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WO2025192095A1 - Ensemble d'encre à deux composants, procédé de formation de produit durci et produit - Google Patents

Ensemble d'encre à deux composants, procédé de formation de produit durci et produit

Info

Publication number
WO2025192095A1
WO2025192095A1 PCT/JP2025/003393 JP2025003393W WO2025192095A1 WO 2025192095 A1 WO2025192095 A1 WO 2025192095A1 JP 2025003393 W JP2025003393 W JP 2025003393W WO 2025192095 A1 WO2025192095 A1 WO 2025192095A1
Authority
WO
WIPO (PCT)
Prior art keywords
ink
silica filler
component
ink set
meth
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/JP2025/003393
Other languages
English (en)
Japanese (ja)
Inventor
千代子 竹村
厚志 仲島
正幸 牛久
夏帆 森山
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 WO2025192095A1 publication Critical patent/WO2025192095A1/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
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • 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
    • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to a two-component ink set, a method for forming a cured product, and a product. More specifically, it relates to an ink set that has a long pot life and can provide excellent film properties as an insulator for use in electronic components.
  • PCBs printed Circuit Boards
  • PCB printed Circuit Boards
  • the layers formed to insulate and protect these wiring are formed by laminating and crimping prepregs containing glass fibers in the case of inner layer wiring in laminated boards.
  • the outermost layers of single-layer boards, double-sided boards, and laminated boards are formed using solder resist as an insulating protective layer.
  • Patent Document 1 uses a one-component inkjet composition consisting of a photocurable compound and a thermosetting compound, thereby improving the film properties after application of the composition.
  • Patent Document 2 uses a two-part inkjet composition consisting of a base agent and a curing agent, which has improved pot life and ejection stability, and aims to improve the film properties after curing.
  • the inkjet composition is a one-component type, so the ink has a short pot life and does not achieve sufficient inkjet ejection properties. Furthermore, because the ink contains a small amount of filler, when the inkjet composition is used as an insulating material, the physical properties of the insulating material do not achieve the desired properties.
  • Inkjet compositions containing silica fillers are unstable components in the ink, and are mixed on a substrate using an inkjet method. Cured films are then formed by UV curing and then thermal curing, but it has been difficult to obtain film properties suitable for insulating materials. Examples of film properties suitable for insulating materials include heat resistance, film strength, durability, thermal cycle suitability, thermal expansion coefficient, glass transition temperature, and toughness.
  • silica filler content in the inkjet composition is reduced to prevent the state of the ink components from becoming unstable, the desired thermal expansion coefficient, toughness, etc. cannot be achieved.
  • the present invention was made in consideration of the above problems and circumstances, and its objective is to provide a two-component ink set, a method for forming a cured product, and a product that has a long pot life and can produce a film with excellent physical properties as an insulator for use in electronic components.
  • the present inventors have conducted extensive research with reference to the prior art with the aim of easily forming an insulating material with excellent physical properties between thick copper wiring or on the surface of wiring by an inkjet process.
  • a silica filler into one or both of the two inks in a two-component ink set consisting of ink A and ink B, each containing a photocurable compound, and have arrived at the present invention. That is, the above-mentioned problems of the present invention are solved by the following means.
  • a two-component inkjet ink set consisting of at least ink A and ink B, the ink A contains at least a photocurable compound, the B ink contains at least a thermosetting compound, At least one of the ink A and the ink B contains a silica filler, and A two-component ink set, wherein the silica filler is surface-modified.
  • the polymerizable functional group of the silica filler contained in the ink A is a (meth)acrylic group, 2.
  • a product having a cured resin composition 6.
  • a product characterized in that the cured product is a cured product consisting of components of the ink A and the ink B that constitute the two-component ink set described in any one of items 1 to 5.
  • the above-described means of the present invention can provide a two-component ink set that has a long pot life and can provide excellent film properties as an insulator for use in electronic components, a method for forming a cured product, and a product.
  • the mechanism by which the effects of the present invention are manifested or the mechanism of action is presumed as follows.
