WO2026014192A1 - Encre pour jet d'encre réticulable par rayonnement d'énergie active et procédé d'impression à jet d'encre - Google Patents

Encre pour jet d'encre réticulable par rayonnement d'énergie active et procédé d'impression à jet d'encre

Info

Publication number
WO2026014192A1
WO2026014192A1 PCT/JP2025/022171 JP2025022171W WO2026014192A1 WO 2026014192 A1 WO2026014192 A1 WO 2026014192A1 JP 2025022171 W JP2025022171 W JP 2025022171W WO 2026014192 A1 WO2026014192 A1 WO 2026014192A1
Authority
WO
WIPO (PCT)
Prior art keywords
ink
monomer
meth
curable inkjet
inkjet ink
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
PCT/JP2025/022171
Other languages
English (en)
Japanese (ja)
Inventor
雅士 宮野
亮 青山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
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 Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of WO2026014192A1 publication Critical patent/WO2026014192A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • 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
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • 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
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

  • This disclosure relates to an actinic radiation-curable inkjet ink and an inkjet recording method.
  • this disclosure relates to an actinic radiation-curable inkjet ink that simultaneously satisfies etching resistance and strippability, and also has excellent plating resistance, ejection stability, and recyclability.
  • etching resists solder resists and markings on printed circuit boards.
  • a method for producing a printed circuit board using an inkjet printer involves drawing a conductor circuit pattern on a copper-clad laminate for a printed wiring board using an inkjet printer, thereby forming an etching resist, and then performing an etching process.
  • This method significantly reduces the number of steps and labor compared to photolithography, which requires a photomask, or screen printing, which requires a screen and uses resist ink or marking ink. It also reduces the amount of consumables, such as developers, various inks, and cleaning solvents, and reduces wastewater, which is expected to contribute to a cleaner environment.
  • Patent Documents 1 and 2 describe actinic radiation-curable inkjet inks containing N-acryloyloxyethylhexahydrophthalimide as the polymerizable monomer. Although these inks improve inkjet ejection stability and etching resistance, they are not intended for use in peeling off the formed cured film, and therefore there is no mention whatsoever of the peelability of the cured film, failing to simultaneously satisfy both etching resistance and peelability. Furthermore, for example, Patent Document 3 discloses an ink containing a monomer having an alicyclic structure.
  • the document relates to a resist resin composition for non-inkjet printing, the structure is completely different from that of the present disclosure, and the inkjet ejection performance was insufficient.
  • the problem to be solved by this disclosure is to provide an actinic radiation-curable inkjet ink and inkjet recording method that simultaneously satisfies etching resistance and strippability, and also has excellent plating resistance, ejection stability, and recyclability.
  • the present inventors have investigated the causes of the above problems in order to solve them. As a result, they have found that by using a (meth)acrylate monomer having a cyclic imide group in combination with a polymerizable monomer having an alicyclic structure and specifying the mass ratio of these monomers, etching resistance and strippability can be simultaneously satisfied. Furthermore, they have found that the resulting composition also has excellent plating resistance, injection stability, and recyclability. That is, the above-mentioned problems related to the present disclosure are solved by the following means.
  • An actinic energy ray-curable inkjet ink that is cured by actinic energy rays,
  • the composition contains a (meth)acrylate monomer having a cyclic imide group and a polymerizable monomer having an alicyclic structure, an actinic ray-curable inkjet ink, wherein the mass ratio (% by mass) of the content of the (meth)acrylate monomer having a cyclic imide group to the content (% by mass) of the polymerizable monomer having an alicyclic structure ((meth)acrylate monomer having a cyclic imide group/polymerizable monomer having an alicyclic structure) is within a range of 0.25 to 8.00.
  • An inkjet recording method comprising ejecting an actinic ray-curable inkjet ink onto a substrate and curing the ink with actinic rays, 15. An inkjet recording method using the actinic ray-curable inkjet ink according to any one of items 1 to 14 as the actinic ray-curable inkjet ink.
  • the above-described means of the present disclosure can provide an actinic radiation-curable inkjet ink and inkjet recording method that can simultaneously satisfy etching resistance and releasability, and that are also excellent in plating resistance, ejection stability, and recyclability.
  • the present disclosure provides excellent releasability against solvents.
  • the mechanism by which the effects of the present disclosure are manifested or acted upon is not clear, but is speculated as follows. Conventionally, to improve etching resistance, it is necessary to improve adhesion between the ink and the substrate, which is the printing medium. However, excessive adhesion leads to a problem of reduced releasability.
  • the durability of the coating film can be increased and plating resistance can be improved at the same time. If the mass ratio of the (meth)acrylate monomer having a cyclic imide group is too low, durability will be insufficient and plating resistance will not be obtained, while if the mass ratio is too high, it will be impossible to achieve both removability and plating resistance. Furthermore, the physical properties of viscosity and surface tension of the (meth)acrylate monomer having a cyclic imide group are suitable for inkjet ejection at an ejection temperature of 60° C. or higher, and therefore inkjet ejection stability is also improved. Furthermore, since the ink components can be efficiently separated from the substrate while maintaining the durability of the coating film, deinking is easy and recycling is improved.
  • FIG. 1 is a diagram illustrating a manufacturing process for a printed circuit board when an ink according to the present disclosure is used to form an etching resist.
  • 1 is a diagram illustrating a manufacturing process for a printed circuit board when an ink according to the present disclosure is used to form an etching resist.
  • FIG. 1 is a diagram illustrating a manufacturing process for a printed circuit board when the ink of the present disclosure is used to form an etching resist.
  • 1 is a diagram illustrating a manufacturing process for a printed circuit board when an ink according to the present disclosure is used to form an etching resist.
  • 1 is a diagram illustrating a manufacturing process for a printed circuit board when the ink of the present disclosure is used to form a plating resist.
  • 1 is a diagram illustrating a manufacturing process for a printed circuit board when the ink of the present disclosure is used to form a plating resist.
  • 1 is a diagram illustrating a manufacturing process for a printed circuit board when the ink of the present disclosure is used to form a plating resist.
  • 1 is a diagram illustrating a manufacturing process for a printed circuit board when the ink of the present disclosure is used to form a plating resist.
  • the active energy ray-curable inkjet ink of the present disclosure contains a (meth)acrylate monomer having a cyclic imide group and a polymerizable monomer having an alicyclic structure, and the mass ratio (% by mass) of the content of the (meth)acrylate monomer having a cyclic imide group to the content (% by mass) of the polymerizable monomer having an alicyclic structure ((meth)acrylate monomer having a cyclic imide group/polymerizable monomer having an alicyclic structure) is within a range of 0.25 to 8.00.
