WO2016111035A1 - Surface treatment agent for metal bases - Google Patents

Surface treatment agent for metal bases Download PDF

Info

Publication number
WO2016111035A1
WO2016111035A1 PCT/JP2015/073422 JP2015073422W WO2016111035A1 WO 2016111035 A1 WO2016111035 A1 WO 2016111035A1 JP 2015073422 W JP2015073422 W JP 2015073422W WO 2016111035 A1 WO2016111035 A1 WO 2016111035A1
Authority
WO
WIPO (PCT)
Prior art keywords
ink
surface treatment
metal substrate
treatment agent
coating film
Prior art date
Application number
PCT/JP2015/073422
Other languages
French (fr)
Japanese (ja)
Inventor
米元　護
賢一 白川
米田　直樹
宇敷　滋
Original Assignee
太陽インキ製造株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 太陽インキ製造株式会社 filed Critical 太陽インキ製造株式会社
Priority to JP2016568267A priority Critical patent/JP6779136B2/en
Publication of WO2016111035A1 publication Critical patent/WO2016111035A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/52—Treatment of copper or alloys based thereon
    • 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
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • 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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal

Definitions

  • the present invention relates to a surface treatment agent for metal substrates (hereinafter, also simply referred to as “surface treatment agent”). Specifically, ink is applied on a metal substrate by an ink jet method to form a high-definition pattern coating film.
  • the present invention relates to a surface treatment agent for a metal substrate used for the purpose and a method for forming a pattern coating film using the same.
  • a metal pattern is obtained by forming an etching resist pattern on a metal substrate such as a copper plate and removing unnecessary portions by etching.
  • a copper circuit of a printed wiring board can be obtained by forming an etching resist having a desired pattern on a copper-clad base material and etching it.
  • the solder resist of the printed wiring board is formed on the copper circuit for circuit protection and solder bridge prevention.
  • Etching resists and solder resists are generally formed by a printing method using a screen plate or the like, or a photolithography method in which exposure and development processes are performed.
  • a method of drawing an etching resist or a solder resist by an ink jet method has been proposed because it can cope with a small lot production and omits a plate or a photomask.
  • Patent Document 1 proposes a method of drawing an etching resist by an ink jet method
  • Patent Document 2 proposes a method of drawing a solder resist by an ink jet method.
  • the viscosity of resist ink that can be applied to the ink jet system is very low, and bleeding occurs when applied to a non-absorbing substrate such as a copper surface.
  • Patent Document 3 the method of heating or cooling the base material to increase the viscosity of the ink after printing with ink is used.
  • Each method of injecting ink has been proposed.
  • Patent Document 5 an apparatus in which an ultraviolet irradiation means is provided in the vicinity of a jet nozzle using an ultraviolet curable ink has been proposed. This technique can reduce bleeding by curing the ink after application in a short time, and is used for printed wiring boards.
  • JP-A-56-263845 JP-A-7-263845 JP-A-5-309831 JP 2011-171453 A Japanese Patent Laid-Open No. 2-283452
  • an object of the present invention is to provide a surface treatment agent used for pretreatment of a metal substrate, capable of drawing a high-definition pattern coating film without bleeding when forming a pattern coating film using an inkjet method. And it is providing the formation method of a pattern coating film.
  • the present inventors have used a surface treatment agent comprising a composition containing phosphoric acid, a surfactant excluding a metal salt of a fatty acid, and water, The inventors have found that the above problems can be solved, and have completed the present invention.
  • the surface treatment agent for a metal substrate of the present invention is a surface treatment agent for a metal substrate that is used prior to forming a pattern coating film by coating ink on a metal substrate by an ink jet method. And a composition containing phosphoric acid, a surfactant excluding a metal salt of a fatty acid, and water.
  • the formation method of the pattern coating film of this invention forms the pattern coating film by coating ink with the inkjet system on the metal base material surface-treated with the surface treating agent for metal base materials of the said invention. It is characterized by.
  • the surface treatment agent for a metal substrate of the present invention it is possible to draw a high-definition pattern coating without bleeding when forming a pattern coating using an inkjet method.
  • the surface treatment agent for a metal substrate of the present invention There is an effect that the peeling time can be shortened.
  • the surface treatment agent for a metal substrate of the present invention is used for pretreatment prior to forming a pattern coating film on a metal substrate by applying ink by an inkjet method, and phosphoric acid,
  • the point which consists of a composition containing surfactant other than the metal salt of a fatty acid and water is important.
  • the conventional method when ink is applied to a metal substrate such as copper having no absorbability by the ink jet method, the conventional method sufficiently suppresses bleeding and produces a high-quality high-definition pattern.
  • the cause is that the surface energy of the metal substrate is too large compared to the surface energy of the ink.
  • the inventors of the present invention can adjust the surface energy, that is, the surface tension, by pre-treating a metal base material with a specific composition, and thereby the ink can be ink-jetted. The present inventors have found that it is possible to draw a high-definition pattern coating film that does not bleed when the coating is applied.
  • the etching resist can be easily peeled off from the metal substrate, and the effect of shortening the peeling time can be obtained.
  • the reason why the surface treatment agent of the present invention requires water is that phosphoric acid is an unstable crystal by itself, so that it is difficult to mix with a surfactant unless it contains water. is there.
  • surfactant As the surfactant used in the surface treatment agent of the present invention, known and conventional surfactants can be used as long as they exclude the fatty acid metal salt. For example, anionic surfactants, nonionic surfactants, cations System surfactants and amphoteric surfactants.
  • Anionic surfactants include sodium lauryl sulfate, sodium alkyl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether Phosphate, alkyl sulfate triethanolamine, polyoxyethylene alkyl ether sulfate triethanolamine, sodium 2-ethylhexyl sulfate, sodium di-2-ethylhexylsulfosuccinate, sodium linear alkylbenzene sulfonate, linear alkylbenzene sulfone Acid, fatty acid sodium methyl taurate, palm oil fatty acid methyl taurate sodium N-decanoyl-N-methyltaurate sodium, ⁇ -sulfo fatty acid methyl ester sodium, fatty acid amide ether sulfate sodium salt, N-oleyl-N
  • Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene isodecyl ether, polyoxyethylene-2-ethylhexyl ether, polyoxy Ethylene branched alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene stearyl ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, sorbitan monocaprylate, sorbitan monolaurate, Sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sol Tansesquiolate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, ethylene glycol distearate, poly
  • Cationic surfactants include tetradecylamine acetate, octadecylamine acetate, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, dioctyldimethylammonium chloride, dodecyltrimethylammonium chloride, cocoalkyltrimethylammonium chloride, hexadecyltrimethylammonium chloride.
  • Amphoteric surfactants include palm oil dimethyl betaine, palm oil fatty acid amidopropyl dimethylaminoacetic acid betaine, palm kernel fatty acid amidopropyl dimethylaminoacetic acid betaine, lauryl dimethylaminoacetic acid betaine, stearyl dimethylaminoacetic acid betaine, lauric acid amidopropyldimethyl Betaine aminoacetate, dodecylaminomethyldimethylsulfopropylbetaine, octadecylaminomethyldimethylsulfopropylbetaine, cocamidopropylhydroxysultain, 2-alkyl-N-carboxymethyl-N-hydroxyethyl-imidazolium betaine, laurylaminodiacetic acid mono Sodium, sodium lauryldiaminoethylglycine, sodium lauroylmethylalanine, sodium lauroylglutamate, Potassium acryloyloxy glutamate,
  • the metal salt of a fatty acid means one in which the fatty acid forms a salt with the metal. This is because if a metal salt of a fatty acid is used as a surfactant, a solid content is precipitated when the metal salt of a fatty acid and phosphoric acid are mixed, and the function as a surfactant cannot be achieved.
  • the mass ratio of phosphoric acid to the surfactant can be preferably 100: 0.1 to 100: 50, and more preferably 100: 0. .2 to 100: 20.
  • the blending amount of water may be the minimum amount as long as phosphoric acid can be dissolved, and the maximum amount can be an amount such that the concentration of the surfactant does not become 0.0001% by mass or less.
  • the amount of the surfactant is 0.001 to 0.1% by mass.
  • the surface treatment agent is applied to the surface of the metal substrate as it is or diluted with water or various water-soluble solvents at an arbitrary concentration. Or it can carry out by immersing, washing
  • Metal base material examples of the metal substrate include metal foils such as copper, iron, tin, aluminum, silver, stainless steel, brass, nickel, titanium, and alloys thereof that are usually used for printed wiring boards.
  • the present invention is particularly suitable for forming a coating film of a resist ink for printed wiring board by applying ink by an ink jet method on a copper foil as a metal substrate disposed on the printed wiring board. Useful. Among these, it is particularly useful when forming a coating film of etching resist ink or solder resist ink.
  • the base material to which the etching resist ink is applied is obtained by forming a metal foil such as copper as a metal base material on an insulating sheet.
  • the insulating sheet is generally a glass cloth, non-woven fabric, paper, or the like impregnated with an epoxy resin or a phenol resin and cured, but a sheet that is not impregnated can be selected depending on the application.
  • thermosetting resin such as polyimide, polyethylene, polypropylene, polystyrene, ABS resin, vinyl chloride resin, methyl methacrylate resin, nylon, polyester resin, fluorine Resin, polycarbonate, polyacetal, polyamide, polyphenylene ether, amorphous polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, thermoplastic polyimide, polyetherimide, liquid crystal polymer and other thermoplastic resins, silicon nitride Ceramics such as a sintered body, a sialon sintered body, a silicon carbide sintered body, an alumina sintered body, and an aluminum nitride sintered body can be suitably used.
  • a method of forming a metal foil on such a sheet a method of attaching a single metal foil using heat fusion or an adhesive, a method of forming a seed layer by plating, and a vapor deposition method There are methods for forming them, and they may be formed in combination.
  • the same base material as that used for the etching resist ink can be used as the base material to which the solder resist ink is applied, and the etching resist is formed by forming a metal foil such as copper on the insulating sheet as a metal base material.
  • a circuit pattern formed by applying an ink and an etching method or a circuit pattern printed directly with a metal paste or the like can be used.
  • a pattern coating film is formed by applying ink by an ink jet method on a metal substrate surface-treated with the surface treatment agent.
  • the surface tension of the metal substrate can be adjusted by subjecting the metal substrate to a surface treatment using the surface treatment agent. Specifically, in the present invention, the surface tension can be reduced by performing a surface treatment on the metal substrate.
  • a metal substrate that is an object to be coated must have a higher surface energy (surface tension) than the ink to be coated. This is because if the metal base material to be coated has a surface energy (surface tension) lower than that of the ink to be coated, repelling and non-sticking occur vigorously and the coating film cannot be formed.
  • the quick-curing type ink jet it has been found that good results are obtained even if the surface energy of the metal substrate is somewhat lower than that of the applied ink.
  • the difference between the wetting index of the metal substrate and the surface tension of the ink can be +2 or less, preferably ⁇ 13 or more and +2 or less, more preferably ⁇ 12.
  • the difference between the wetting index of the metal substrate and the surface tension of the ink is the surface tension of the ink (the same value as the surface tension (unit: mN / m)) of the metal substrate. (Unit: mN / m). It is preferable that the difference between the wetting index of the metal substrate and the surface tension of the ink is +2 or less because both the line and the characters become clearer.
  • the surface tension of the metal substrate is generally adjusted because the surface tension of the metal substrate is too large compared to the ink, so it is difficult to adjust the surface tension of the ink and bring it closer to the metal substrate. Because.
  • a specific method of the surface treatment for the metal substrate in addition to using the surface treatment agent of the present invention, for example, a method of applying a metal surface conditioner to the surface of the metal substrate can be mentioned.
  • solder resist ink As the ink used in the present invention, at least one of solder resist ink and etching resist ink can be used.
  • any composition can be used as long as it has a low viscosity that can be applied by an ink jet method and can be peeled off after etching. Is desirable.
  • Such a composition can be produced by a combination of a carboxyl group-containing monomer, a monofunctional monomer, a polyfunctional monomer, a photopolymerization initiator, and other optional components.
  • carboxyl group-containing monomer examples include acid-modified epoxy (meth) acrylate, (meth) acrylic acid, (meth) acrylic acid dimer, crotonic acid, ⁇ -chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, Citraconic acid, mesaconic acid, ⁇ -carboxyethyl (meth) acrylate, ⁇ -carboxypolycaprolactone mono (meth) acrylate, succinic acid mono [2- (meth) acryloyloxyethyl], mono [2- (meth) acryloyl maleate Oxyethyl], 2-acryloyloxyethyl succinate, a reaction product of phthalic anhydride and hydroxyethyl (meth) acrylate, a reaction product of hexahydrophthalic anhydride and hydroxyethyl (meth) acrylate, and the like.
  • Monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate And (meth) acrylates such as hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycidyl methacrylate, ⁇ -butyrolactone acrylate and ⁇ -butyrolactone methacrylate, and acryloylmorpholine.
  • Polyfunctional monomers include polyethylene glycol diacrylates such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyurethane diacrylates and corresponding methacrylates, pentaerythritol triacrylate, triethylene glycol Methylolpropane triacrylate, trimethylolmethane triacrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane triacrylate, epichlorohydrin modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, tetramethylolmethane methacrylate La acrylate, ethylene oxide-modified phosphoric acid triacrylate, epichlorohydrin-modified glycerol triacrylate, dipentaerythritol hexaacrylate, dipentaerythri
  • photopolymerization initiators include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2- Acetophenones such as phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( Aminoacetophenones such as 4-morpholinophenyl) -butan-1-one, N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, etc.
  • thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; 2,4,5 -Triarylimidazole dimer; riboflavin tetrabutyrate; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; 2,4,6-tris-s-triazine, 2,2 Organic halogen compounds such as 1,2-tribromoethanol and tribromomethylphenylsulfone; benzophenones such as benzophenone and 4,4′-bisdiethylaminobenzophenone or xanthones; Such as trimethyl benzoyl diphenyl
  • the solder resist ink can be used as long as it has a low viscosity enough to be applied by an ink jet method and can be cured by heat or ultraviolet rays and has heat resistance after curing. Then, a composition that is further cured by heat is desirable.
  • a composition can be produced by combining various optional components with a curing agent such as an epoxy compound or an isocyanate compound, in addition to a combination of various monomers used in the etching resist ink.
  • Example 1 to 10 and Comparative Examples 1 to 13 were prepared with the blending amounts (parts by mass) shown in Tables 1 to 3 below, diluted 50 times with water, and the surface treatment agent and did.
  • a base material an FR-4 copper-clad laminate (copper thickness: 18 ⁇ m) having a size of 150 ⁇ 90 mm was used to roughen the surface by scrubbing, and this was immersed in each surface treatment agent at 23 ° C. for 60 seconds. Thereafter, the substrate was washed with running water and dried to obtain each coating substrate.
  • the wet index of the untreated substrate is considered to be about several hundred to 1,000. Tables 4 to 7 below show the wetting indices of the substrates after the surface treatment.
  • the measurement of the wetting index is performed in accordance with the method described in JIS K6768.
  • a wetting tension test mixed solution manufactured by Wako Pure Chemical Industries, Ltd. is used for the wetting index 30 to 42.
  • a mixed solution to which pure water and ethanol, and in some cases, a fluorosurfactant was added was used, and the surface tension was measured with a dynometer manufactured by BYK-GARDNER and used after adjustment.
  • the value of the wetting index is the same as the surface tension (unit: mN / m).
  • Nonionic surfactant 1 Polyoxyethylene lauryl ether * 2)
  • Nonionic surfactant 2 Sorbitan monooleate * 3)
  • Cationic surfactant 1 Lauryltrimethylammonium chloride * 4)
  • Cationic surfactant 2 Dioctyldimethylammonium chloride * 5)
  • Anionic surfactant 1 Polyoxyethylene alkylphenyl ether phosphate * 6)
  • Amphoteric surfactant 2 Lauryldimethylamine N-oxide * 9)
  • Metal salt of fatty acid 1 Potassium stearate * 10)
  • Metal salt of fatty acid 2 Sodium myristate
  • etching resist ink 4-hydroxybutyl acrylate 20 g, isobornyl acrylate 20 g, 2-acryloyloxyethyl succinate 30 g, ⁇ -butyrolactone methacrylate 15 g, pentaerythritol triacrylate 5 g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 5 g, phenylbis ( 2,4,6-trimethylbenzoyl) phosphine oxide 3g and acrylic polymerization leveling agent 0.3g were mixed, stirred and homogenized, filtered with accuracy of 1 ⁇ m, and measured with BYK-GARDNER dynometer. Thus, an etching resist ink having a surface tension of 38 mN / m was obtained.
  • solder resist ink 30 g of trimethylolpropane triacrylate, 30 g of 1,6-hexanediol diacrylate, 10 g of butyl acrylate, 5 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 3 g of phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide , 1,2-hexamethylene diisocyanate trimer blocked with 20g of dimethylpyrazole and 0.01g of silicone leveling agent, blended and homogenized, filtered with accuracy of 1 ⁇ m, manufactured by BYK-GARDNER As a result, a solder resist ink having a surface tension of 27 mN / m was obtained.
  • the difference in line width from the design value is about 20 to 30 ⁇ m, It can be seen that a high-definition pattern without bleeding is obtained, and that the peelability of the etching resist is improved. Further, in the examples, the difference between the wetting index of the copper substrate and the surface tension of the ink is ⁇ 10 to +2, and it can be seen that the lines are clear and no bleeding is confirmed.
  • Comparative Examples 1 to 8 where the pretreatment was performed using a composition containing a surfactant and no phosphoric acid, or a composition containing a metal salt of phosphoric acid and a fatty acid was used. Comparative Examples 9 and 10, Comparative Examples 11 and 12 subjected to pretreatment using a composition containing a surfactant and concentrated sulfuric acid or concentrated hydrochloric acid instead of phosphoric acid, and containing a surfactant containing phosphoric acid In Comparative Example 13 in which pretreatment was performed using a composition having no difference, the difference in the line width from the design value exceeded 100 ⁇ m, bleeding was observed visually, and further, it took time to remove the etching resist. It was. In all of the comparative examples, the difference between the wetting index of the copper substrate and the surface tension of the ink was +3 or more, and bleeding was observed visually.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Ink Jet (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