  • Either ink A or ink B, or both, that make up the two-component ink set of the present invention contain a surface-modified filler. Therefore, the two-component ink set of the present invention has the effect of improving the dispersion stability of the ink and reducing the viscosity of the ink compared to ink sets that contain fillers that are not surface-modified. It also has the effect of ensuring inkjet ejection stability, such as improving the ink landing accuracy and suppressing the generation of satellite droplets when ejecting ink.
  • the two-component ink set of the present invention has excellent inkjet ejection properties, resulting in excellent pattern accuracy.
  • the A ink and B ink that make up the two-component ink set of the present invention are ejected by the inkjet method, land on a substrate, and are in a highly fluid state when mixed together. Furthermore, by irradiating both inks with UV light, the inks are able to flow until they are cured.
  • Patent Document 1 allows the ink to contain filler, but from the standpoint of thickness accuracy of the cured film, voids, and inkjet ejection properties, the lower the filler content, the better. Specifically, it describes that the filler content is preferably 5% by mass or less, and most preferably 0.5% by mass or less.
  • a cured film formed using an ink with such a low filler content does not have the excellent physical properties, such as a low thermal expansion coefficient, that would make it suitable for use as a planarization material for thick copper substrates.
  • silica filler 10% by mass of silica filler is added to the ink, but this silica filler is not surface-modified. Furthermore, silica filler that is not surface-modified does not provide dispersion stability, resulting in thickening or aggregation/sedimentation, making it impossible to obtain a dispersion with excellent inkjet ejection properties.
  • the surface-modified silica filler contained in either or both of the A and B inks that make up the two-component ink set of the present invention should be present in a larger amount, within the range that allows for inkjet ejection, resulting in excellent ink dispersibility.
  • Improved droplet landing accuracy improves the mixing of the two components.
  • the amount of filler added can be increased while keeping the viscosity low, the glass transition temperature (Tg) can be maintained high and the thermal expansion coefficient can be reduced, resulting in high insulation resistance and excellent film toughness in the cured film after curing of the ink set.
  • a cured film with a low coefficient of thermal expansion (CTE), a high glass transition temperature (Tg), high insulation resistance, and good film toughness can be obtained with good pattern accuracy.
  • CTE coefficient of thermal expansion
  • Tg glass transition temperature
  • good film toughness can be obtained with good pattern accuracy.
  • a cured film is suitable for use as an insulating material that requires thickness for electrical materials, and is particularly suitable for insulating materials that require durability in harsh environments, such as those used in power electronics.
  • An example of a printing machine configuration An example of a schematic diagram of the structure of the glass epoxy substrate used to prepare the evaluation sample An example of a schematic diagram of an evaluation sample obtained by curing ink An example of a schematic diagram of a Teflon (registered trademark) plate evaluation sample
  • the two-component ink set of the present invention is a two-component ink set for inkjet printing composed of at least an A ink and a B ink, characterized in that the A ink contains at least a photocurable compound, the B ink contains at least a thermosetting compound, and at least one of the A ink and the B ink contains a silica filler, and the silica filler is surface-modified.
  • This feature is a technical feature common to or corresponding to each of the following embodiments (aspects).
  • the silica filler has a polymerizable functional group, from the viewpoint of improving film properties such as film strength and thermal expansion coefficient after ink set curing.
  • the polymerizable functional group is a glycidyl group or a (meth)acrylic group, from the viewpoint of improving film properties such as film strength and thermal expansion coefficient after curing of the ink set.
  • both the A ink and the B ink contain a surface-modified silica filler, from the viewpoint of improving film properties such as film strength and thermal expansion coefficient after ink set curing.
  • the polymerizable functional group of the silica filler contained in the ink A is a (meth)acrylic group
  • the polymerizable functional group of the silica filler contained in the ink B is a glycidyl group.
  • the ink A and the ink B that make up the two-component ink set are ejected from separate inkjet head nozzles. This extends the pot life of the two-component ink set.
  • the two-component ink set is applied to an object to be coated, forming a coating film, and the cured product is then formed by irradiating the coating film with active energy rays, resulting in a cured product with good pattern precision and excellent lamination suitability.
  • the film obtained by laminating the ink composition can be made thicker, and it also effectively functions to flatten various components when used in electronic components, etc.