  • This feature is a technical feature common to or corresponding to each of the following embodiments.
  • the total content of the (meth)acrylate monomer having a cyclic imide group and the polymerizable monomer having an alicyclic structure is preferably 30% by mass or more relative to the total ink. This allows the (meth)acrylate monomer having a cyclic imide group and the polymerizable monomer having an alicyclic structure to be contained in an appropriate blend ratio, simultaneously achieving etching resistance and strippability, and providing excellent plating resistance, recyclability, and injection stability.
  • the content of the (meth)acrylate monomer having a cyclic imide group is greater than 30% by mass of the total ink. This allows the ink to simultaneously satisfy etching resistance and strippability, and to have excellent plating resistance, recyclability, and ejection stability.
  • the (meth)acrylate monomer having a cyclic imide group is N-acryloyloxyethylhexahydrophthalimide, as this further improves etching resistance and plating resistance.
  • the polymerizable monomer having an alicyclic structure contains a monofunctional monomer with a molecular weight in the range of 200 to 300, as this improves solvent strippability from the standpoint of compatibility with the solvent, and improves jettisonability from the standpoint of volatility.
  • the ink of the present disclosure preferably contains an aromatic monomer in terms of plating resistance and solvent removability.
  • the aromatic monomer it is preferable for the aromatic monomer to contain a monomer with a molecular weight in the range of 200 to 300, as this improves solvent removability from the standpoint of compatibility with the solvent.
  • Containing a monomer having an acrylamide group is preferable from the viewpoint of plating resistance.
  • containing acryloylmorpholine as the monomer having an acrylamide group is even more preferable from the viewpoint of plating resistance and etching resistance.
  • the ink of the present disclosure preferably contains a polyfunctional monomer, as this further improves recyclability, etching resistance, and plating resistance. Furthermore, the ink of the present disclosure preferably contains a dye, as this further improves etching resistance and plating resistance. Furthermore, the ink of the present disclosure preferably contains a gelling agent, which further improves etching resistance. The gelling agent also enables ink droplets that land on a recording medium to be pinned, preventing the droplets from coalescing, thereby enabling the formation of high-resolution images.
  • the ink of the present disclosure is suitably used as an etching resist or a plating resist.
  • the inkjet ink recording method of the present disclosure is an inkjet recording method in which an actinic ray-curable inkjet ink is ejected onto a substrate and cured by actinic rays, and the actinic ray-curable inkjet ink of the present disclosure described above is used as the inkjet curable composition.
  • This makes it possible to simultaneously satisfy etching resistance and plating resistance in terms of substrate adhesion, as well as releasability, and also provides excellent ejection stability and recyclability.
  • the actinic ray-curable inkjet ink of the present disclosure is an actinic ray-curable inkjet ink that is cured by actinic ray, and contains a (meth)acrylate monomer having a cyclic imide group and a polymerizable monomer having an alicyclic structure, and the mass ratio of the content (mass %) of the (meth)acrylate monomer having a cyclic imide group to the content (mass %) of the polymerizable monomer having an alicyclic structure ((meth)acrylate monomer having a cyclic imide group/polymerizable monomer having an alicyclic structure) is within the range of 0.25 to 8.00.
  • the total content of the (meth)acrylate monomer having a cyclic imide group and the polymerizable monomer having an alicyclic structure is 30 mass % or more with respect to the total ink. Furthermore, it is preferable that the content of the (meth)acrylate monomer having a cyclic imide group is more than 30 mass % with respect to the total ink.
  • active energy ray-curable inkjet ink refers to an inkjet ink that is cured by irradiation with active energy rays. In this specification, it is also simply referred to as "ink.”
  • active energy rays refers to radiation that acts physically and chemically on a polymerization initiator or a polymerizable compound to promote a crosslinking reaction and a polymerization reaction.
  • Specific examples of active energy rays include visible light, ultraviolet light, X-rays, electron beams, ⁇ -rays, ⁇ -rays, and ⁇ -rays.
  • (meth)acrylate is a general term for "acrylate” and "methacrylate” and means either or both of them.
  • the ink of the present disclosure may contain, as necessary, a polymerization initiator, an aromatic monomer, a monomer having an acrylamide group, a polyfunctional monomer, a dye, or a gelling agent.
  • a polymerization initiator an aromatic monomer
  • a monomer having an acrylamide group a monomer having an acrylamide group
  • a polyfunctional monomer a dye, or a gelling agent.
  • Examples of the (meth)acrylate monomer having a cyclic imide group include a monomer having a structure represented by the following general formula (1) and a monomer having a structure represented by the following general formula (2).
  • R represents a hydrogen atom or a methyl group.
  • An example of the compound of general formula (1) in which R is a hydrogen atom is N-acryloyloxyethylhexahydrophthalimide.
  • Commercially available N-acryloyloxyethylhexahydrophthalimide products include, for example, Aronix M-140 (manufactured by Toagosei Co., Ltd.) and Miramer M1088 (manufactured by Miwon Co., Ltd.).
  • the content of the (meth)acrylate monomer having a cyclic imide group is preferably within a range of 10 to 60% by mass, more preferably within a range of 20 to 55% by mass, based on the total mass of the ink, and particularly preferably greater than 30% by mass.
  • the ink has good etching resistance, and at the same time, solvent strippability, plating resistance, and recyclability, and has ink physical properties that allow it to be ejected by inkjet printing.
  • a polymerizable monomer having an alicyclic structure is also called an alicyclic monomer.
  • the alicyclic monomer may be a monofunctional monomer (alicyclic monofunctional monomer) or a polyfunctional monomer having an alicyclic structure (alicyclic polyfunctional monomer), but is preferably an alicyclic monofunctional monomer.
  • the alicyclic monomer is preferably an alicyclic monofunctional monomer having a molecular weight in the range of 200 to 300.
  • the alicyclic monomer is preferably an alicyclic (meth)acrylate monomer.
  • the amount to be added is calculated as a (meth)acrylate having a cyclic imide group, not as an alicyclic monomer.
  • alicyclic monofunctional monomers include isobornyl acrylate, 3,5,5-trimethylcyclohexyl acrylate, 4-tert-butylcyclohexyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, etc. These alicyclic monofunctional monomers are preferred in that they have excellent dilution properties and improve the tack-free properties of the resulting cured coating.
  • Examples of the alicyclic polyfunctional monomer include cyclohexanedimethanol di(meth)acrylate, tricyclodecane dimethanol diacrylate, etc. These alicyclic polyfunctional monomers are preferred in terms of improving the strength of the cured coating.
  • Examples of commercially available alicyclic monomers include Miramer M1130 (manufactured by Miwon), Miramer M1140 (manufactured by Miwon), FA-512AS (manufactured by Resonac), FA-511AS (manufactured by Resonac), and FA-513AS (manufactured by Resonac).
  • the content of the alicyclic monofunctional monomer and the alicyclic polyfunctional monomer is preferably within a range of 10 to 50% by mass with respect to the total mass of the ink.