Provided are: a surface treatment agent for metal bases, which is used for a pretreatment of a metal base, and which enables drawing of a high-definition patterned coating film that is free from blurring when the patterned coating film is formed by an inkjet method; and a method for forming a patterned coating film. A surface treatment agent for metal bases, which is used in advance of the formation of a patterned coating film on a metal base by application of an ink by an inkjet method. This surface treatment agent for metal bases is composed of a composition that contains phosphoric acid, a surfactant other than a metal salt of a fatty acid, and water.

Description

金属基材用表面処理剤Surface treatment agent for metal substrates
　本発明は、金属基材用表面処理剤（以下、単に「表面処理剤」とも称する）に関し、詳しくは、金属基材上にインキをインクジェット方式により塗工して高精細なパターン塗膜を形成するために用いられる金属基材用の表面処理剤およびこれを用いたパターン塗膜の形成方法に関する。 The present invention relates to a surface treatment agent for metal substrates (hereinafter, also simply referred to as “surface treatment agent”). Specifically, ink is applied on a metal substrate by an ink jet method to form a high-definition pattern coating film. The present invention relates to a surface treatment agent for a metal substrate used for the purpose and a method for forming a pattern coating film using the same.
　一般に、金属のパターンは、銅板などの金属基材上にエッチングレジストパターンを形成し、不要部分をエッチングにて除去することにより得られる。例えば、プリント配線板の銅回路は、銅張りの基材上に所望のパターンのエッチングレジストを形成し、エッチングすることにより得られる。さらに、プリント配線板のソルダーレジストは、回路の保護やはんだブリッジ防止のために、銅回路上に形成される。 Generally, a metal pattern is obtained by forming an etching resist pattern on a metal substrate such as a copper plate and removing unnecessary portions by etching. For example, a copper circuit of a printed wiring board can be obtained by forming an etching resist having a desired pattern on a copper-clad base material and etching it. Furthermore, the solder resist of the printed wiring board is formed on the copper circuit for circuit protection and solder bridge prevention.
　エッチングレジストやソルダーレジストは、一般に、スクリーン版などを用いた印刷法や、露光および現像工程を行うフォトリソグラフィー法により形成される。また、小ロット生産への対応が可能であって、版やフォトマスクなどが省けることから、インクジェット方式によりエッチングレジストやソルダーレジストをパターン描画する方法も提案されている。 Etching resists and solder resists are generally formed by a printing method using a screen plate or the like, or a photolithography method in which exposure and development processes are performed. In addition, a method of drawing an etching resist or a solder resist by an ink jet method has been proposed because it can cope with a small lot production and omits a plate or a photomask.
　例えば、特許文献１では、エッチングレジストをインクジェット方式で描画する方法が、特許文献２では、ソルダーレジストをインクジェット方式で描画する方法が、それぞれ提案されている。しかし、インクジェット方式に適用できるレジストインキの粘度は非常に低く、銅の表面のような吸収性のない基材に塗布すると、滲みが発生してしまう。 For example, Patent Document 1 proposes a method of drawing an etching resist by an ink jet method, and Patent Document 2 proposes a method of drawing a solder resist by an ink jet method. However, the viscosity of resist ink that can be applied to the ink jet system is very low, and bleeding occurs when applied to a non-absorbing substrate such as a copper surface.
　そこで、例えば、特許文献３では、基材を加熱または冷却して、インキによる印字後にインキの粘度を高める方法が、特許文献４では、凸版反転印刷法で隔壁を形成しその内側にインクジェット方式によりインキを注入する方法が、それぞれ提案されている。また、特許文献５のように、紫外線硬化型のインキを用いて、噴射ノズルの近傍に紫外線照射手段を設けた装置も提案されている。この技術は、塗布後のインキを短時間で硬化させることにより、にじみを少なくすることができるものであり、プリント配線板用として使用されている。 Therefore, for example, in Patent Document 3, the method of heating or cooling the base material to increase the viscosity of the ink after printing with ink is used. Each method of injecting ink has been proposed. Further, as in Patent Document 5, an apparatus in which an ultraviolet irradiation means is provided in the vicinity of a jet nozzle using an ultraviolet curable ink has been proposed. This technique can reduce bleeding by curing the ink after application in a short time, and is used for printed wiring boards.
特開昭５６－２６３８４５号公報JP-A-56-263845 特開平７－２６３８４５号公報JP-A-7-263845 特開平５－３０９８３１号公報JP-A-5-309831 特開２０１１－１７１４５３号公報JP 2011-171453 A 特開平２－２８３４５２号公報Japanese Patent Laid-Open No. 2-283452
　インクジェット方式を用いてインキを塗布するにあたり、被塗布物が金属表面のような吸収性を有しない基材である場合には、上述したように、特許文献５に記載されているような装置を用いれば、滲みを少なくすることが可能である。 When applying the ink using the inkjet method, if the object to be coated is a base material that does not have an absorptivity such as a metal surface, an apparatus as described in Patent Document 5 is used as described above. If used, it is possible to reduce bleeding.
　しかしながら、その効果は充分なものではなく、結果的には満足できるような高精細なパターン塗膜は得られず、従来の、スクリーン版などを用いる印刷法や露光および現像工程を行うフォトリソグラフィー法と比較して、描画品質的に劣ったものしか得られていなかった。特に、マーキングインキの場合、この問題が顕著であった。 However, the effect is not sufficient, and as a result, a satisfactory high-definition pattern coating film cannot be obtained, and a conventional photolithography method using a printing method using a screen plate or the like and an exposure and development process. Compared to the above, only the inferior drawing quality was obtained. In particular, in the case of marking ink, this problem was remarkable.
　そこで、本発明の目的は、インクジェット方式を用いてパターン塗膜を形成するにあたり、滲みのない高精細なパターン塗膜を描画することが可能な、金属基材の前処理に用いられる表面処理剤、および、パターン塗膜の形成方法を提供することにある。 Accordingly, an object of the present invention is to provide a surface treatment agent used for pretreatment of a metal substrate, capable of drawing a high-definition pattern coating film without bleeding when forming a pattern coating film using an inkjet method. And it is providing the formation method of a pattern coating film.
　本発明者らは、上記課題を解決するために鋭意検討した結果、リン酸と、脂肪酸の金属塩を除く界面活性剤と、水と、を含む組成物からなる表面処理剤を用いることにより、上記課題を解決できることを見出して、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have used a surface treatment agent comprising a composition containing phosphoric acid, a surfactant excluding a metal salt of a fatty acid, and water, The inventors have found that the above problems can be solved, and have completed the present invention.
　すなわち、本発明の金属基材用表面処理剤は、金属基材上に、インキをインクジェット方式により塗工してパターン塗膜を形成するに先立って用いられる金属基材用表面処理剤であって、リン酸と、脂肪酸の金属塩を除く界面活性剤と、水と、を含む組成物からなることを特徴とするものである。 That is, the surface treatment agent for a metal substrate of the present invention is a surface treatment agent for a metal substrate that is used prior to forming a pattern coating film by coating ink on a metal substrate by an ink jet method. And a composition containing phosphoric acid, a surfactant excluding a metal salt of a fatty acid, and water.
　また、本発明のパターン塗膜の形成方法は、上記本発明の金属基材用表面処理剤により表面処理した金属基材上に、インキをインクジェット方式により塗工してパターン塗膜を形成することを特徴とするものである。 Moreover, the formation method of the pattern coating film of this invention forms the pattern coating film by coating ink with the inkjet system on the metal base material surface-treated with the surface treating agent for metal base materials of the said invention. It is characterized by.
　本発明の金属基材用表面処理剤によれば、インクジェット方式を用いてパターン塗膜を形成するにあたり、滲みのない高精細なパターン塗膜を描画することが可能となる。また、エッチングレジストを介した金属基材のエッチング処理にて回路を形成する場合、エッチングレジストを金属基材から剥離する必要があるが、本発明の金属基材用表面処理剤によれば、この剥離時間を短縮できる効果がある。 According to the surface treatment agent for a metal substrate of the present invention, it is possible to draw a high-definition pattern coating without bleeding when forming a pattern coating using an inkjet method. In addition, when forming a circuit by etching a metal substrate through an etching resist, it is necessary to peel the etching resist from the metal substrate. According to the surface treatment agent for a metal substrate of the present invention, There is an effect that the peeling time can be shortened.
　以下、本発明の実施の形態を、詳細に説明する。
　本発明の金属基材用表面処理剤は、金属基材上に、インキをインクジェット方式により塗工してパターン塗膜を形成するに先立って、前処理に用いられるものであり、リン酸と、脂肪酸の金属塩を除く界面活性剤と、水と、を含む組成物からなる点が重要である。 Hereinafter, embodiments of the present invention will be described in detail.
The surface treatment agent for a metal substrate of the present invention is used for pretreatment prior to forming a pattern coating film on a metal substrate by applying ink by an inkjet method, and phosphoric acid, The point which consists of a composition containing surfactant other than the metal salt of a fatty acid and water is important.