  • the product of the present invention is a product having a cured product of a resin composition, characterized in that the cured product is a cured product consisting of the components of the ink A and the ink B that make up the two-component ink set of the present invention.
  • the two-component ink set of the present invention can be suitably used in the product of the present invention.
  • the product can be suitably used on thick copper substrates.
  • the two-component ink set of the present invention is a two-component ink set for inkjet printing composed of at least an A ink and a B ink, characterized in that the A ink contains at least a photocurable compound, the B ink contains at least a thermosetting compound, and at least one of the A ink and the B ink contains a silica filler, and the silica filler is surface-modified.
  • the amount of surface-modified silica filler contained in ink A and/or ink B constituting the two-component ink set of the present invention is preferably as large as possible within the range that allows inkjet ejection.
  • the cured film formed by ink with a high filler content has excellent film properties, including a low thermal expansion coefficient, making it suitable for use as a planarization material for thick copper substrates.
  • surface-modified silica filler disperses easily in monomers, making it possible to obtain a dispersion with excellent inkjet ejection properties. Furthermore, cured films formed from inks containing surface-modified silica filler have sufficient toughness.
  • the ink set of the present invention is a two-component type
  • the A ink and B ink according to the present invention do not mix until they are ejected, for example, by an inkjet head. Therefore, there is an advantage in that the pot life of the A ink or B ink alone is longer than that of a one-component ink set.
  • the ink A according to the present invention contains at least a photocurable compound. It is preferable that the ink A contains a surface-modified silica filler. If the ink A does not contain a surface-modified silica filler, the ink B described below will contain a surface-modified silica filler. The ink A may also contain a filler other than the surface-modified silica filler. The ink A may also contain a thermosetting catalyst, a thermosetting agent, a photopolymerization initiator, a reactive diluent, and other components. The term “reactive" in the above "reactive diluent” includes both photoreactivity and heat reactivity.
  • Photocurable compound Ink A according to the present invention contains at least a photocurable compound. This improves the pattern accuracy after application of the ink set, contributes to thickening of the film after curing of the ink set, and provides excellent flatness, improving lamination suitability.
  • Photocurable compound refers to a compound having a curable functional group, and is a compound that polymerizes (cures) when exposed to actinic rays such as ultraviolet light or electron beams. If the B ink according to the present invention, described below, contains a photocurable compound with a lower viscosity, the viscosity of the B ink will be lower. If the B ink contains a photocurable compound with a high glass transition temperature, the glass transition temperature of the cured film formed by curing an ink set containing the B ink will be higher.
  • the photocurable compound contained in Ink A according to the present invention is preferably a radically polymerizable compound.
  • photocurable compounds examples include curable compounds having a (meth)acryloyl group, curable compounds having a vinyl group, and curable compounds having a maleimide group.
  • curable compounds having a (meth)acryloyl group examples include curable compounds having a (meth)acryloyl group, curable compounds having a vinyl group, and curable compounds having a maleimide group.
  • acrylics examples include acrylics, cationic photocurable compounds such as alicyclic epoxy compounds and oxetane compounds.
  • a curable compound having a (meth)acryloyl group refers to a compound having at least one of a methacryloyl group and an acryloyl group.
  • (meth)acrylate refers to acrylate or methacrylate.
  • (meth)acrylic refers to acrylic or methacrylic.
  • the photocurable compound have a (meth)acryloyl group. Only one type of the photocurable compound may be used, or two or more types may be used in combination.
  • photocurable compound a photocurable compound having one (meth)acryloyl group may be used, or a photocurable compound having two or more (meth)acryloyl groups may be used.
  • photocurable compounds having one (meth)acryloyl group include monofunctional compounds.
  • photocurable compounds having two or more (meth)acryloyl groups include polyfunctional compounds.
  • polyfunctional compounds include (meth)acrylic acid adducts of polyhydric alcohols, (meth)acrylic acid adducts of alkylene oxide-modified polyhydric alcohols, urethane (meth)acrylates, and polyester (meth)acrylates.
  • polyhydric alcohols examples include diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, and polypropylene glycol.