  • the mass ratio ((meth)acrylate monomer having a cyclic imide group/alicyclic monomer) of the content (mass%) of the (meth)acrylate monomer having a cyclic imide group to the content (mass%) of the alicyclic monomer is within the range of 0.25 to 8.00. It is preferable that this mass ratio is within the range of 1.00 to 5.00.
  • the total content of the (meth)acrylate monomer having a cyclic imide group and the alicyclic monomer is preferably 30% by mass or more based on the total ink. This total content is preferably within the range of 35 to 90% by mass, and more preferably 40 to 70% by mass, based on the total ink.
  • the polymerization initiator is preferably a radical polymerization initiator.
  • radical polymerization initiators include intramolecular cleavage-type photopolymerization initiators and hydrogen abstraction-type polymerization initiators.
  • a hydrogen abstraction type polymerization initiator By using a hydrogen abstraction type polymerization initiator, gradual crosslinking of polymer chains due to hydrogen abstraction proceeds in the formed coating film, and etching resistance and plating resistance can be improved without deteriorating releasability.
  • the ink may contain only one type of photopolymerization initiator, or may contain two or more types in combination.
  • intramolecular cleavage-type photopolymerization initiators include acetophenone-based initiators such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzil dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino(4-methylthiophenyl)propan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone; benzoin-based initiators such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; and acylphosphine oxide-based initiators such as 2,4,6-trimethylbenzoindiphenylphosphine oxide and bis(2,4,6-trimethylbenzoin)phenylphosphine oxide.
  • acetophenone-based initiators such as 2-hydroxy-2-methyl-1-
  • intramolecular cleavage-type photopolymerization initiators include Omnirad 127, Omnirad 184, Omnirad 651, Omnirad 2959, Omnirad 819, Omnirad 907, Esacure One (manufactured by IGM Resins), and SPEEDCURE 73 (manufactured by Sartomer).
  • hydrogen abstraction photopolymerization initiators include benzophenone-based initiators such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 3,3'-dimethyl-4-methoxybenzophenone, as well as thioxanthone-based initiators such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and high molecular weight thioxanthone.
  • benzophenone-based initiators such as benzophenone, methyl o-benzoylbenzoate
  • hydrogen abstraction photoinitiators include SpeedCure 2-ITX, SpeedCure 7010, and SpeedCure BP.
  • the content of the polymerization initiator is preferably within the range of 1 to 10% by mass, and more preferably within the range of 1.5 to 8% by mass, of the total ink.
  • the content of the hydrogen abstraction type photopolymerization initiator is preferably within the range of 0 to 5% by mass, and even more preferably within the range of 2 to 4.5% by mass, of the total ink.
  • the aromatic monomer is a monomer having an aromatic ring, and preferably has a molecular weight in the range of 200 to 300.
  • aromatic monomers include 2-phenoxyethyl (meth)acrylate, bisphenol A diacrylate, o-phenylphenoxyethyl (meth)acrylate, and m-phenoxybenzyl (meth)acrylate.
  • aromatic monomers include ethoxylated phenoxy (meth)acrylate, alkoxylated phenol (meth)acrylate, and 2-hydroxy-o-phenylphenolpropyl (meth)acrylate.
  • Examples of commercially available aromatic monomers include Miramer M1182 (manufactured by Miwon), Miramer M142 (manufactured by Miwon), Miramer M1142 (manufactured by Miwon), and SR339NS (manufactured by Sartomer).
  • the ink does not necessarily contain an aromatic monomer, and the content of the aromatic monomer is preferably within the range of 0 to 40% by mass relative to the total mass of the ink.
  • ⁇ Monomers having an acrylamide group examples include N,N-dimethylacrylamide, N-hydroxyethylacrylamide, acryloylmorpholine, N,N-diethylacrylamide, N-isopropylacrylamide, and diacetone acrylamide.
  • Commercially available monomers having an acrylamide group include, for example, DMAA, HEAA, ACMO, DEAA, NIPAM, and DAAM manufactured by KJ Chemicals.
  • the ink does not necessarily contain a monomer having an acrylamide group, and the content of the monomer having an acrylamide group is preferably in the range of 0 to 30% by mass, and more preferably in the range of 5 to 25% by mass, based on the total mass of the ink.
  • the polyfunctional monomer may be any monomer having two or more functional groups in the molecule.
  • the polyfunctional monomer is preferably a bifunctional or trifunctional or higher functional (meth)acrylate monomer.
  • the polyfunctional monomer may be the above-mentioned polyfunctional polymerizable monomer having an acidic group or the above-mentioned alicyclic polyfunctional monomer.
  • bifunctional (meth)acrylate monomers include triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, bisphenol A PO adduct di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate.
  • trifunctional or higher (meth)acrylate monomers include tricyclodecane dimethanol diacrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin propoxy tri(meth)acrylate, and pentaerythritol ethoxy tetra(meth)acrylate.
  • the (meth)acrylate monomer may be modified.
  • the modified product include ethylene oxide-modified (meth)acrylate compounds such as ethylene oxide-modified trimethylolpropane tri(meth)acrylate and ethylene oxide-modified pentaerythritol tetraacrylate.
  • the modified product include caprolactone-modified (meth)acrylate compounds such as caprolactone-modified trimethylolpropane tri(meth)acrylate.
  • examples of the modified product include caprolactam-modified (meth)acrylate compounds such as caprolactam-modified dipentaerythritol hexa(meth)acrylate. These may be used alone or in combination of two or more.
  • the polyfunctional monomer examples include M222 (bifunctional acrylate monomer having a propylene oxide skeleton, manufactured by Miwon), M210 (bifunctional acrylate monomer, neopentyl glycol hydroxypivalate diacrylate, manufactured by Miwon), A-DOG (dioxane glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 326), A-DCP (tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 304), SR444 (trifunctional acrylate monomer, manufactured by Sartomer), and M262 (bifunctional acrylate monomer having a cyclic structure, manufactured by Miwon).
  • M222 bifunctional acrylate monomer having a propylene oxide skeleton, manufactured by Miwon
  • M210 bifunctional acrylate monomer, neopentyl glycol hydroxypivalate diacrylate, manufactured by
  • the ink does not necessarily contain a polyfunctional monomer, but the content of the polyfunctional monomer is preferably within the range of 0 to 30% by mass of the total ink in terms of the hardness of the coating film, and more preferably within the range of 2 to 30% by mass.
  • the ink of the present disclosure may contain other monomers in addition to the above-mentioned monomers.
  • the other monomers include (meth)acrylates such as caprolactone (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, tetrahydrofurfuryl acrylate, and stearyl (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate.
  • monomers having an ethylene glycol moiety are particularly preferred.
  • Examples of commercially available products of the other monomers include Miramer M1110 (manufactured by Miwon Co., Ltd.), Miramer M150 (manufactured by Miwon Co., Ltd.), and SR551 (manufactured by Sartomer Co., Ltd.) Compounds having an ethylene oxide moiety are particularly preferred.
  • the inks of the present disclosure may optionally contain a colorant.
  • the colorant may be a dye or a pigment, but a dye is preferred because it has excellent etching resistance and plating resistance.
  • a dye By including a dye in the ink, the ink colored by the dye is cured to form a coating film, and the resist pattern becomes clear.