　前述したように、吸収性を有しない銅などの金属基材に対し、インクジェット方式でインキの塗工を行った場合、従来の方法では、滲みを十分に抑制して高品質の高精細パターンを得ることはできなかった。本発明者らは鋭意検討した結果、その原因が、インキの表面エネルギーに比べて、金属基材の表面エネルギーが大きすぎる点にあることを見出した。本発明者らはさらに検討した結果、金属基材に対し、特定の組成物を用いて前処理を行うことにより、その表面エネルギー、すなわち表面張力を調整することができ、これによりインクジェット方式でインキを塗工した場合において、滲みのない高精細なパターン塗膜を描画することが可能となることを見出したものである。また、本発明の表面処理剤により前処理を行うことで、エッチングレジストが金属基材から剥離しやすくなり、剥離時間を短縮できる効果も得ることができる。ここで、本発明の表面処理剤が水を必須とするのは、リン酸は単体では不安定な結晶であるため、水を含まないと、界面活性剤と混合することが困難であるためである。 As described above, when ink is applied to a metal substrate such as copper having no absorbability by the ink jet method, the conventional method sufficiently suppresses bleeding and produces a high-quality high-definition pattern. Couldn't get. As a result of intensive studies, the present inventors have found that the cause is that the surface energy of the metal substrate is too large compared to the surface energy of the ink. As a result of further investigation, the inventors of the present invention can adjust the surface energy, that is, the surface tension, by pre-treating a metal base material with a specific composition, and thereby the ink can be ink-jetted. The present inventors have found that it is possible to draw a high-definition pattern coating film that does not bleed when the coating is applied. In addition, by performing the pretreatment with the surface treating agent of the present invention, the etching resist can be easily peeled off from the metal substrate, and the effect of shortening the peeling time can be obtained. Here, the reason why the surface treatment agent of the present invention requires water is that phosphoric acid is an unstable crystal by itself, so that it is difficult to mix with a surfactant unless it contains water. is there.
（リン酸）
　本発明の表面処理剤に用いるリン酸としては、特に制限されず、いかなるものも用いることができる。 (phosphoric acid)
It does not restrict | limit especially as phosphoric acid used for the surface treating agent of this invention, What can be used.
（界面活性剤）
　本発明の表面処理剤に用いる界面活性剤としては、脂肪酸の金属塩を除くものであれば、公知慣用のものを用いることができ、例えば、アニオン系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤が挙げられる。 (Surfactant)
As the surfactant used in the surface treatment agent of the present invention, known and conventional surfactants can be used as long as they exclude the fatty acid metal salt. For example, anionic surfactants, nonionic surfactants, cations System surfactants and amphoteric surfactants.
　アニオン系界面活性剤としては、ラウリル硫酸エステルナトリウム、アルキル硫酸エステルナトリウム、ポリオキシエチレンラウリルエーテル硫酸エステルナトリウム、ポリオキシエチレンアルキルエーテル硫酸エステルナトリウム、ポリオキシエチレンアルキルエーテルフォスフェート、ポリオキシエチレンアルキルフェニルエーテルフォスフェート、アルキル硫酸エステルトリエタノールアミン、ポリオキシエチレンアルキルエーテル硫酸エステルトリエタノールアミン、２－エチルヘキシル硫酸エステルナトリウム、ジ－２－エチルヘキシルスルホコハク酸ナトリウム、直鎖型アルキルベンゼンスルホン酸ナトリウム、直鎖型アルキルベンゼンスルホン酸、脂肪酸メチルタウリン酸ナトリウム、ヤシ油脂肪酸メチルタウリン酸ナトリウム、Ｎ－デカノイル－Ｎ－メチルタウリン酸ナトリウム、α－スルホ脂肪酸メチルエステルナトリウム、脂肪酸アミドエーテル硫酸エステルナトリウム、Ｎ－オレイル－Ｎ－メチルグリシン、Ｎ－ラウロイル－Ｎ－メチルグリシンナトリウム、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩、ポリオキシエチレンアリールエーテル硫酸エステル塩、ポリオキシアルキレンアルキルエーテルリン酸エステル、ポリアクリル酸ナトリウム、スルホネート等が挙げられる。 Anionic surfactants include sodium lauryl sulfate, sodium alkyl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether Phosphate, alkyl sulfate triethanolamine, polyoxyethylene alkyl ether sulfate triethanolamine, sodium 2-ethylhexyl sulfate, sodium di-2-ethylhexylsulfosuccinate, sodium linear alkylbenzene sulfonate, linear alkylbenzene sulfone Acid, fatty acid sodium methyl taurate, palm oil fatty acid methyl taurate sodium N-decanoyl-N-methyltaurate sodium, α-sulfo fatty acid methyl ester sodium, fatty acid amide ether sulfate sodium salt, N-oleyl-N-methylglycine, N-lauroyl-N-methylglycine sodium, polyoxyethylene Examples include polycyclic phenyl ether sulfate, polyoxyethylene aryl ether sulfate, polyoxyalkylene alkyl ether phosphate, sodium polyacrylate, sulfonate, and the like.
　ノニオン系界面活性剤としては、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンイソデシルエーテル、ポリオキシエチレン－２－エチルヘキシルエーテル、ポリオキシエチレン分岐アルキルエーテル、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、ポリオキシプロピレンステアリルエーテル、ポリオキシエチレンモノラウレート、ポリオキシエチレンモノステアレート、ポリオキシエチレンモノオレート、ソルビタンモノカプリレート、ソルビタンモノラウレート、ソルビタンモノミリステート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノオレート、ソルビタンセスキオレート、ソルビタントリオレート、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタンモノオレート、エチレングリコールジステアレート、ポリエチレングリコールジステアレート、ポリエチレングリコールジオレート、ポリプロピレングリコールジステアレート、ポリプロピレングリコールジサクシネート、グリセリロールモノステアレート、グリセリロールモノミリステート、ポリオキシエチレンヤシ脂肪酸グリセリル、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレントリイソステアリン酸、ポリオキシエチレンテトラオレイン酸、ポリグリセリンオレイン酸エステル、ポリグリセリンラウリン酸エステル、ポリグリセリンステアリン酸エステル、Ｎ－ヒドロキシエチルラウリルアミン、ポリオキシエチレンラウリルアミン、ポリオキシエチレンポリオキシプロピレンラウリルアミン、ポリオキシエチレンアルキルアミン、ポリオキシエチレンステアリルアミン、ポリオキシエチレンオレイルアミン、ポリオキシエチレン牛脂アルキルアミン、ポリオキシエチレンアルキルプロピレンジアミン、ヤシ脂肪酸ジエタノールアミド、牛脂肪酸ジエタノールアミド、ラウリン酸ジエタノールアミド、ヤシ脂肪酸ジエタノールアミド、オレイン酸ジエタノールアミド、ヤシ脂肪酸モノエタノールアミド、ラウリン酸イソプロパノールアミド、ポリオキシエチレン脂肪酸モノエタノールアミド、ポリオキシアリールエーテル、ポリオキシアルキレンアリールエーテル、ポリオキシエチレンクミルフェニルエーテル、ポリオキシエチレンポリオキシプロピレンブロックポリマー、ポリオキシエチレンオレエート、ポリオキシエチレンアルキルアミンエーテル等が挙げられる。 Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene isodecyl ether, polyoxyethylene-2-ethylhexyl ether, polyoxy Ethylene branched alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene stearyl ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, sorbitan monocaprylate, sorbitan monolaurate, Sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sol Tansesquiolate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, ethylene glycol distearate, polyethylene glycol distearate, polyethylene glycol diolate, polypropylene glycol Distearate, polypropylene glycol disuccinate, glyceryl monostearate, glyceryl monomyristate, glyceryl polyoxyethylene coconut fatty acid, polyoxyethylene hydrogenated castor oil, polyoxyethylene triisostearic acid, polyoxyethylene tetraoleic acid, Polyglycerol oleate, polyglycerol laurate, polyglycerol stearis Acid ester, N-hydroxyethyl lauryl amine, polyoxyethylene lauryl amine, polyoxyethylene polyoxypropylene lauryl amine, polyoxyethylene alkylamine, polyoxyethylene stearylamine, polyoxyethylene oleylamine, polyoxyethylene tallow alkylamine, poly Oxyethylene alkylpropylenediamine, coconut fatty acid diethanolamide, bovine fatty acid diethanolamide, lauric acid diethanolamide, coconut fatty acid diethanolamide, oleic acid diethanolamide, coconut fatty acid monoethanolamide, lauric acid isopropanolamide, polyoxyethylene fatty acid monoethanolamide, Polyoxyaryl ether, polyoxyalkylene aryl ether, polyoxyethylene Ncumylphenyl ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene oleate, polyoxyethylene alkylamine ether and the like.
　カチオン系界面活性剤としては、テトラデシルアミン酢酸塩、オクタデシルアミン酢酸塩、ラウリルトリメチルアンモニウムクロライド、セチルトリメチルアンモニウムクロライド、ジオクチルジメチルアンモニウムクロライド、ドデシルトリメチルアンモニウムクロライド、ヤシアルキルトリメチルアンモニウムクロライド、ヘキサデシルトリメチルアンモニウムクロライド、牛脂アルキルトリメチル－アンモニウムクロライド、オクタデシルトリメチルアンモニウムクロライド、ベヘニルトリメチルアンモニウムクロライド、ジデシルジメチルアンモニウムクロライド、ジ硬化牛脂アルキルジメチルアンモニウムクロライド、ジオレイルジメチルアンモニウムクロライド、ヤシアルキルジメチルベンジルアンモニウムクロライド、テトラデシルジメチルベンジルアンモニウムクロライド、Ｎ，Ｎ－ジアシルオキシエチル－Ｎ－ヒドロキシエチル－Ｎ－メチルアンモニウムメチルサルフェート、１－メチル－１－ヒドロキシエチル－２－牛脂アルキルイミダゾニウムクロライド、アルキルアンモニウムハイドライド等が挙げられる。 Cationic surfactants include tetradecylamine acetate, octadecylamine acetate, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, dioctyldimethylammonium chloride, dodecyltrimethylammonium chloride, cocoalkyltrimethylammonium chloride, hexadecyltrimethylammonium chloride. Tallow alkyltrimethyl-ammonium chloride, octadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, didecyldimethylammonium chloride, di-cured tallow alkyldimethylammonium chloride, dioleyldimethylammonium chloride, palm alkyldimethylbenzylammonium chloride, tet Examples include decyldimethylbenzylammonium chloride, N, N-diacyloxyethyl-N-hydroxyethyl-N-methylammonium methyl sulfate, 1-methyl-1-hydroxyethyl-2-tallow alkylimidazolium chloride, alkylammonium hydride, and the like. .