  • Other examples include trimethylolpropane, cyclohexanedimethanol, tricyclodecanedimethanol, alkylene oxide adducts of bisphenol A, and pentaerythritol.
  • At least one of the photocurable compounds contained in the ink A is a tri- or higher functional (meth)acrylic monomer, which is preferable from the viewpoints of printing precision and 3D formability, since this increases the UV curing speed.
  • trifunctional (meth)acrylates include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, alkylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane tri((meth)acryloyloxypropyl)ether, alkylene oxide-modified isocyanuric acid tri(meth)acrylate, dipentaerythritol propionate tri(meth)acrylate, tri((meth)acryloyloxyethyl)isocyanurate, and sorbitol tri(meth)acrylate.
  • tetrafunctional (meth)acrylates include pentaerythritol tetra(meth)acrylate and sorbitol tetra(meth)acrylate.
  • Other examples include ditrimethylolpropane tetra(meth)acrylate and dipentaerythritol propionate tetra(meth)acrylate.
  • pentafunctional (meth)acrylates examples include sorbitol penta(meth)acrylate and dipentaerythritol penta(meth)acrylate.
  • hexafunctional (meth)acrylates include dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, and alkylene oxide-modified hexa(meth)acrylate of phosphazene.
  • Examples of commercially available photocurable compounds include monofunctional commercially available products such as “SR285" (tetrahydrofurfuryl acrylate) and “SR203" (tetrahydrofurfuryl methacrylate) manufactured by Sartomer, "A0144” (2-ethylhexyl acrylate) manufactured by TCI, "Light Acrylate PO-A” (phenoxyethyl acrylate) manufactured by Kyoeisha Chemical Co., Ltd., "Light Acrylate IB-XA” (isobornyl acrylate) manufactured by Kyoeisha Chemical Co., Ltd., “Light Ester IB-X” (isobornyl methacrylate) manufactured by Kyoeisha Chemical Co., Ltd., “Light Acrylate MPD-A” (3-methyl-1,5 pentanediol acrylate) manufactured by Kyoeisha Chemical Co., Ltd., and "Light Acrylate P2H-A” (
  • bifunctional products include, for example, Sartomer's "SR230" (diethylene glycol diacrylate), “SR212” (1,3-butylene glycol diacrylate), Shin-Nakamura Chemical's "A-HD-N” (1,6-hexanediol diacrylate), “A-NOD-N” (1,9-nonanediol diacrylate), “A-DOD-N” (1,10-decanediol diacrylate), “A-NPG” (neopentyl glycol diacrylate), and “A-200” (polyethylene glycol diacrylate), all manufactured by Miwon. These can also be used as reactive diluents.
  • the ink A according to the present invention preferably contains a surface-modified silica filler, which improves the dispersibility and inkjet ejection properties of the ink, and also improves the film properties such as film strength and thermal expansion coefficient after the ink is set and cured.
  • Silane coupling agents include, for example, various alkyl silanes including methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, and n-octadecyldimethyl(3-(trimethoxysilyl)propyl)ammonium chloride; various fluoroalkyl silanes including trifluoromethylethyltrimethoxysilane and heptadecafluorodecyltrimethoxysilane; various amino group-containing silanes including N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoeth
  • the average particle size of the filler is preferably within the range of 0.1 to 2 ⁇ m. More preferably, the average particle size is within the range of 0.1 to 1 ⁇ m, with a maximum average particle size of 2 ⁇ m. If the average particle size of the filler is smaller than 0.1 ⁇ m, the viscosity of the ink composition will be high and it will not be usable in inkjet printing. Furthermore, if the average particle size of the filler is larger than 2 ⁇ m, it may cause a deterioration in ejection stability, such as the accuracy of ink droplet placement. Furthermore, the filler will settle in the ink composition, and the filler and the resin components in the ink will easily separate within the tank containing the ink composition or within the inkjet head. Therefore, it will not be possible to apply a homogeneous ink composition.
  • the average particle size is the particle size at 50% of the cumulative value in the particle size distribution on a volume basis, measured by laser diffraction/scattering.