  • the dye is not particularly limited, but it is preferable to include at least one dye selected from the group consisting of dyes having an anthraquinone skeleton and an amino group, dyes having a naphthalene skeleton and an amino group, and dyes having a phthalocyanine skeleton. These dyes are preferred because they have a relatively rigid skeleton and are therefore highly effective in preventing color fading.
  • dyes having an anthraquinone skeleton and an amino group include Solvent Red 122 and Solvent Blue 35.
  • dyes having a naphthalene skeleton and an amino group include Solvent Blue 5 and Basic Blue 7.
  • An example of a dye having a phthalocyanine skeleton is Direct Blue 87.
  • the dye content is preferably within the range of 0.01 to 3 mass% of the total ink, more preferably 0.03 to 2 mass%, and even more preferably 0.05 to 1.5 mass%. A dye content within this range will result in a well-colored cured film and improved etching resistance.
  • the dye may be a dye other than a dye having an anthraquinone skeleton and an amino group, a dye having a naphthalene skeleton and an amino group, a dye having a triarylmethane structure, or a dye having a phthalocyanine skeleton.
  • the dye having an anthraquinone skeleton and an amino group, a dye having a naphthalene skeleton and an amino group, or a dye having a phthalocyanine skeleton is contained in a greater amount than the other dyes.
  • One type of dye may be used alone, or multiple types may be used in combination.
  • the gelling agent can gel ink droplets that have landed on the oxide film and temporarily fix them (pin them). When the ink is pinned in a gel state, the ink is prevented from wetting and spreading, making it difficult for adjacent dots to coalesce, allowing for the formation of images with higher resolution.
  • the ink of the present disclosure may contain only one type of gelling agent, or two or more types.
  • gelling agents examples include dialkyl ketones, fatty acid esters, fatty acid amides, oil gelling agents, etc., but it is preferable that the gelling agents used in this disclosure do not have acidic groups such as -OH or -COOH at the end of the alkyl chain.
  • a gelling agent without acidic groups does not necessarily mean a 100% pure gelling agent that is composed only of those without acidic groups, but also includes cases where gelling agents with acidic groups are contained as impurities to the extent that the intended effects of the present invention are not impaired, and it is sufficient that the acid value is 10 mgKOH/g or less.
  • Particularly preferred gelling agents include at least one compound selected from compounds having structures represented by the following general formulas (G1) and (G2).
  • General formula (G2): R 3 -COO-R 4 [In the formula, R 1 to R 4 each independently represent an alkyl chain having 12 or more carbon atoms and a linear portion, which may be branched.]
  • the ketone wax represented by the general formula (G1) or the ester wax represented by the general formula (G2) has a linear or branched hydrocarbon group (alkyl chain) with 12 or more carbon atoms. This increases the crystallinity of the gelling agent and creates more space in the house-of-card structure described below. As a result, ink media such as solvents and photopolymerizable compounds are more easily encapsulated in the space, improving the pinning ability of the ink. Furthermore, the number of carbon atoms in the linear or branched hydrocarbon group (alkyl chain) is preferably 26 or less.
  • R 1 and R 2 or R 3 and R 4 are linear hydrocarbon groups having 12 to 23 carbon atoms.
  • R1 or R2 , or either R3 or R4 is a saturated hydrocarbon group having from 12 to 23 carbon atoms.
  • both R 1 and R 2 , or both R 3 and R 4 are saturated hydrocarbon groups having 11 or more but less than 23 carbon atoms.
  • ketone waxes represented by the above general formula (G1) include dilignoceryl ketone (C24-C24), dibehenyl ketone (C22-C22), distearyl ketone (C18-C18), dieicosyl ketone (C20-C20), dipalmityl ketone (C16-C16), dimyristyl ketone (C14-C14), dilauryl ketone (C12-C12), and lauryl myristyl ketone.
  • dilignoceryl ketone C24-C24
  • dibehenyl ketone C22-C22
  • distearyl ketone C18-C18
  • dieicosyl ketone C20-C20
  • dipalmityl ketone C16-C16
  • dimyristyl ketone C14-C14
  • dilauryl ketone C12-C12
  • lauryl myristyl ketone lauryl my
  • C12-C14 lauryl palmityl ketone (C12-C16), myristyl palmityl ketone (C14-C16), myristyl stearyl ketone (C14-C18), myristyl behenyl ketone (C14-C22), palmityl stearyl ketone (C16-C18), palmityl behenyl ketone (C16-C22), and stearyl behenyl ketone (C18-C22).
  • the number of carbon atoms in the parentheses indicates the number of carbon atoms in each of the two hydrocarbon groups separated by the carbonyl group.
  • ketone waxes represented by general formula (G1) include Stearonne (manufactured by Alfa Aeser; Stearon), 18-Pentatriacontanon (manufactured by Alfa Aeser), Hentriacontan-16-on (manufactured by Alfa Aeser), and Kaowax T-1 (manufactured by Kao Corporation).
  • fatty acids or ester waxes represented by general formula (G2) include behenyl behenate (C21-C22), icosanoic acid icosyl (C19-C20), stearyl stearate (C17-C18), palmityl stearate (C17-C16), lauryl stearate (C17-C12), cetyl palmitate (C15-C16), and stearyl palmitate (C15-C1 8), myristyl myristate (C13-C14), cetyl myristate (C13-C16), octyldodecyl myristate (C13-C20), stearyl oleate (C17-C18), stearyl erucate (C21-C18), stearyl linoleate (C17-C18), behenyl oleate (C18-C22), and arachidyl linoleate (C17-C20).
  • ester waxes represented by general formula (G2) include Unistar M-2222SL and Sperm Acetate, manufactured by NOF Corporation ("Unistar” is a registered trademark of the company), and Exseparl SS and Exseparl MY-M, manufactured by Kao Corporation (“Exseparl” is a registered trademark of the company).
  • ester waxes include EMALEX CC-18 and EMALEX CC-10, manufactured by Nippon Emulsion Co., Ltd. (“EMALEX” is a registered trademark of the company), and Amreps PC, manufactured by Kokyu Alcohol Kogyo Co., Ltd. (“Amreps” is a registered trademark of the company).
  • gelling agents are often mixtures of two or more types, and therefore may be separated and purified as necessary before being incorporated into the ink.
  • these gelling agents ketone wax, ester wax, higher fatty acid, higher alcohol, and fatty acid amide are preferred from the viewpoint of further enhancing pinning properties.
  • the gelling agent content is preferably within the range of 0.5 to 5.0% by mass relative to the total mass of the ink. By keeping the gelling agent content within this range, excellent etching resistance and plating resistance are achieved, and the gelling agent's solubility in solvent components and pinning effect are improved. From the above perspective, it is even more preferable that the gelling agent content in the inkjet ink be within the range of 0.5 to 2.5% by mass.
  • the gelling agent crystallizes in the ink at a temperature below the gelling temperature of the ink.
  • the gelling temperature is the temperature at which the gelling agent undergoes a phase transition from sol to gel when ink that has been solated or liquefied by heating is cooled, causing a sudden change in the viscosity of the ink.
  • the solated or liquefied ink is cooled while its viscosity is measured using a viscoelasticity measuring device (e.g., MCR300, manufactured by Physica), and the temperature at which the viscosity suddenly increases can be determined to be the gelling temperature of the ink.
  • a structure may be formed in which the ink medium, such as the solvent and the photopolymerizable compound, is enclosed in the three-dimensional space formed by the gelling agent crystallized into plates.
  • This structure is hereinafter referred to as a "house of cards structure.”
  • the liquid ink medium is retained within the space, making it more difficult for the ink droplets to spread, and improving the ink pinning ability.
  • the ink pinning ability is improved, ink droplets that land on the recording medium are less likely to coalesce, making it possible to form higher-resolution images.