　両性界面活性剤としては、ヤシ油ジメチルベタイン、ヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン、パーム核油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン、ラウリルジメチルアミノ酢酸ベタイン、ステアリルジメチルアミノ酢酸ベタイン、ラウリン酸アミドプロピルジメチルアミノ酢酸ベタイン、ドデシルアミノメチルジメチルスルホプロピルベタイン、オクタデシルアミノメチルジメチルスルホプロピルベタイン、コカミドプロピルヒドロキシスルタイン、２－アルキル－Ｎ－カルボキシメチル－Ｎ－ヒドロキシエチル－イミダゾリウムベタイン、ラウリルアミノジ酢酸モノナトリウム、ラウリルジアミノエチルグリシンナトリウム、ラウロイルメチルアラニンナトリウム、ラウロイルグルタミン酸ナトリウム、ラウロイルグルタミン酸カリウム、ラウロイルメチル－β－アラニン、ラウリルジメチルアミンＮ‐オキシド、オレイルジメチルアミンＮ‐オキシド等が挙げられる。 Amphoteric surfactants include palm oil dimethyl betaine, palm oil fatty acid amidopropyl dimethylaminoacetic acid betaine, palm kernel fatty acid amidopropyl dimethylaminoacetic acid betaine, lauryl dimethylaminoacetic acid betaine, stearyl dimethylaminoacetic acid betaine, lauric acid amidopropyldimethyl Betaine aminoacetate, dodecylaminomethyldimethylsulfopropylbetaine, octadecylaminomethyldimethylsulfopropylbetaine, cocamidopropylhydroxysultain, 2-alkyl-N-carboxymethyl-N-hydroxyethyl-imidazolium betaine, laurylaminodiacetic acid mono Sodium, sodium lauryldiaminoethylglycine, sodium lauroylmethylalanine, sodium lauroylglutamate, Potassium acryloyloxy glutamate, lauroyl methyl -β- alanine, lauryl dimethylamine N- oxide, oleyl dimethylamine N- oxides and the like.
　界面活性剤であっても、ミリスチン酸カリウム、ラウリン酸カリウム、ヤシ脂肪酸カリウム、パルミチン酸カリウム、ステアリン酸カリウム、オレイン酸カリウム、ヤシ脂肪酸ナトリウム、ミリスチン酸ナトリウム、ステアリン酸ナトリウム、オレイン酸ナトリウム等の脂肪酸の金属塩は、本発明において効果が見られない。ここで、本発明において脂肪酸の金属塩とは、脂肪酸が金属と塩を形成しているものを意味する。これは、界面活性剤として脂肪酸の金属塩を用いると、脂肪酸の金属塩とリン酸とが混ざった際に固形分が析出して、界面活性剤としての機能を奏し得なくなるためである。 Fatty acids such as potassium myristate, potassium laurate, potassium palm fatty acid, potassium palmitate, potassium stearate, potassium oleate, sodium palm fatty acid, sodium myristate, sodium stearate, sodium oleate This metal salt has no effect in the present invention. Here, in the present invention, the metal salt of a fatty acid means one in which the fatty acid forms a salt with the metal. This is because if a metal salt of a fatty acid is used as a surfactant, a solid content is precipitated when the metal salt of a fatty acid and phosphoric acid are mixed, and the function as a surfactant cannot be achieved.
　本発明の表面処理剤として用いられる組成物において、リン酸と界面活性剤との質量比率は、好適には１００：０．１～１００：５０とすることができ、より好適には１００：０．２～１００：２０である。各成分の比率を上記範囲とすることで、滲みのない高精細なパターン塗膜をより確実に得ることができるものとなる。一方、水の配合量は、最小量はリン酸が溶ける量であればよく、最大量は界面活性剤の濃度が０．０００１質量％以下にならない量とすることができ、より好適には、界面活性剤の濃度が０．００１～０．１質量％となる量である。 In the composition used as the surface treating agent of the present invention, the mass ratio of phosphoric acid to the surfactant can be preferably 100: 0.1 to 100: 50, and more preferably 100: 0. .2 to 100: 20. By setting the ratio of each component in the above range, a high-definition pattern coating without bleeding can be obtained more reliably. On the other hand, the blending amount of water may be the minimum amount as long as phosphoric acid can be dissolved, and the maximum amount can be an amount such that the concentration of the surfactant does not become 0.0001% by mass or less. The amount of the surfactant is 0.001 to 0.1% by mass.
　本発明の表面処理剤による金属基材の処理は、上記表面処理剤を、そのままか、または、任意の濃度で水や各種水溶性溶剤で希釈した状態で、金属基材の表面に塗布するかまたは浸漬して、必要に応じて洗浄し、乾燥させることにより行うことができる。 In the treatment of the metal substrate with the surface treatment agent of the present invention, the surface treatment agent is applied to the surface of the metal substrate as it is or diluted with water or various water-soluble solvents at an arbitrary concentration. Or it can carry out by immersing, washing | cleaning as needed, and making it dry.
（金属基材）
　金属基材としては、プリント配線板に通常使用される銅、鉄、錫、アルミニウム、銀、ステンレス、真鍮、ニッケル、チタン、および、それらの合金などの金属箔が挙げられる。本発明は、特には、プリント配線板上に配設された金属基材としての銅箔上に、インキをインクジェット方式により塗工して、プリント配線板用レジストインキの塗膜を形成する際に有用である。中でも、エッチングレジストインキやソルダーレジストインキの塗膜を形成する際に特に有用である。 (Metal base material)
Examples of the metal substrate include metal foils such as copper, iron, tin, aluminum, silver, stainless steel, brass, nickel, titanium, and alloys thereof that are usually used for printed wiring boards. The present invention is particularly suitable for forming a coating film of a resist ink for printed wiring board by applying ink by an ink jet method on a copper foil as a metal substrate disposed on the printed wiring board. Useful. Among these, it is particularly useful when forming a coating film of etching resist ink or solder resist ink.
　エッチングレジストインキを塗布する基材は、絶縁性のシートに、金属基材としての、銅などの金属箔を形成したものである。絶縁性のシートは、一般的には、ガラスクロス、不織布、紙等にエポキシ樹脂、フェノール樹脂を含浸させ硬化させたものであるが、用途に応じて含浸させていないものも選択できる。例えば、エポキシ樹脂、メラミン樹脂、フェノール樹脂、尿素樹脂、不飽和ポリエステル樹脂、ポリイミド等の熱硬化樹脂、ポリエチレン、ポリプロピレン、ポリスチレン、ＡＢＳ樹脂、塩化ビニル樹脂、メタクリル酸メチル樹脂、ナイロン、ポリエステル樹脂、フッ素樹脂，ポリカーボネート、ポリアセタール、ポリアミド、ポリフェニレンエーテル、非晶ポリアリレート、ポリサルフォン、ポリエーテルサルフォン、ポリフェニレンスルファイド、ポリエーテルエーテルケトン、熱可塑性ポリイミド、ポリエーテルイミド、液晶ポリマー等の熱可塑性樹脂、窒化ケイ素焼結体、サイアロン焼結体、炭化ケイ素焼結体、アルミナ焼結体、窒化アルミニウム焼結体等のセラミックを好適に使用することができる。このようなシート上への金属箔の形成方法としては、単体の金属箔を熱融着や接着剤を用いて張り付ける方法、シード層をつけてめっき法にて形成する方法、蒸着法にて形成する方法等があり、それらを組み合わせて形成してもよい。 The base material to which the etching resist ink is applied is obtained by forming a metal foil such as copper as a metal base material on an insulating sheet. The insulating sheet is generally a glass cloth, non-woven fabric, paper, or the like impregnated with an epoxy resin or a phenol resin and cured, but a sheet that is not impregnated can be selected depending on the application. For example, epoxy resin, melamine resin, phenol resin, urea resin, unsaturated polyester resin, thermosetting resin such as polyimide, polyethylene, polypropylene, polystyrene, ABS resin, vinyl chloride resin, methyl methacrylate resin, nylon, polyester resin, fluorine Resin, polycarbonate, polyacetal, polyamide, polyphenylene ether, amorphous polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, thermoplastic polyimide, polyetherimide, liquid crystal polymer and other thermoplastic resins, silicon nitride Ceramics such as a sintered body, a sialon sintered body, a silicon carbide sintered body, an alumina sintered body, and an aluminum nitride sintered body can be suitably used. As a method of forming a metal foil on such a sheet, a method of attaching a single metal foil using heat fusion or an adhesive, a method of forming a seed layer by plating, and a vapor deposition method There are methods for forming them, and they may be formed in combination.
　ソルダーレジストインキを塗布する基材は、エッチングレジストインキに使用したものと同様の基材が使用でき、絶縁性のシートに金属基材としての、銅などの金属箔を形成したものに、エッチングレジストインキを塗布してエッチング法により回路パターンを形成したものや、金属ペーストなどで直接回路パターンを印刷したものなどが使用できる。 The same base material as that used for the etching resist ink can be used as the base material to which the solder resist ink is applied, and the etching resist is formed by forming a metal foil such as copper on the insulating sheet as a metal base material. A circuit pattern formed by applying an ink and an etching method or a circuit pattern printed directly with a metal paste or the like can be used.
　本発明のパターン塗膜の形成方法においては、上記表面処理剤により表面処理した金属基材上に、インキをインクジェット方式により塗工してパターン塗膜を形成する。 In the method for forming a patterned coating film of the present invention, a pattern coating film is formed by applying ink by an ink jet method on a metal substrate surface-treated with the surface treatment agent.
　前述したように、本発明においては、かかる金属基材に上記表面処理剤を用いて表面処理を施すことで、金属基材の表面張力を調整することができる。具体的には、本発明においては、金属基材に対し表面処理を施すことで、その表面張力を低下させることができる。なお、通常、被塗布物である金属基材は、塗布するインキよりも高い表面エネルギー（表面張力）でなければならない。これは、被塗布物である金属基材が、塗布するインキよりも低い表面エネルギー（表面張力）を有すると、はじきや未着が激しく発生して、塗膜として成り立たなくなるからである。しかし、即硬化型のインクジェットにおいては、常識を覆し、金属基材の表面エネルギーが塗布するインキよりもある程度低い値であっても、良好な結果となることが判った。 As described above, in the present invention, the surface tension of the metal substrate can be adjusted by subjecting the metal substrate to a surface treatment using the surface treatment agent. Specifically, in the present invention, the surface tension can be reduced by performing a surface treatment on the metal substrate. In general, a metal substrate that is an object to be coated must have a higher surface energy (surface tension) than the ink to be coated. This is because if the metal base material to be coated has a surface energy (surface tension) lower than that of the ink to be coated, repelling and non-sticking occur vigorously and the coating film cannot be formed. However, in the quick-curing type ink jet, it has been found that good results are obtained even if the surface energy of the metal substrate is somewhat lower than that of the applied ink.