  • the average particle size can be measured, for example, using a laser diffraction/scattering particle size distribution measuring device: Zetasizer Nano S90 (manufactured by Malvern Instruments).
  • the weight-average molecular weight of the surface modifier is not particularly limited, but is preferably in the range of 1,000 to 50,000.
  • the weight-average molecular weight of the surface modifier can be measured by gel permeation chromatography (GPC).
  • Surface modifiers can be used alone or in combination of two or more types. Furthermore, surface modifiers may be synthetic or commercially available.
  • the filler content is preferably 5% by mass or more, and more preferably 10% by mass or more, relative to 100% by mass of the ink A according to the present invention. This improves the ejection properties of the ink A. It is preferable that as much filler as possible be contained in the ink A, but if there is too much, the viscosity of the ink will become too high and it will not be possible to eject it by inkjet. Therefore, the filler content is preferably 40% by mass or less, and more preferably 30% by mass or less, relative to 100% by mass of the ink A according to the present invention.
  • the silica filler has a polymerizable functional group, from the viewpoint of improving film properties such as film strength and thermal expansion coefficient after curing of the ink set.
  • the silica filler according to the present invention is surface-modified with a surface modifier.
  • a surface modifier there are no particular restrictions on the surface modifier, but it is preferable that the surface modifier be a surface modifier having a polymerizable functional group.
  • silane coupling agents having a polymerizable functional group examples include silane coupling agents having a vinyl group, glycidyl group, styryl group, methacryl group, or acrylic group.
  • silane coupling agents containing a vinyl group examples include vinyltrimethoxysilane and vinyltriethoxysilane.
  • silane coupling agents containing a glycidyl group examples include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane.
  • examples of other silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane.
  • silane coupling agents containing a styryl group examples include p-styryltrimethoxysilane.
  • silane coupling agents containing a methacryl group examples include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane.
  • silane coupling agents containing an acrylic group examples include 3-acryloxypropyltrimethoxysilane.
  • the surface-modified silica filler according to the present invention has a polymerizable functional group, from the viewpoint of improving film properties such as film strength and thermal expansion coefficient after ink set curing.
  • the polymerizable functional group contained in Ink A according to the present invention is a glycidyl group, from the viewpoint of improving film properties such as film strength and thermal expansion coefficient after ink set curing. It is also preferable that the polymerizable functional group contained in Ink A according to the present invention is a (meth)acrylic group, from the viewpoint of improving film properties such as film strength and thermal expansion coefficient after ink set curing.
  • the polymerizable functional group is a glycidyl group or a (meth)acrylic group, from the viewpoint of improving film properties such as film strength and thermal expansion coefficient after curing of the ink set.
  • both the A ink and the B ink contain a surface-modified silica filler, from the viewpoint of improving film properties such as film strength and thermal expansion coefficient after ink set curing.
  • the polymerizable functional group of the silica filler contained in the ink A is a (meth)acrylic group
  • the polymerizable functional group of the silica filler contained in the ink B is a glycidyl group.
  • surface-modified silica fillers include, for example, "SC2500-SEJ” (Admafine 0.5 ⁇ m, epoxy treatment) manufactured by Admatechs Co., Ltd.
  • Other examples include “SC2300-SVJ” (Admafine 0.5 ⁇ m, vinyl treatment) and “SC2500-SXJ” (Admafine 0.5 ⁇ m, phenylamine treatment) manufactured by the same company.
  • Other examples include “SC2500-SMJ” (Admafine 0.5 ⁇ m, methacrylic treatment) and "SC2500-SPJ” (Admafine 0.5 ⁇ m, phenyl treatment) manufactured by the same company.
  • Thermosetting catalyst refers to a catalyst for controlling the heat-accelerated curing speed and curing temperature.
  • a thermosetting catalyst is contained in the A ink according to the present invention, for example, when an epoxy resin is used in the B ink according to the present invention, the thermosetting catalyst is used in an amount of 0.1 to 2.0 mass % relative to the epoxy resin, calculated after mixing of the two liquids.
  • the thermosetting catalyst does not form the main skeleton and is not incorporated into the cured film formed by the ink set of the present invention, and therefore does not have a significant effect on the physical properties of the cured film.