  • the ink medium such as the solvent in the ink, the photopolymerizable compound, and the gelling agent are compatible with each other.
  • the ink medium such as the solvent in the ink, the photopolymerizable compound, and the gelling agent are phase-separated, it may be difficult to form a house-of-cards structure.
  • the ink of the present disclosure may further contain other components, including a polymerization inhibitor and a surfactant, as long as the effects of the present disclosure are obtained. Only one type of these components may be contained in the ink of the present disclosure, or two or more types may be contained.
  • polymerization inhibitor examples include (alkyl)phenols, hydroquinone, catechol, resorcinol, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone, nitrosobenzene, 2,5-di-t-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cupferron, aluminum N-nitrosophenylhydroxyamine, tri-p-nitrophenylmethyl, N-(3-oxyanilino-1,3-dimethylbutylidene)aniline oxide, dibutyl cresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxime, and
  • the amount of polymerization inhibitor can be set as desired as long as the effects of the present disclosure are achieved.
  • the amount of polymerization inhibitor can be, for example, 0.001% by mass or more and less than 1.0% by mass of the total ink.
  • surfactant examples include anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates, and fatty acid salts; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, and polyoxyethylene-polyoxypropylene block copolymers; cationic surfactants such as alkylamine salts and quaternary ammonium salts; and silicone-based and fluorine-based surfactants.
  • anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates, and fatty acid salts
  • nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, and polyoxyethylene-polyoxypropylene block copolymers
  • cationic surfactants
  • silicone surfactants include polyether-modified polysiloxane compounds.
  • polyether-modified polysiloxane compounds include Tego Rad 2250, manufactured by Evonik; KF-351A, KF-352A, KF-642, and X-22-4272, manufactured by Shin-Etsu Chemical Co., Ltd.; BYK 307, BYK 345, BYK 347, and BYK 348, manufactured by BYK ("BYK" is a registered trademark of the company); and TSF 4452, manufactured by Momentive Performance Materials.
  • the fluorine-based surfactant refers to a surfactant in which some or all of the hydrogen atoms bonded to the carbon atoms of the hydrophobic group in a normal surfactant are substituted with fluorine.
  • fluorine-based surfactants include Megafac F manufactured by DIC Corporation ("Megafac” is a registered trademark of DIC), Surflon manufactured by AGC Sei Chemical Co., Ltd. ("Surflon” is a registered trademark of AGC Sei Chemical Co., Ltd.), Fluorad FC manufactured by 3M Corporation (“Fluorad” is a registered trademark of 3M), Monflor manufactured by Imperial Chemical Industries, Ltd., Zonyls manufactured by E.I. duPont Nemelas and Company, Licowet VPF manufactured by Lubewerke-Hoechst, and FTERGENT manufactured by Neos Corporation (“FTERGENT” is a registered trademark of 3M).
  • the amount of surfactant can be set as desired as long as the effects of the present disclosure are achieved.
  • the amount of surfactant can be, for example, 0.001% by mass or more and less than 1.0% by mass of the total ink.
  • the ink of the present disclosure contains a gelling agent, it preferably has a phase transition point in the range of 40° C. or higher and lower than 100° C. If the phase transition point is 40° C. or higher, the ink quickly gels after landing on a recording medium, thereby improving pinning properties. Furthermore, if the phase transition point is lower than 100° C., the ink is easy to handle and has high ejection stability. From the viewpoint of enabling the ink to be ejected at a lower temperature and reducing the load on the image forming apparatus, it is more preferable that the phase transition point of the ink of the present disclosure be within the range of 40 to 60°C.
  • the viscosity and phase transition point of the ink of the present disclosure at 40 to 90° C. can be determined by measuring the temperature change of the dynamic viscoelasticity of the ink using a rheometer.
  • these viscosities and phase transition points are values obtained by the following method.
  • the ink of the present disclosure is heated to 100°C, and while measuring the viscosity using a Physica MCR301 (manufactured by Anton Paar) at a shear rate of 1000 (1/s), the ink is cooled to 20°C under conditions of a shear rate of 11.7 (1/s) and a temperature decrease rate of 0.1°C/s, to obtain a temperature change curve of the viscosity.
  • the viscosity at 40 to 90° C. can be determined by reading the viscosity at 40 to 90° C. on the temperature change curve of viscosity.
  • the phase transition point can be determined as the temperature at which the viscosity becomes 200 mPa s on the temperature change curve of viscosity.
  • the ink of the present disclosure can be used to form insulating films, protective films, etching resists, and plating resists in various fields, such as metal processing, electronic circuits, printed circuit boards, plate making, semiconductors, and color filters.
  • the ink of the present disclosure is preferably used for etching resists or plating resists, and is particularly preferably used for plating resists because of its good stripping properties with a stripping solution containing an organic solvent.
  • Aqueous stripping solutions containing an organic solvent are even more preferred as stripping solutions.
  • the ink preferably has a configuration in which the cured film formed can be removed with a stripper containing water, or with NMP (N-methyl-2-pyrrolidone), MEK (methyl ethyl ketone), toluene, dichloromethane, carbon tetrachloride, etc.
  • NMP N-methyl-2-pyrrolidone
  • MEK methyl ethyl ketone
  • toluene dichloromethane
  • dichloromethane carbon tetrachloride
  • the ink must have a configuration in which the cured film formed can be removed with an organic solvent or a stripper containing an organic solvent, etc.
  • the inkjet recording method of the present disclosure is an inkjet recording method in which an actinic ray-curable inkjet ink is ejected onto a substrate and cured by actinic rays, and the actinic ray-curable inkjet ink of the present disclosure described above is used as the inkjet curable composition.
  • the inkjet recording method of the present disclosure is an inkjet recording method in which an actinic ray-curable inkjet ink is ejected onto a substrate and cured by actinic rays, and the actinic ray-curable inkjet ink of the present disclosure described above is used as the inkjet curable composition.
  • the inkjet recording method preferably includes: (1) a step of ejecting the ink of the present disclosure from a nozzle of an inkjet head and causing it to land on an oxide film on a substrate; and (2) a step of irradiating the ink that has landed on the oxide film with actinic light rays to cure the ink.
  • a method for producing a printed circuit board will be described using an example in which the ink of the present disclosure is used to form an etching resist.
  • 1 to 4 are diagrams illustrating the manufacturing process of a printed circuit board when the ink of the present disclosure is used to form an etching resist.
  • a conductive oxide film 2 is formed on a substrate 1, which is a recording medium.
  • Droplets of ink are ejected from an inkjet head 5 onto the oxide film 2 shown in Fig. 1 and landed at positions corresponding to the etching resist film 3 to be formed, thereby patterning the oxide film 2 (see Fig. 2).
  • the ejection method from the inkjet head may be either an on-demand method or a continuous method.
  • the on-demand inkjet head may be of any of the following types: electromechanical conversion type, such as single cavity type, double cavity type, bender type, piston type, shear mode type, and shared wall type; and electrothermal conversion type, such as thermal inkjet type and Bubble Jet (registered trademark) type. Bubble Jet is a registered trademark of Canon Inc.
