 is Example 3
  • Example 8 is Using the same thing as Example 4, respectively, undercoat layer 3 was formed in the surface of the above-mentioned base material layer 2, respectively, immediately after formation of this undercoat layer 3, after 1 hour each at room temperature (20 ° C), The test was conducted in the same manner as in Example 3 except that the film was allowed to stand for 20 hours, 24 hours, and 72 hours, and then a dry film was bonded at a hot plate temperature of 20 ° C. (not heated; room temperature).
  • This adhesion evaluation test is for evaluating the stability of the undercoat layer 3 and for evaluating how long the oxidation of the active surface in the
  • Comparative Examples 13 to 16 In Comparative Examples 13 to 16, the substrate layers 2 respectively used in Comparative Examples 5 to 8 correspond to the Comparative Examples 5 to 8, respectively, and copper plates (50 mm ⁇ 50 mm ⁇ t1 mm, average), which are test substrates, respectively.
  • Comparative Example 13 was Comparative Example 5
  • Comparative Example 14 was Comparative Example 6
  • Comparative Example 15 is the same as Comparative Example 7
  • Comparative Example 16 is the same as Comparative Example 8, respectively, to form the undercoat layer 3 on the surface of the base material layer 2, respectively, immediately after the formation of the undercoat layer 3, Except for 1 hour, 20 hours, 24 hours, and 72 hours at room temperature (20 ° C), respectively, and then a dry film was bonded at a hot plate temperature of 20 ° C (not heated. Room temperature).
  • Example 5 and tested similarly.
  • This adhesion evaluation test evaluates the stability of the active surface in the base material layer 2 and confirms how much the oxidation of the active surface in the base material layer 2 proceeds with time. This is for confirming a change in adhesion between the layer 2 and the dry film (resin layer 1). The results are shown in Table 4.
  • the undercoat layer 3 was formed on the surface of the copper base material (base material layer 2), and three days or more passed immediately after the formation of the undercoat layer 3. Even if it exists, it is recognized that it can adhere
  • Example 9 A mixed acid aqueous solution consisting of 4.5% by weight of sulfuric acid, 2.0% by weight of hydrochloric acid, 0.2% by weight of polyoxyethylene styrenated phenyl ether and 93.3% by weight of water was used.
  • the substrate layer 2 is immersed for 3 minutes at a temperature of 25 ° C. to remove the oxide film of the substrate layer 2 and activate its surface, and then treated with an acidic aqueous solution containing the following undercoat layer forming agent.
  • a test piece was prepared in the same manner as in Example 1 except that the undercoat layer 3 was formed, and the adhesion evaluation test was performed in the same manner as in Example 1.
  • Example 9 The acidic aqueous solution containing the undercoat layer forming agent used in Example 9 was 0.25 wt% hydrochloric acid, 1.1 wt% tartaric acid, 0.9 wt% pyrogallol, polyoxyethylene styrenated phenyl ether 0 .2% by weight and water 97.55% by weight. The results are shown in Table 5.
  • Example 10 In the treatment method of the two-component aqueous solution of Example 9, the undercoat layer 3 was treated with a neutral aqueous solution consisting of 2% by weight of pyrogallol and 98% by weight of water instead of the acidic hydrochloric acid solution containing the undercoat layer forming agent.
  • a test piece was prepared in the same manner as in Example 1 except that the adhesive evaluation test was performed in the same manner as in Example 1. That is, in this case as well, it was treated with a two-component aqueous solution. The results are shown in Table 5.
  • Example 11 In the treatment method of the two-component aqueous solution of Example 9, instead of the acidic hydrochloric acid solution containing the undercoat layer forming agent, pyrogallol 1.4% by weight, sodium carbonate 4.8% by weight, sodium hydroxide 1.1% by weight % And water were treated with an alkaline aqueous solution consisting of 92.7% by weight, and a test piece was prepared in the same manner as in Example 1 except that the undercoat layer 3 was formed. went. That is, in this case as well, it was treated with a two-component aqueous solution. The results are shown in Table 5.
  • Example 12 to 14 In Examples 1, 3, and 9, tests were performed in the same manner as in Examples 1, 3, and 9 except that the material of the base material layer 2 was changed to a phenol resin. All the results were evaluated as “ ⁇ ”.
  • the resin layer such as a dry film can be pressure-bonded to the undercoat layer without heating. Therefore, there is no occurrence of distortion, floatation, loosening, etc.
  • the resin layer can be neatly formed on the surface. As a result, high-density and high-precision conductor patterns can be realized, and printed wiring boards and electroformed parts with highly reliable fine conductor patterns can be obtained. It is obtained.
  • UV-curable resin layer 10
  • Cured mask (layer) 11
  • Electroforming mold (mold part) 2
  • Base material layer 21
  • Metal seed layer (base material layer) 22
  • Metal layer (base material layer) 3
  • Undercoat layer 30
  • Acidic aqueous solution 31 containing undercoat layer forming agent
  • UV curable mask layer 4
  • Printed wiring board 5
  • Electroformed component Screen printing plate making 60 Mesh sheet (base material layer) 61 Opening A Pattern