  • thermosetting catalyst can be mixed as a core material for microcapsules, or its catalytic action can be controlled by molecular modification so that catalytic action occurs at a certain temperature. It can also be contained in the A ink without being mixed into the B ink.
  • the B ink does not contain a thermosetting catalyst, as this promotes the curing reaction after the two inks are mixed and extends the pot life of the B ink.
  • Thermosetting catalysts used in the present invention include, for example, basic catalysts.
  • Basic catalyst examples include tertiary amines, tertiary amine salts, imidazole derivatives, phosphine compounds, phosphonium salts, etc. These basic catalysts may be used alone or in appropriate combination of two or more.
  • tertiary amines or tertiary amine salts examples include DBU (1,8-diazabicyclo(5,4,0)-undecene-7), DBN (1,5-diazabicyclo(4,3,0)-nonene-5), organic acid salts of DBU or DBN, 2,4,6-tris(dimethylaminomethyl)phenol, piperidine, N,N-dimethylpiperazine, triethylenediamine, benzyldimethylamine, and 2-(dimethylaminomethyl)phenol.
  • imidazole derivatives include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole.
  • Phosphine compounds and phosphonium salts include, for example, tributylphosphine, triphenylphosphine, benzyltriphenylphosphonium bromide, and ethyltriphenylphosphonium methanesulfonate.
  • Other examples include tetraphenylphosphonium tetraphenylborate and tetra-n-butylphosphonium tetraphenylborate.
  • tertiary amines or tertiary amine salts, and imidazole derivatives are preferred from the standpoints of solubility, reactivity, and latency.
  • thermosetting catalysts include those classified as DBU, DBN, and imidazole.
  • DBU Commercially available products classified as DBU include, for example, "U-CAT SA102” (2-ethylhexane salt of 1,8-diazabicyclo[5,4,0]undecene-7) manufactured by San-Apro Co., Ltd., "U-CAT SA1” (phenol salt of 1,8-diazabicyclo[5,4,0]undecene-7) manufactured by the same company, and "U-CAT SA603” (formate of 1,8-diazabicyclo[5,4,0]undecene-7) manufactured by the same company.
  • Examples of such products include "U-CAT SA810” (o-phthalate salt of 1,8-diazabicyclo[5,4,0]undecene-7) and "U-CAT SA506” (p-toluenesulfonate salt of 1,8-diazabicyclo[5,4,0]undecene-7) manufactured by the same company.
  • DBN Commercially available products classified as DBN include, for example, "U-CAT 1102" (1,5-diazabicyclo[4.3.0]nonene-5, 2-ethylhexanoate) manufactured by San-Apro Co., Ltd.
  • the heat curing agent that can be contained in the ink A according to the present invention can be the same as the heat curing agent that can be contained in the ink B, which will be described later.
  • photopolymerization initiators examples include photoradical polymerization initiators and photocationic polymerization initiators. There are no particular restrictions on the photopolymerization initiator, but it is preferable to use a photoradical polymerization initiator, and the photoradical polymerization initiators may be used alone or in combination of two or more types.
  • photoradical polymerization initiator refers to a compound that generates radicals upon irradiation with light and initiates a radical polymerization reaction.
  • photoradical polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; alkylphenone compounds such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one; acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone; and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane- aminoacetophenone compounds such as 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1--
  • Thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; ketal compounds such as acetophenone dimethyl ketal and benzil dimethyl ketal; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 1,2-octanedione, 1-[4-(phenylthio)-2-(o-benzoyloxime)], ethanol
  • suitable oxime compounds include oxime ester compounds such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime); and titanocene compounds such as bis(cyclopentadienyl)-dip
  • the content of the photoradical polymerization initiator is preferably within the range of 1 to 10 mass% of the total amount of radical polymerization monomers contained in Ink A.
  • photopolymerization initiators include alkylphenone-based commercially available products and acylphosphine oxide-based commercially available products.