　本発明においては、具体的には例えば、金属基材の濡れ指数とインキの表面張力との差を、＋２以下とすることができ、好適には－１３以上＋２以下、より好適には－１２以上＋２以下とする。ここで、本発明において、金属基材の濡れ指数とインキの表面張力との差とは、金属基材の濡れ指数（表面張力（単位：ｍＮ／ｍ）と同値）から、インキの表面張力（単位：ｍＮ／ｍ）を引いた値である。金属基材の濡れ指数とインキの表面張力との差が＋２以下であると、ラインおよび文字共により鮮明になる点で好ましい。なお、金属基材の表面張力を調整するのは、一般に、金属基材の表面張力はインキと比較して大きすぎるため、インキの表面張力を調整して金属基材に近づけることは困難であるためである。なお、金属基材に対する表面処理の具体的な方法としては、本発明の上記表面処理剤を用いる他、例えば、金属基材の表面に、金属表面調整剤を塗布する方法が挙げられる。 In the present invention, specifically, for example, the difference between the wetting index of the metal substrate and the surface tension of the ink can be +2 or less, preferably −13 or more and +2 or less, more preferably −12. Above +2 Here, in the present invention, the difference between the wetting index of the metal substrate and the surface tension of the ink is the surface tension of the ink (the same value as the surface tension (unit: mN / m)) of the metal substrate. (Unit: mN / m). It is preferable that the difference between the wetting index of the metal substrate and the surface tension of the ink is +2 or less because both the line and the characters become clearer. The surface tension of the metal substrate is generally adjusted because the surface tension of the metal substrate is too large compared to the ink, so it is difficult to adjust the surface tension of the ink and bring it closer to the metal substrate. Because. In addition, as a specific method of the surface treatment for the metal substrate, in addition to using the surface treatment agent of the present invention, for example, a method of applying a metal surface conditioner to the surface of the metal substrate can be mentioned.
（インキ）
　本発明に用いられるインキとしては、ソルダーレジストインキおよびエッチングレジストインキの少なくともいずれか１種を用いることができる。 (ink)
As the ink used in the present invention, at least one of solder resist ink and etching resist ink can be used.
　エッチングレジストインキとしては、インクジェット方式で塗布可能な程度の低粘度であって、エッチング後に剥離可能な組成物であれば使用できるが、塗布後に紫外線により硬化し、アルカリ水溶液にて剥離可能な組成物が望ましい。このような組成物は、カルボキシル基含有モノマー、単官能モノマー、多官能モノマー、光重合開始剤、および、その他任意成分の組み合わせで製造できる。 As the etching resist ink, any composition can be used as long as it has a low viscosity that can be applied by an ink jet method and can be peeled off after etching. Is desirable. Such a composition can be produced by a combination of a carboxyl group-containing monomer, a monofunctional monomer, a polyfunctional monomer, a photopolymerization initiator, and other optional components.
　カルボキシル基含有モノマーとしては、酸変性エポキシ（メタ）アクリレート、（メタ）アクリル酸、（メタ）アクリル酸ダイマー、クロトン酸、α－クロルアクリル酸、ケイ皮酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸、β－カルボキシエチル（メタ）アクリレート、ω－カルボキシポリカプロラクトンモノ（メタ）アクリレート、コハク酸モノ［２－（メタ）アクリロイルオキシエチル］、マレイン酸モノ［２－（メタ）アクリロイルオキシエチル］、２－アクリロイルオキシエチルサクシネート、無水フタル酸とヒドロキシエチル（メタ）アクリレートとの反応物、無水ヘキサヒドロフタル酸とヒドロキシエチル（メタ）アクリレートとの反応物などが挙げられる。 Examples of the carboxyl group-containing monomer include acid-modified epoxy (meth) acrylate, (meth) acrylic acid, (meth) acrylic acid dimer, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, Citraconic acid, mesaconic acid, β-carboxyethyl (meth) acrylate, ω-carboxypolycaprolactone mono (meth) acrylate, succinic acid mono [2- (meth) acryloyloxyethyl], mono [2- (meth) acryloyl maleate Oxyethyl], 2-acryloyloxyethyl succinate, a reaction product of phthalic anhydride and hydroxyethyl (meth) acrylate, a reaction product of hexahydrophthalic anhydride and hydroxyethyl (meth) acrylate, and the like.
　単官能モノマーとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、グリシジルメタクリレート、γ－ブチロラクトンアクリレート、γ－ブチロラクトンメタクリレート等の（メタ）アクリレート類や、アクリロイルモルホリンなどが挙げられる。 Monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate And (meth) acrylates such as hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycidyl methacrylate, γ-butyrolactone acrylate and γ-butyrolactone methacrylate, and acryloylmorpholine.
　多官能モノマーとしては、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート等のポリエチレングリコールジアクリレート、あるいは、ポリウレタンジアクリレート類およびそれ等に対応するメタアクリレート類、ペンタエリスリトールトリアクリレート、トリメチロールプロパントリアクリレート、トリメチロールメタントリアクリレート、エチレンオキシド変性トリメチロールプロパントリアクリレート、プロピレンオキシド変性トリメチロールプロパントリアクリレート、エピクロルヒドリン変性トリメチロールプロパントリアクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールテトラメタクリレート、テトラメチロールメタンテトラアクリレート、エチレンオキシド変性リン酸トリアクリレート、エピクロルヒドリン変性グリセロールトリアクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールモノヒドロキシペンタアクリレート、ビスフェノールフルオレンジヒドロキシアクリレート、ビスフェノールフルオレンジメタクリレートなどが挙げられる。 Polyfunctional monomers include polyethylene glycol diacrylates such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyurethane diacrylates and corresponding methacrylates, pentaerythritol triacrylate, triethylene glycol Methylolpropane triacrylate, trimethylolmethane triacrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane triacrylate, epichlorohydrin modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, tetramethylolmethane methacrylate La acrylate, ethylene oxide-modified phosphoric acid triacrylate, epichlorohydrin-modified glycerol triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxy pentaacrylate, bisphenol fluorene dihydroxy acrylate, and bisphenol fluorene methacrylate.
　光重合開始剤としては、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインとベンゾインアルキルエーテル類；アセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、１，１－ジクロロアセトフェノン等のアセトフェノン類；２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタン－１－オン、Ｎ，Ｎ－ジメチルアミノアセトフェノン等のアミノアセトフェノン類；２－メチルアントラキノン、２－エチルアントラキノン、２－ｔ－ブチルアントラキノン、１－クロロアントラキノン等のアントラキノン類；２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２－クロロチオキサントン、２，４－ジイソプロピルチオキサントン等のチオキサントン類；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類；２，４，５－トリアリールイミダゾール二量体；リボフラビンテトラブチレート；２－メルカプトベンゾイミダゾール、２－メルカプトベンゾオキサゾール、２－メルカプトベンゾチアゾール等のチオール化合物；２，４，６－トリス－ｓ－トリアジン、２，２，２－トリブロモエタノール、トリブロモメチルフェニルスルホン等の有機ハロゲン化合物；ベンゾフェノン、４，４’－ビスジエチルアミノベンゾフェノン等のベンゾフェノン類またはキサントン類；２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイドなどが挙げられる。 Examples of photopolymerization initiators include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2- Acetophenones such as phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( Aminoacetophenones such as 4-morpholinophenyl) -butan-1-one, N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, etc. Anthraquinones; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; 2,4,5 -Triarylimidazole dimer; riboflavin tetrabutyrate; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; 2,4,6-tris-s-triazine, 2,2 Organic halogen compounds such as 1,2-tribromoethanol and tribromomethylphenylsulfone; benzophenones such as benzophenone and 4,4′-bisdiethylaminobenzophenone or xanthones; Such as trimethyl benzoyl diphenyl phosphine oxide.
　ソルダーレジストインキとしては、インクジェット方式で塗布可能な程度の低粘度であって、熱や紫外線などにより硬化可能で、硬化後に耐熱性をもつ組成物であれば使用できるが、塗布後に紫外線により硬化し、その後、熱によりさらに硬化する組成物が望ましい。このような組成物は、エッチングレジストインキに使用する各種モノマーの組み合わせに加えて、エポキシ化合物やイソシアネート化合物などの硬化剤と各種任意成分を組み合わせることで製造できる。 The solder resist ink can be used as long as it has a low viscosity enough to be applied by an ink jet method and can be cured by heat or ultraviolet rays and has heat resistance after curing. Then, a composition that is further cured by heat is desirable. Such a composition can be produced by combining various optional components with a curing agent such as an epoxy compound or an isocyanate compound, in addition to a combination of various monomers used in the etching resist ink.
　以下、本発明を、実施例を用いてより詳細に説明する。 Hereinafter, the present invention will be described in more detail using examples.
（塗布用基材の調製）
　下記の表１～３に示す配合量（質量部）で、実施例１～１０および比較例１～１３の各高濃度液を作製し、水にて５０倍に希釈して、表面処理剤とした。基材としては、１５０×９０ｍｍの大きさのＦＲ－４銅張積層版（銅厚１８μｍ）を用いて、スクラブ研磨にて表面を粗化し、これを２３℃の各表面処理剤に６０秒間浸漬して、その後、流水にて洗浄し、乾燥させて各塗布用基材とした。なお、未処理の基材の濡れ指数は、数百～１０００程度と考えられる。表面処理後の基材の濡れ指数を、下記の表４～７に示す。 (Preparation of coating substrate)
The high concentration liquids of Examples 1 to 10 and Comparative Examples 1 to 13 were prepared with the blending amounts (parts by mass) shown in Tables 1 to 3 below, diluted 50 times with water, and the surface treatment agent and did. As a base material, an FR-4 copper-clad laminate (copper thickness: 18 μm) having a size of 150 × 90 mm was used to roughen the surface by scrubbing, and this was immersed in each surface treatment agent at 23 ° C. for 60 seconds. Thereafter, the substrate was washed with running water and dried to obtain each coating substrate. The wet index of the untreated substrate is considered to be about several hundred to 1,000. Tables 4 to 7 below show the wetting indices of the substrates after the surface treatment.