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Families Citing this family (5)

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CN110100047B (zh) * 2016-12-23 2022-04-01 3M创新有限公司 电铸微结构制品的方法
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004058640A (ja) * 2002-07-29 2004-02-26 Needs:Kk スクリーン印刷用印刷版
JP2005039097A (ja) * 2003-07-16 2005-02-10 Matsushita Electric Ind Co Ltd 銅箔の配線形成方法と配線転写基材及び配線基板
JP2006156605A (ja) * 2004-11-29 2006-06-15 Matsushita Electric Works Ltd 多層回路基板の製造方法
JP2006235499A (ja) * 2005-02-28 2006-09-07 Hitachi Chem Co Ltd 感光性樹脂組成物、これを用いた感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法並びに光硬化物の除去方法
JP2007334058A (ja) * 2006-06-15 2007-12-27 Murata Mfg Co Ltd スクリーン印刷用版およびその製造方法
JP2009154517A (ja) * 2007-02-22 2009-07-16 Fujifilm Corp 平版印刷版原版および平版印刷方法
JP2012237064A (ja) * 2011-04-28 2012-12-06 Hokuriku Roka:Kk 表面改質処理剤および表面改質方法
JP2014051575A (ja) * 2012-09-06 2014-03-20 Tosoh Corp 洗浄組成物

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3541360B2 (ja) * 2002-05-17 2004-07-07 独立行政法人 科学技術振興機構 多層回路構造の形成方法及び多層回路構造を有する基体
JP2005136223A (ja) * 2003-10-30 2005-05-26 Fuji Photo Film Co Ltd プリント配線板の製造方法
JP4620174B2 (ja) * 2009-04-20 2011-01-26 旭化成イーマテリアルズ株式会社 感光性樹脂積層体
JP6068123B2 (ja) * 2012-12-14 2017-01-25 上村工業株式会社 プリント配線基板の製造方法およびその方法により製造されたプリント配線基板

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004058640A (ja) * 2002-07-29 2004-02-26 Needs:Kk スクリーン印刷用印刷版
JP2005039097A (ja) * 2003-07-16 2005-02-10 Matsushita Electric Ind Co Ltd 銅箔の配線形成方法と配線転写基材及び配線基板
JP2006156605A (ja) * 2004-11-29 2006-06-15 Matsushita Electric Works Ltd 多層回路基板の製造方法
JP2006235499A (ja) * 2005-02-28 2006-09-07 Hitachi Chem Co Ltd 感光性樹脂組成物、これを用いた感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法並びに光硬化物の除去方法
JP2007334058A (ja) * 2006-06-15 2007-12-27 Murata Mfg Co Ltd スクリーン印刷用版およびその製造方法
JP2009154517A (ja) * 2007-02-22 2009-07-16 Fujifilm Corp 平版印刷版原版および平版印刷方法
JP2012237064A (ja) * 2011-04-28 2012-12-06 Hokuriku Roka:Kk 表面改質処理剤および表面改質方法
JP2014051575A (ja) * 2012-09-06 2014-03-20 Tosoh Corp 洗浄組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI651994B (zh) * 2018-03-06 2019-02-21 易華電子股份有限公司 提升乾膜與基材結合穩固性之系統

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