  • Ejection stability can be improved by ejecting ink droplets from the inkjet head in a heated state.
  • the temperature of the ink when ejected is preferably in the range of 40 to 100°C, and more preferably in the range of 60 to 90°C to further improve ejection stability.
  • the temperature of the ink when filled into the inkjet head be set to between (gelation temperature + 10)°C and (gelation temperature + 30)°C. If the temperature of the ink inside the inkjet head is below (gelation temperature + 10)°C, the ink will gel inside the inkjet head or on the nozzle surface, which will likely reduce the ejection properties of the ink. On the other hand, if the temperature of the ink inside the inkjet head exceeds (gelation temperature + 30)°C, the ink will become too hot, which may cause the ink components to deteriorate.
  • the method for heating the ink is not particularly limited.
  • at least one of the ink supply system such as the ink tank constituting the head carriage, the supply pipe, and the anterior ink tank immediately before the head, the piping with a filter, and the piezo head can be heated by a panel heater, a ribbon heater, or heated water.
  • the amount of ink droplets ejected is preferably within the range of 2 to 20 pL in terms of recording speed and image quality.
  • the substrate is not particularly limited, but examples thereof include copper-clad laminates of all grades (such as FR-4) made of materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, copper-clad laminates for high-frequency circuits using fluorine, polyethylene, PPO, cyanate ester, etc., as well as polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, stainless steel plates, aluminum substrates, etc. Copper-clad laminates and aluminum substrates are particularly preferred. Examples of conductive oxide films include copper, gold, silver, aluminum, nickel, and ITO.
  • the ink that has landed on the oxide film in the step (1) is irradiated with actinic rays, and the ink is cured to form an etching resist film.
  • the actinic ray can be selected from, for example, electron beams, ultraviolet rays, ⁇ rays, ⁇ rays, and X-rays, and is preferably ultraviolet rays.
  • the ultraviolet light can be irradiated at a wavelength of 395 nm using, for example, a water-cooled LED manufactured by Phoseon Technology, Inc. By using an LED as the light source, poor ink curing caused by the ink melting due to the radiant heat of the light source can be suppressed.
  • the ultraviolet light irradiation is carried out so that the peak irradiance of ultraviolet light having a wavelength in the range of 360 to 410 nm on the surface of the resist film is preferably in the range of 0.5 to 10 W/cm 2 , more preferably in the range of 1 to 5 W/cm 2.
  • the amount of light irradiated onto the resist film is preferably 350 to less than 3000 mJ/cm 2 .
  • the irradiation of actinic rays can be carried out within 0.001 to 60 seconds after the ink has landed, preferably within 0.001 to 1.0 seconds after the ink has landed, and more preferably within 0.001 to 0.5 seconds in order to form a highly precise resist film.
  • the irradiation with actinic rays may be carried out in two stages.
  • the ink may be pre-cured by irradiating it with actinic rays for 0.001 to 2.0 seconds after the ink has landed, and then after all printing is completed, the ink may be fully cured by irradiating it with actinic rays.
  • shrinkage of the recording material that occurs when the ink is cured is more unlikely to occur.
  • an etching resist film is formed by the inkjet method. After the etching resist film is formed, a resist pattern such as a circuit, pattern, character, or image is obtained on the substrate by etching.
  • the reaction mechanism of wet etching using a liquid is to corrode and remove the substrate.
  • etching is performed by forcibly corroding the metal by oxidizing and dissolving it.
  • etching resistance refers to a protective function that inhibits corrosion of the substrate.
  • a cured film produced using the ink of the present disclosure can inhibit corrosion of the substrate in the area where the cured film is applied, thereby imparting etching resistance.
  • etching solutions include aqueous ferric chloride solution, aqueous cupric chloride solution, aqueous ammonia copper solution, highly concentrated aqueous sodium hydroxide solution, highly concentrated hydrochloric acid, aqueous hydrogen fluoride solution, and aqueous ferric nitrate solution.
  • the etching solutions exemplified above may be used alone or in combination.
  • the etching treatment may be carried out, for example, at a temperature of 40 to 60°C.
  • the copper dissolves in the aqueous solution of ferric chloride, and the iron is replaced by copper to generate copper chloride, which progresses the etching of the copper substrate.
  • stripping solutions include toluene, commercially available stripping solutions containing toluene, MEK, commercially available stripping solutions containing MEK, NMP, commercially available stripping solutions containing NMP, DMSO, and commercially available stripping solutions containing DMSO.
  • the ink of the present disclosure can also be used to form a plating resist.
  • 5 to 8 are diagrams illustrating the manufacturing process of a printed circuit board when the ink of the present disclosure is used to form a plating resist.
  • ink droplets are ejected from an inkjet head 5 onto a substrate 1, which is a recording medium (see FIG. 5). Then, the ink droplets are caused to land at positions corresponding to the plating resist film 3a to be formed, thereby forming a pattern (see FIG. 6).
  • the deposited ink is irradiated with actinic rays, and the ink is cured to form a plating resist film 3a.
  • the plating layer 4 is formed on the substrate 1 by carrying out the following plating process.
  • the plating process can be suitably performed using any of electrolytic plating, electroless plating in an acidic bath, a neutral bath, and an alkaline bath. Electroless plating is preferred, and an acidic bath is also preferred.
  • the plating process forms a plating layer on the exposed metal layer on the surface of the substrate (the portion other than the plating resist film).
  • the plated layer is formed of a metal such as, but not limited to, gold, silver, platinum, rhodium, palladium, copper, or nickel.
  • the plating process preferably includes a nickel plating process or a gold plating process.
  • the nickel plating process is preferable from the viewpoint of protecting the copper and being suitable for the soldering process.
  • the gold plating process is preferable from the viewpoint of the long-term stability of the nickel plating layer.
  • the plating process preferably includes a degreasing step using a weak alkaline solution, an acid cleaning step, a palladium activation step, a nickel plating step, a gold plating step, and the like.
  • the plating process includes immersion in an acid solution and immersion at high temperatures of about 60 to 90°C, and therefore forms a plating layer that simultaneously has acid resistance and heat resistance as coating film properties, thereby improving plating resistance.
  • the plating resist film 3a other than the plating layer 4 is stripped off with an organic solvent or a water-based stripping solution containing an organic solvent.
  • organic solvents include not only solvents that are readily soluble in water, but also poorly soluble and water-insoluble organic solvents.
  • organic solvents include linear, branched, secondary, or polyhydric alcohols such as ethanol, propanol, 2-propanol, butanol, 2-butanol, hexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, trimethylolpropane, neopentyl glycol, glycerin, 1,2,4-butanetriol, 1,2-butanediol, 1,4-butanediol, and diacetone alcohol; aromatic alcohols such as benzyl alcohol; ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether; polyethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and triethylene glycol monomethyl ether; propylene glycol alkyl,