　ここで、濡れ指数の測定は、ＪＩＳ　Ｋ６７６８に記載の方法に準拠して行い、濡れ指数３０から４２までは和光純薬工業社製のぬれ張力試験用混合液を使用し、濡れ指数２８から２９までは純水とエタノールと、場合によってはさらにフッ素系界面活性剤とを添加した混合液を使用し、ＢＹＫ－ＧＡＲＤＮＥＲ社製のダイノメーターで表面張力を測定して、調整して用いた。なお、濡れ指数の値は、表面張力（単位：ｍＮ／ｍ）と同値である。 Here, the measurement of the wetting index is performed in accordance with the method described in JIS K6768. For the wetting index 30 to 42, a wetting tension test mixed solution manufactured by Wako Pure Chemical Industries, Ltd. is used. Up to this point, a mixed solution to which pure water and ethanol, and in some cases, a fluorosurfactant was added was used, and the surface tension was measured with a dynometer manufactured by BYK-GARDNER and used after adjustment. Note that the value of the wetting index is the same as the surface tension (unit: mN / m).
Figure JPOXMLDOC01-appb-T000001
 ＊１）ノニオン系界面活性剤１：ポリオキシエチレンラウリルエーテル
＊２）ノニオン系界面活性剤２：ソルビタンモノオレート
＊３）カチオン系界面活性剤１：ラウリルトリメチルアンモニウムクロライド
＊４）カチオン系界面活性剤２：ジオクチルジメチルアンモニウムクロライド
＊５）アニオン系界面活性剤１：ポリオキシエチレンアルキルフェニルエーテルフォスフェート
＊６）アニオン系界面活性剤２：アルキル硫酸エステルトリエタノールアミン
＊７）両性界面活性剤１：２－アルキル－Ｎ－カルボキシメチル－Ｎ－ヒドロキシエチル－イミダゾリウムベタイン
＊８）両性界面活性剤２：ラウリルジメチルアミンＮ－オキシド
＊９）脂肪酸の金属塩１：ステアリン酸カリウム
＊１０）脂肪酸の金属塩２：ミリスチン酸ナトリウム
Figure JPOXMLDOC01-appb-T000001
 * 1) Nonionic surfactant 1: Polyoxyethylene lauryl ether * 2) Nonionic surfactant 2: Sorbitan monooleate * 3) Cationic surfactant 1: Lauryltrimethylammonium chloride * 4) Cationic surfactant 2: Dioctyldimethylammonium chloride * 5) Anionic surfactant 1: Polyoxyethylene alkylphenyl ether phosphate * 6) Anionic surfactant 2: Alkyl sulfate triethanolamine * 7) Amphoteric surfactant 1: 2 -Alkyl-N-carboxymethyl-N-hydroxyethyl-imidazolium betaine * 8) Amphoteric surfactant 2: Lauryldimethylamine N-oxide * 9) Metal salt of fatty acid 1: Potassium stearate * 10) Metal salt of fatty acid 2: Sodium myristate
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
（エッチングレジストインキの調製）
　４－ヒドロキシブチルアクリレート２０ｇ、イソボロニルアクリレート２０ｇ、２－アクリロイルオキシエチルサクシネート３０ｇ、γ―ブチロラクトンメタクリレート１５ｇ、ペンタエリスリトールトリアクリレート５ｇ、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキシド５ｇ、フェニルビス（２，４，６－トリメチルベンゾイル）ホスフィンオキシド３ｇ、および、アクリル重合系レベリング剤０．３ｇを配合、撹拌して均一化し、１μｍ精度の濾過を行い、ＢＹＫ－ＧＡＲＤＮＥＲ社製のダイノメーターで測定して、表面張力３８ｍＮ／ｍのエッチングレジストインキを得た。 (Preparation of etching resist ink)
4-hydroxybutyl acrylate 20 g, isobornyl acrylate 20 g, 2-acryloyloxyethyl succinate 30 g, γ-butyrolactone methacrylate 15 g, pentaerythritol triacrylate 5 g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 5 g, phenylbis ( 2,4,6-trimethylbenzoyl) phosphine oxide 3g and acrylic polymerization leveling agent 0.3g were mixed, stirred and homogenized, filtered with accuracy of 1μm, and measured with BYK-GARDNER dynometer. Thus, an etching resist ink having a surface tension of 38 mN / m was obtained.
（ソルダーレジストインキの調製）
　トリメチロールプロパントリアクリレート３０ｇ、１，６－ヘキサンジオールジアクリレート３０ｇ、アクリル酸ブチル１０ｇ、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキシド５ｇ、フェニルビス（２，４，６－トリメチルベンゾイル）ホスフィンオキシド３ｇ、１，６－ヘキサメチレンジイソシアネートのトリマーをジメチルピラゾールでブロックしたブロックイソシアネート２０ｇ、および、シリコーン系レベリング剤０．０１ｇを配合、撹拌して均一化し、１μｍ精度の濾過を行い、ＢＹＫ－ＧＡＲＤＮＥＲ社製のダイノメーターで測定して、表面張力２７ｍＮ／ｍのソルダーレジストインキを得た。 (Preparation of solder resist ink)
30 g of trimethylolpropane triacrylate, 30 g of 1,6-hexanediol diacrylate, 10 g of butyl acrylate, 5 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 3 g of phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide , 1,2-hexamethylene diisocyanate trimer blocked with 20g of dimethylpyrazole and 0.01g of silicone leveling agent, blended and homogenized, filtered with accuracy of 1μm, manufactured by BYK-GARDNER As a result, a solder resist ink having a surface tension of 27 mN / m was obtained.
（インクジェット塗布）
　各塗布用基材上に、上記で調製したエッチングレジストインキおよびソルダーレジストインキを用いて、富士フィルム社製のインクジェットプリンターＤｉｍａｔｉｘ　Ｍａｔｅｒｉａｌｓ　Ｐｒｉｎｔｅｒ　ＤＭＰ－２８３１により、線幅２００μｍのラインを描画した。この際、プリントヘッドの側面にスポット型のＵＶ照射器を取り付け、描画しながら即時に硬化を行った。 (Inkjet application)
A line having a line width of 200 μm was drawn on each coating substrate using the etching resist ink and the solder resist ink prepared as described above, using an inkjet printer Dimatix Materials Printer DMP-2831 manufactured by Fuji Film. At this time, a spot type UV irradiator was attached to the side surface of the print head, and curing was performed immediately while drawing.
（ライン幅の評価）
　各基材について、描画されたラインの線幅を測定し、設計値との差を算出した。エッチングレジストの結果を下記の表４，５に、ソルダーレジストの結果を下記の表６，７に、それぞれ示す。 (Evaluation of line width)
About each base material, the line width of the drawn line was measured and the difference with a design value was computed. The results of the etching resist are shown in Tables 4 and 5 below, and the results of the solder resist are shown in Tables 6 and 7 below.
（目視評価）
　描画されたラインを目視にて観察し、鮮明さを評価した。ラインが鮮明で滲みが確認されないものを○、滲みが見られラインが太く見えるものを×とした。エッチングレジストの結果を下記の表４，５に、ソルダーレジストの結果を下記の表６，７に、それぞれ示す。 (Visual evaluation)
The drawn lines were observed visually to evaluate the clarity. The case where the line was clear and no blur was observed was indicated by ○, and the case where the blur was observed and the line appeared thick was indicated by ×. The results of the etching resist are shown in Tables 4 and 5 below, and the results of the solder resist are shown in Tables 6 and 7 below.
（剥離性）
　エッチングレジストを塗布した基材について、塩化第二鉄系のエッチング液でレジストがパターニングされていない部分の銅箔をエッチングした後、４０℃の３％水酸化ナトリウム水溶液に浸漬して、剥離時間を観察した。３０秒以内で剥離できたものを○、４５秒以内で剥離できたものを△、それ以上時間がかかったものを×とした。結果を、下記の表４，５に示す。 (Peelability)
For the base material coated with the etching resist, after etching the portion of the copper foil where the resist was not patterned with a ferric chloride-based etchant, the substrate was immersed in a 3% aqueous sodium hydroxide solution at 40 ° C. to increase the peeling time. Observed. Those that could be peeled off within 30 seconds were marked with ◯, those that could be peeled within 45 seconds were marked with Δ, and those that took longer than that were marked with ×. The results are shown in Tables 4 and 5 below.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　上記表中に示す各実施例の結果から、リン酸と界面活性剤とを併用した組成物を表面処理剤として用いることで、設計値との線幅の差が２０～３０μｍ程度であって、滲みのない高精細なパターンが得られており、さらに、エッチングレジストに関しては、剥離性が向上していることがわかる。また、実施例では、銅基材の濡れ指数とインキの表面張力との差が－１０～＋２であって、ラインが鮮明で滲みが確認されないことがわかる。 From the results of the examples shown in the above table, using a composition in which phosphoric acid and a surfactant are used in combination as a surface treatment agent, the difference in line width from the design value is about 20 to 30 μm, It can be seen that a high-definition pattern without bleeding is obtained, and that the peelability of the etching resist is improved. Further, in the examples, the difference between the wetting index of the copper substrate and the surface tension of the ink is −10 to +2, and it can be seen that the lines are clear and no bleeding is confirmed.
　これに対し、界面活性剤を含みリン酸を含まない組成物を用いて前処理を行った比較例１～８や、リン酸と脂肪酸の金属塩とを含む組成物を用いて前処理を行った比較例９，１０、界面活性剤と、リン酸に代えて濃硫酸または濃塩酸とを含む組成物を用いて前処理を行った比較例１１，１２、リン酸を含み界面活性剤を含まない組成物を用いて前処理を行った比較例１３では、いずれも設計値との線幅の差が１００μｍを超えており、目視で滲みが見られ、さらに、エッチングレジストの剥離に時間が掛かった。また、比較例では、いずれも銅基材の濡れ指数とインキの表面張力との差が＋３以上であり、目視で滲みが見られた。 In contrast, Comparative Examples 1 to 8 where the pretreatment was performed using a composition containing a surfactant and no phosphoric acid, or a composition containing a metal salt of phosphoric acid and a fatty acid was used. Comparative Examples 9 and 10, Comparative Examples 11 and 12 subjected to pretreatment using a composition containing a surfactant and concentrated sulfuric acid or concentrated hydrochloric acid instead of phosphoric acid, and containing a surfactant containing phosphoric acid In Comparative Example 13 in which pretreatment was performed using a composition having no difference, the difference in the line width from the design value exceeded 100 μm, bleeding was observed visually, and further, it took time to remove the etching resist. It was. In all of the comparative examples, the difference between the wetting index of the copper substrate and the surface tension of the ink was +3 or more, and bleeding was observed visually.