  • alkylphenone products include IGM Resins' "Omnirad 369” (2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone), IGM Resins' "Omnirad 651” (2,2-dimethoxy-2-phenylacetophenone), IGM Resins' "Omnirad 184" (1-hydroxycyclohexyl-phenyl ketone), IGM Resins' "Omnirad 1173” (2-hydroxy-2-methyl-1-phenylpropanone), IGM Resins' "Omnirad 2959” (1-[4-(2-hydroxyethoxy )-phenyl]-2-hydroxy-methylpropanone), Omnirad 127 (2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one), Omnirad 907 (2-methyl-1-[4-(methylthio)phenyl]-2-morpholino
  • acylphosphine oxide products include “Omnirad TPO” (diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide) manufactured by IGM Resins.
  • Other examples include “Omnirad 819” (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) manufactured by the same company.
  • a "cationic photopolymerization initiator” is a compound for photopolymerizing a cationically polymerizable monomer. Any known photoacid generator can be used as the cationic photopolymerization initiator. Examples of photoacid generators include compounds used in chemically amplified photoresists and cationic photopolymerization (see Organic Electronics Materials Research Group, "Organic Materials for Imaging,” Bunshin Publishing (1993), pp. 187-192).
  • examples include B(C 6 F 5 ) 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , and CF 3 SO 3 ⁇ salts of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium, and phosphonium.
  • examples include sulfonates that generate sulfonic acid.
  • examples include halides that photogenerate hydrogen halide.
  • examples include iron allene complexes.
  • photocationic polymerization initiators include, for example, diaryliodonium or triallylsulfonium hexafluorophosphate, hexafluoroantimonate, or pentafluorophenylborate salts. These are commercially available under trade names such as Irgacure-261 (manufactured by BASF Japan), SP-150, SP-170 (all manufactured by ADEKA), PI2074, and UVI-6992 (manufactured by Dow Chemical).
  • the content of the above-mentioned photocationic polymerization initiator is preferably within the range of 1 to 10 mass% of the total amount of cationic polymerization monomers contained in Ink A.
  • Photosensitizer is an additive that absorbs light energy that cannot be excited by an initiator and transmits it to a photopolymerization initiator, thereby improving the polymerization rate, deep curing, and curing properties (adhesion, surface hardness, etc.).
  • Ink A of the present invention can also be used in combination with a photosensitizer to make the curing reaction more efficient.
  • Photosensitizers include, for example, amines such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino)ethyl benzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, and 2-ethylhexyl 4-dimethylaminobenzoate, cyanine, phthalocyanine, merocyanine, porphyrin, spiro compounds, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, fluorene, fluorine ...
  • amines such as triethanolamine, methyldiethanolamine, triisopropanolamine
  • methyl 4-dimethylaminobenzoate ethyl 4-
  • photosensitizers include ethenothiazine, polyene, azo compounds, diphenylmethane, triphenylmethane, polymethine acridine, coumarin, ketocoumarin, quinacridone, indigo, styryl, pyrylium compounds, pyrromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, and thiobarbituric acid derivatives.
  • compounds described in European Patent No. 568993, U.S. Patent Nos. 4,508,811 and 5,227,227, Japanese Patent Application Laid-Open Nos. 2001-125255 and 1999-271969 may also be used.
  • the amount of photosensitizer used is preferably in the range of 0.01 to 10.00% by mass of the ink composition.
  • Reactive diluent is a colorless, low-viscosity liquid that is added to a substance to reduce its viscosity and make it easier to handle.
  • Ink A according to the present invention preferably contains a reactive diluent, which can reduce the viscosity of the ink A.
  • the purpose of adding a reactive diluent is to lower the viscosity of the ink to the point where it can be inkjet-ejected, but using a monomer with a high glass transition temperature is particularly preferable, as it can increase the glass transition temperature of the cured film.
  • Reactive diluents include, for example, photoreactive diluents and thermally reactive diluents.
  • the photoreactive diluents may be, for example, the photocurable compounds described above, and the thermally reactive diluents may be, for example, the thermosetting compounds described below. These reactive diluents may be used alone or in combination of two or more.
  • the reason for using a photocurable compound and/or a thermosetting compound as described above is that after the ink set of the present invention is cured, the curable compound is fixed in the cured film and does not volatilize or bleed out.