  • Acetate esters such as ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, glycerin monoacetate, and glycerin diacetate; lactic acid esters such as ethyl lactate and butyl lactate; adipic acid esters such as diethyl adipate and dibutyl adipate; phthalate esters such as diethyl phthalate and dibutyl phthalate; dialkyl glycol esters such as diethylene glycol diethyl ether;
  • suitable solvents include ethers, ketones such as methyl ethyl ketone, cyclohexanone, and isophorone, aromatic hydrocarbons such as toluene and xylene, petroleum-based aromatic mixed solvents such as the Swazol series (manufactured by Maruzen Petrochemical Co., Ltd.)
  • aromatic alcohols such as 1-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone), 2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, dimethylacetamide, methyl ethyl ketone, and benzyl alcohol are preferred because they have high permeability to ultraviolet-curable inks containing a (meth)acrylate monomer having a cyclic imide group.
  • Particularly preferred organic solvents are aromatic alcohols such as benzyl alcohol.
  • the mass ratio of the content (mass%) of the (meth)acrylate monomer having a cyclic imide group to the content (mass%) of the polymerizable monomer having an alicyclic structure ((meth)acrylate monomer having a cyclic imide group/polymerizable monomer having an alicyclic structure) be within the range of 0.25 to 8.00.
  • the stripping liquid contains an aromatic alcohol, it may be either a water-based or organic solvent-based stripping liquid.
  • the etching resist film after the etching treatment or the plating resist film with an organic solvent after the plating treatment can be peeled off by an immersion method, a spray peeling method, an immersion method followed by irradiation with ultrasonic waves or the like, or the like.
  • peeling is performed by immersion, the substrate may be immersed in the stripping solution or organic solvent at 40 to 60° C. for 1 to 60 minutes. This operation may be performed only once, or the same operation may be performed multiple times.
  • the substrate may be washed with the stripping solution, organic solvent, or other solvent used in the peeling step.
  • the prepared ink was loaded into an inkjet recording apparatus having an inkjet recording head equipped with a piezoelectric inkjet nozzle, KM1800iSHC-C (manufactured by Konica Minolta, Inc.). Using this device, a pattern was formed on a copper-clad laminate for printed wiring boards (FR-4, thickness 1.6 mm, size 150 mm ⁇ 95 mm).
  • the ink supply system consisted of an ink tank, an ink flow path, a sub-ink tank immediately before the inkjet recording head, piping with a metal filter, and a piezo head. The ink was heated to 80°C from the ink tank to the head.
  • the ink temperature inside the inkjet head was heated to 80°C by the inkjet head with a built-in heater.
  • droplets were printed at a volume of 6.0 pl to form a 20 mm x 50 mm solid pattern on the substrate to a thickness of 20 ⁇ m.
  • the ink layer was then cured by irradiating it with a FireJetTM FJ100 (manufactured by Phoseon Technology, wavelength 395 nm) at 2 W/cm 2 and 3000 mJ/cm 2 to obtain a cured film.
  • the cured film sample was treated in the following five steps to obtain a plated sample.
  • First step The plate was immersed in a 0.5% aqueous solution of ACL-009 (manufactured by Uemura Kogyo Co., Ltd.) as a weak alkaline cleaner at 50° C. for 5 minutes, and then rinsed with pure water for 3 minutes.
  • Second step The substrate was immersed in a 50 mL/L aqueous sulfuric acid solution at room temperature for 3 minutes, and then washed with pure water for 3 minutes.
  • hird step The substrate was immersed in the prepared activation solution at 25° C. for 2 minutes, and then washed with pure water for 2 minutes.
  • the activation solution was prepared as follows: 700 mL of ion-exchanged water was slowly mixed with 30 mL of 62.5% by mass diluted sulfuric acid while stirring. After confirming that the liquid temperature was 40°C or less, 100 mL of Accemalta MNK-4-M (manufactured by Uemura Kogyo Co., Ltd.) was added and stirred, and 170 mL of ion-exchanged water was added to prepare the activation solution. (Fourth step) The plate was immersed in the prepared nickel plating solution at 80° C. for 10 minutes while stirring, and then rinsed with pure water for 3 minutes.
  • the nickel plating solution was prepared as follows: 150 mL of NPR-4-M (manufactured by Uemura Kogyo Co., Ltd.) and 45 mL of NPR-4-A (manufactured by Uemura Kogyo Co., Ltd.) were added to 500 mL of ion-exchanged water, and 305 mL of ion-exchanged water was added and heated to 80°C with stirring. Then, 3 mL of NPR-4-D (manufactured by Uemura Kogyo Co., Ltd.) was added and stirred to prepare the nickel plating solution. (Fifth step) The plated sample was immersed in the prepared gold plating solution at 80° C.
  • the gold plating solution was prepared as follows: 75 mL of TAM-LCM-75 (manufactured by Uemura Kogyo Co., Ltd.) and 45 mL of TAM-LCR (manufactured by Uemura Kogyo Co., Ltd.) were added to 500 mL of ion-exchanged water and stirred.
  • the gold-containing solution was prepared by dissolving 0.5 g of KCN and 147 g of potassium aurous cyanide in 1000 mL of ion-exchanged water.
  • a cross-cut tape peeling test was carried out on the plated samples. The number of remaining cross-cuts out of 100 was counted and the plating resistance was evaluated according to the following criteria. Criteria A, B, and C were considered acceptable for practical use. (standard) A: The remaining number is 100 out of 100. B: The remaining number is 90 to 99 out of 100. C: The remaining number is 70 to 89 out of 100. D: The remaining number is 69 or less out of 100.
  • ⁇ Injection stability> Using a printer equipped with a piezo inkjet head (KM1800iSHC-C, manufactured by Konica Minolta, Inc.), ink was continuously ejected (driven) while circulating using the piezo head under conditions of a droplet volume of 3.5 pL, a droplet speed of 7 m/s, an ejection frequency of 40 kHz, and a printing rate of 100%, and the number of nozzles with ejection failures was counted 10 minutes after the start of driving.
  • the ejection stability was evaluated according to the following criteria. Criteria A, B, and C below were considered to be acceptable for practical use.
  • A The number of nozzles with ejection failure was 0 or more and less than 2 nozzles.
  • B The number of nozzles with ejection failure was 2 or more but less than 5 nozzles.
  • C The number of nozzles with ejection failure was 5 or more and less than 20 nozzles.
  • D The number of nozzles with ejection failure was 20 or more.
  • a PP sheet with a corona coating manufactured by Okamoto Corporation was used to form a 20 ⁇ m thick cured film in the same manner as the inkjet pattern formation.
  • the resulting cured film was then immersed in a 10% NaOH aqueous solution, and the recyclability was evaluated according to the following criteria. Criteria A, B, and C were considered to be acceptable for practical use. (standard) A: The cured film peeled off from the PP sheet within 1 minute. B: The cured film peeled off from the PP sheet in 1 minute or more and less than 2 minutes. C: The cured film peeled off from the PP sheet in 2 minutes or more but less than 3 minutes. D: The cured film did not peel off from the PP sheet even after immersion for 3 minutes.
  • the ink of the present disclosure is superior to the ink of the comparative example in terms of etching resistance, solvent strippability, plating resistance, ejection stability, and recyclability.
  • the present disclosure can be used in actinic radiation-curable inkjet inks and inkjet recording methods that simultaneously satisfy etching resistance and peelability, and also have excellent plating resistance, ejection stability, and recyclability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