Claims (5)

  1. 　金属基材上に、インキをインクジェット方式により塗工してパターン塗膜を形成するに先立って用いられる金属基材用表面処理剤であって、
    　リン酸と、脂肪酸の金属塩を除く界面活性剤と、水と、を含む組成物からなることを特徴とする金属基材用表面処理剤。     A metal substrate surface treatment agent that is used prior to forming a pattern coating film by applying ink by an inkjet method on a metal substrate,
    A surface treatment agent for a metal substrate comprising a composition containing phosphoric acid, a surfactant excluding a metal salt of a fatty acid, and water.
  2. 　請求項１記載の金属基材用表面処理剤により表面処理した金属基材上に、インキをインクジェット方式により塗工してパターン塗膜を形成することを特徴とするパターン塗膜の形成方法。 A method for forming a pattern coating film, comprising: applying a ink by an inkjet method on a metal substrate surface-treated with the surface treatment agent for a metal substrate according to claim 1.
  3. 　前記金属基材がプリント配線板上に配設されていることを特徴とする請求項２記載のパターン塗膜の形成方法。 3. The pattern coating film forming method according to claim 2, wherein the metal substrate is disposed on a printed wiring board.
  4. 　前記インキが、プリント配線板用レジストインキであることを特徴とする請求項２記載のパターン塗膜の形成方法。 The method for forming a pattern coating film according to claim 2, wherein the ink is a resist ink for a printed wiring board.
  5. 　前記プリント配線板用レジストインキが、ソルダーレジストインキおよびエッチングレジストインキの少なくともいずれか１種であることを特徴とする請求項４記載のパターン塗膜の形成方法。
          5. The method for forming a patterned coating film according to claim 4, wherein the printed wiring board resist ink is at least one of a solder resist ink and an etching resist ink.
PCT/JP2015/073422 2015-01-07 2015-08-20 Surface treatment agent for metal bases WO2016111035A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2016568267A JP6779136B2 (en) 2015-01-07 2015-08-20 Surface treatment agent for metal substrates