Une encre pour jet d'encre réticulable par rayonnement d'énergie active selon la présente divulgation est réticulée par un rayon d'énergie active, et contient un monomère de méthacrylate ayant un groupe imide cyclique et un monomère polymérisable ayant une structure alicyclique, le rapport massique (monomère de méthacrylate ayant un groupe imide cyclique/monomère polymérisable ayant une structure alicyclique) de la teneur (% en masse) du monomère de méthacrylate ayant le groupe imide cyclique et de la teneur (% en masse) du monomère polymérisable ayant la structure alicyclique étant compris entre 0,25 et 8,00.
PCT/JP2025/022171 2024-07-12 2025-06-19 Encre pour jet d'encre réticulable par rayonnement d'énergie active et procédé d'impression à jet d'encre Pending WO2026014192A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024-112129 2024-07-12
JP2024112129 2024-07-12

Publications (1)

Publication Number Publication Date
WO2026014192A1 true WO2026014192A1 (fr) 2026-01-15

Family

ID=98386451

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2025/022171 Pending WO2026014192A1 (fr) 2024-07-12 2025-06-19 Encre pour jet d'encre réticulable par rayonnement d'énergie active et procédé d'impression à jet d'encre

Country Status (1)

Country Link
WO (1) WO2026014192A1 (fr)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005539391A (ja) * 2002-09-20 2005-12-22 アベシア・リミテッド 電子装置を製造する方法及びインク
JP2011057751A (ja) * 2009-09-07 2011-03-24 Chisso Corp 重合性組成物
JP2011095602A (ja) * 2009-10-30 2011-05-12 Fuji Seal International Inc シュリンクラベル
JP2016102138A (ja) * 2014-11-27 2016-06-02 互応化学工業株式会社 インクジェットエッチングレジスト用紫外線硬化性組成物
WO2017078079A1 (fr) * 2015-11-06 2017-05-11 コニカミノルタ株式会社 Procédé de formation d'image à jet d'encre
JP2017537986A (ja) * 2014-09-29 2017-12-21 アグフア−ゲヴエルト 導電パターン製造用エッチ抵抗性インクジェットインク
JP2019167467A (ja) * 2018-03-23 2019-10-03 株式会社タムラ製作所 インクジェット用硬化性樹脂組成物
WO2021001937A1 (fr) * 2019-07-02 2021-01-07 コニカミノルタ株式会社 Encre à jet d'encre thermodurcissable
JP2022545915A (ja) * 2019-08-26 2022-11-01 アグフア－ゲヴエルト，ナームローゼ・フエンノートシヤツプ メッキ用途のための放射線硬化性組成物
JP2023136700A (ja) * 2022-03-17 2023-09-29 コニカミノルタ株式会社 インクジェットインク組成物、記録物、インクジェット記録方法及びインクジェット記録システム

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005539391A (ja) * 2002-09-20 2005-12-22 アベシア・リミテッド 電子装置を製造する方法及びインク
JP2011057751A (ja) * 2009-09-07 2011-03-24 Chisso Corp 重合性組成物
JP2011095602A (ja) * 2009-10-30 2011-05-12 Fuji Seal International Inc シュリンクラベル
JP2017537986A (ja) * 2014-09-29 2017-12-21 アグフア−ゲヴエルト 導電パターン製造用エッチ抵抗性インクジェットインク
JP2016102138A (ja) * 2014-11-27 2016-06-02 互応化学工業株式会社 インクジェットエッチングレジスト用紫外線硬化性組成物
WO2017078079A1 (fr) * 2015-11-06 2017-05-11 コニカミノルタ株式会社 Procédé de formation d'image à jet d'encre
JP2019167467A (ja) * 2018-03-23 2019-10-03 株式会社タムラ製作所 インクジェット用硬化性樹脂組成物
WO2021001937A1 (fr) * 2019-07-02 2021-01-07 コニカミノルタ株式会社 Encre à jet d'encre thermodurcissable
JP2022545915A (ja) * 2019-08-26 2022-11-01 アグフア－ゲヴエルト，ナームローゼ・フエンノートシヤツプ メッキ用途のための放射線硬化性組成物
JP2023136700A (ja) * 2022-03-17 2023-09-29 コニカミノルタ株式会社 インクジェットインク組成物、記録物、インクジェット記録方法及びインクジェット記録システム

Similar Documents

Publication Publication Date Title
JP5626520B2 (ja) 紫外線硬化型インクジェット用インク組成物
CN101978001B (zh) 抗蚀用喷墨油墨组合物
CN106715607B (zh) 用于制造导电图案的抗蚀刻喷墨油墨
JP5630605B2 (ja) 紫外線硬化型インクジェット用インク組成物
CN104066590B (zh) 可辐射固化的耐蚀刻喷墨油墨印刷
JP5255307B2 (ja) エッチングレジスト用インクジェットインキ組成物
JP5664850B2 (ja) 紫外線硬化型インクジェット用インク組成物
CN1694934A (zh) 制备电子装置的方法和油墨
JP7528937B2 (ja) 熱硬化性インクジェットインク
JPWO2014041940A1 (ja) 硬化性組成物および画像形成方法
JP5589177B2 (ja) 紫外線硬化型インクジェット用インク組成物
JP7020349B2 (ja) レジスト用インクジェットインク
JP7740251B2 (ja) 硬化性組成物、ソルダーレジスト用インク及びプリント回路基板
JP7753937B2 (ja) インクジェットインク組成物、記録物、インクジェット記録方法及びインクジェット記録システム
JP2016199688A (ja) インクジェットインク
TW201544907A (zh) 使用轉印膜之三維基材成像法
JP7025571B2 (ja) プリント回路基板を製造するためのインキジェットインキ
JP6952859B1 (ja) 活性エネルギー線硬化型インクジェット用インク組成物
JP5518311B2 (ja) エッチングレジスト用インクジェットインキ組成物
JP2021515092A (ja) プリント回路基板を製造するためのインキジェットインキ
JP7231074B2 (ja) レジスト用インクジェットインク、レジスト膜及びレジスト膜の形成方法
JP2012219255A (ja) 紫外線硬化型インク組成物、記録方法
JP4606011B2 (ja) 紫外線硬化型インクジェットインク組成物
WO2008156523A1 (fr) Agent de réserve pour jet d'encre polymérisable aux rayons ultraviolets
WO2026014192A1 (fr) Encre pour jet d'encre réticulable par rayonnement d'énergie active et procédé d'impression à jet d'encre

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: 25836754

Country of ref document: EP

Kind code of ref document: A1