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015001744 2015-01-07
JP2015-001744 2015-01-07
JP2015-068418 2015-03-30
JP2015068418 2015-03-30

Publications (1)

Publication Number Publication Date
WO2016111035A1 true WO2016111035A1 (en) 2016-07-14

Family

ID=56355749

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/JP2015/073422 WO2016111035A1 (en) 2015-01-07 2015-08-20 Surface treatment agent for metal bases
PCT/JP2015/073423 WO2016111036A1 (en) 2015-01-07 2015-08-20 Surface treatment agent for metal base

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/073423 WO2016111036A1 (en) 2015-01-07 2015-08-20 Surface treatment agent for metal base

Country Status (2)

Country Link
JP (2) JP6779136B2 (en)
WO (2) WO2016111035A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018116780A1 (en) * 2016-12-22 2018-06-28 三洋化成工業株式会社 Resist substrate preprocessing composition and resist substrate manufacturing method
WO2019082681A1 (en) 2017-10-23 2019-05-02 メック株式会社 Method for producing film formation substrate, film formation substrate, and surface treatment agent

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112020234A (en) * 2019-05-31 2020-12-01 广东高仕电研科技有限公司 Preparation method of PCB and PCB

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04506528A (en) * 1989-05-04 1992-11-12 オリン・コーポレイシヨン Etching solution for metal layers patterned with photoresist
JPH0770767A (en) * 1993-09-01 1995-03-14 Mitsubishi Gas Chem Co Inc Surface treating liquid for copper-clad laminated plate and surface treating method
JP2009532205A (en) * 2006-04-05 2009-09-10 マクダーミッド インコーポレーテッド Method for forming a pattern on a copper surface

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05245974A (en) * 1992-03-03 1993-09-24 Matsushita Electric Works Ltd Laminated sheet
GB9425090D0 (en) * 1994-12-12 1995-02-08 Alpha Metals Ltd Copper coating
US6284309B1 (en) * 1997-12-19 2001-09-04 Atotech Deutschland Gmbh Method of producing copper surfaces for improved bonding, compositions used therein and articles made therefrom
JP3494399B2 (en) * 1998-07-22 2004-02-09 帝国インキ製造株式会社 Thick film print and thick film printing method
US6506314B1 (en) * 2000-07-27 2003-01-14 Atotech Deutschland Gmbh Adhesion of polymeric materials to metal surfaces
US6872321B2 (en) * 2002-09-25 2005-03-29 Lsi Logic Corporation Direct positive image photo-resist transfer of substrate design
JP2004268422A (en) * 2003-03-10 2004-09-30 Yokogawa Electric Corp Printing device for substrate
JP2005290423A (en) * 2004-03-31 2005-10-20 Best Ginning Enterprise Co Ltd Surface adhesion accelerator for copper and copper alloy, and its use method
JP2009299096A (en) * 2008-06-10 2009-12-24 Ebara Densan Ltd Surface treatment solution and surface treatment method of copper and copper alloy for printed circuit board
JP2012012654A (en) * 2010-06-30 2012-01-19 Adeka Corp Surface roughening agent for copper-containing material and method for surface-roughening copper-containing material
JP5219008B1 (en) * 2012-07-24 2013-06-26 メック株式会社 Copper microetching agent, replenisher thereof, and method for manufacturing wiring board

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04506528A (en) * 1989-05-04 1992-11-12 オリン・コーポレイシヨン Etching solution for metal layers patterned with photoresist
JPH0770767A (en) * 1993-09-01 1995-03-14 Mitsubishi Gas Chem Co Inc Surface treating liquid for copper-clad laminated plate and surface treating method
JP2009532205A (en) * 2006-04-05 2009-09-10 マクダーミッド インコーポレーテッド Method for forming a pattern on a copper surface

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018116780A1 (en) * 2016-12-22 2018-06-28 三洋化成工業株式会社 Resist substrate preprocessing composition and resist substrate manufacturing method
KR20190069496A (en) * 2016-12-22 2019-06-19 산요가세이고교 가부시키가이샤 Resist Substrate Pretreatment Composition and Method of Manufacturing Resist Substrate
JPWO2018116780A1 (en) * 2016-12-22 2019-06-24 三洋化成工業株式会社 Resist substrate pretreatment composition and method of manufacturing resist substrate
CN109964546A (en) * 2016-12-22 2019-07-02 三洋化成工业株式会社 The manufacturing method of resist substrate pretreatment compositions and resist substrate
KR102120022B1 (en) 2016-12-22 2020-06-05 산요가세이고교 가부시키가이샤 Resist substrate pretreatment composition and method for manufacturing resist substrate
TWI698413B (en) * 2016-12-22 2020-07-11 日商三洋化成工業股份有限公司 Pretreatment composition of resist substrate and manufacturing method of resist substrate
CN109964546B (en) * 2016-12-22 2021-09-10 三洋化成工业株式会社 Resist substrate pretreatment composition and method for producing resist substrate
WO2019082681A1 (en) 2017-10-23 2019-05-02 メック株式会社 Method for producing film formation substrate, film formation substrate, and surface treatment agent
JPWO2019082681A1 (en) * 2017-10-23 2020-04-16 メック株式会社 Method for producing film-forming substrate, film-forming substrate and surface treatment agent
KR20200076684A (en) 2017-10-23 2020-06-29 멕크 가부시키가이샤 Method for manufacturing film-forming substrate, film-forming substrate and surface treatment agent
EP3702049A4 (en) * 2017-10-23 2021-08-11 Mec Company., Ltd. Method for producing film formation substrate, film formation substrate, and surface treatment agent

Also Published As

Publication number Publication date
JP6779136B2 (en) 2020-11-04
JP6578304B2 (en) 2019-09-18
JPWO2016111035A1 (en) 2017-11-02
JPWO2016111036A1 (en) 2017-10-19
WO2016111036A1 (en) 2016-07-14

Similar Documents

Publication Publication Date Title
JP5731746B2 (en) Improved hot melt composition
DE69826456T2 (en) AQUEOUS URETHANE ACRYLATE PHOTORESIS
DE60305333T2 (en) PRESSURE PROCESS AND SOLDERING MASK COLOR COMPOSITION
JP4936725B2 (en) Photocurable / thermosetting composition for inkjet and printed wiring board using the same
JP5860096B2 (en) Curable composition for inkjet and method for producing electronic component
DE60307485T2 (en) METHOD AND INK FOR PRODUCING ELECTRONIC COMPONENTS
WO2013146706A1 (en) Photo-curable thermosetting composition, method of manufacturing cured product thereof, cured product, and printed circuit board having same
DE112009000690T5 (en) Inkjet ink composition for etch resists
JP6578304B2 (en) Surface treatment agent for metal substrates
JP6577712B2 (en) Image formation of three-dimensional substrate using transfer film
WO2012039372A1 (en) Curable composition for inkjet and method for producing electronic component
JP5965642B2 (en) Curable composition for inkjet and method for producing electronic component
JP6324788B2 (en) Forming method of coating film
US20080308003A1 (en) UV inkjet resist
JP6209690B1 (en) Curable composition for inkjet, cured product, and printed wiring board
JP6524579B2 (en) UV curable composition for inkjet etching resist
JP2012216588A (en) Solder resist layer, formation method of the same, print circuit board having solder resist layers, manufacturing method of the same and print circuit board manufactured by using the method
JP6066559B2 (en) Curable composition for inkjet and method for producing electronic component
JP2014055288A (en) Curable composition for ink-jet and method for producing electronic component
JPH05255631A (en) Ultraviolet-curable ink composition, formation of cured coating films and use of ultraviolet-curable ink composition
JP2004139754A (en) Silver oxide paste and manufacturing method of metal silver from silver oxide paste
JP2023116288A (en) Manufacturing method of printed wiring board, printed wiring board and ink jet solder resist composition
JPH05194902A (en) Resist ink composition and formation of solder resist film by using the same
JP2008111104A (en) Printing ink, method for producing coating film using the ink, and method for forming electrode pattern by using the method

Legal Events

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

Ref document number: 15876908

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016568267

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15876908

Country of ref document: EP

Kind code of ref document: A1