  • a photocurable compound is preferred as the reactive diluent.
  • the reactive diluent When a photocurable compound is used as the reactive diluent, there are no particular restrictions on the amount of reactive diluent that can be contained in Ink A, as long as the viscosity of Ink A can be adjusted to an optimum level.
  • a thermosetting compound when used as the reactive diluent, it is necessary to maintain UV curability to the extent that it loses fluidity when exposed to UV light. For this reason, there is an appropriate range for the amount of photocurable compound, and if it is too much, it is not desirable as the desired film properties will not be achieved after UV curing and thermosetting.
  • the amount of reactive diluent contained is determined taking into consideration the ink temperature and viscosity at which the ink can be ejected from the inkjet head, with the upper limit of the ink viscosity at 25°C being approximately 100 cp.
  • the function of the reactive diluent is to lower the viscosity of the ink, so ink A with a viscosity of 30 cp or less is preferred, 15 cp or less is more preferred, and 10 cp or less is even more preferred.
  • Reactive diluents that can be contained in Ink A include low-viscosity photocurable compounds and low-viscosity thermosetting compounds, but photocurable compounds are preferred in consideration of their reactivity with thermosetting catalysts.
  • the reactive diluent content is preferably within the range of 1 to 70% by mass relative to 100% by mass of Ink A according to the present invention.
  • a reactive diluent content of 1% by mass or more improves the compatibility of Ink A, allowing the components of Ink A to be dispersed uniformly.
  • a reactive diluent content of 70% by mass or less provides the effect of improving heat resistance.
  • the ink A according to the present invention may contain other components, such as water, organic solvents, adhesion aids such as coupling agents, pigments, dyes, leveling agents, antifoaming agents, and polymerization inhibitors.
  • adhesion aids such as coupling agents, pigments, dyes, leveling agents, antifoaming agents, and polymerization inhibitors.
  • the water contained in Ink A according to the present invention is not particularly limited, and may be ion-exchanged water, distilled water, or pure water. However, it is preferable to keep the water content to 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.2% by mass or less, relative to 100% by mass of Ink A.
  • bisphenol-type epoxy compound examples include bisphenol A-type epoxy compounds and bisphenol F-type epoxy compounds, as well as 2,2'-diallyl bisphenol A-type epoxy compounds, hydrogenated bisphenol-type epoxy compounds, and polyoxypropylene bisphenol A-type epoxy compounds.
  • bifunctional products include “Epogose HD (D)” (1,6-hexanediol diglycidyl ether) and “Epogose NPG (D)” (neopentyl glycol diglycidyl ether), both manufactured by Yokkaichi Synthetic Co., Ltd.
  • Other examples include “Epogose BD (D)” (1,4-butanediol diglycidyl ether) and “DY-BP” (butyl glycidyl ether), both manufactured by the same company. These can also be used as reactive diluents.
  • thermosetting compound (3.2) Heat Curing Agent
  • the heat curing agent according to the present invention can be contained in either ink A or ink B to finally heat cure the thermosetting compound.
  • the heat curing agents contained in the B ink according to the present invention include types that cure at relatively low temperatures, such as aliphatic polyamines, polyaminoamides, and polymercaptans. Other types do not cure unless heated to high temperatures, such as aromatic polyamines, acid anhydrides, phenol novolac resins, and dicyandiamide. To obtain a cured film with high heat resistance, a low thermal expansion coefficient, a high glass transition temperature, and excellent film strength and insulation properties, a high-temperature heat curing agent is preferred.
  • acid anhydrides are more preferred due to their high solubility in the epoxy resins and reactive diluents used in the ink materials. This results in a cured film with a low coefficient of thermal expansion (CTE), a high glass transition temperature (Tg), high insulation resistance, and good film toughness.
  • solid materials such as dicyandiamide can precipitate even after dissolving, making it difficult to achieve inkjet suitability, such as ejection stability.
  • solid materials may require heating to dissolve, which can shorten the ink's pot life.
  • acid anhydride examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, and dodecylsuccinic anhydride.Other examples include chlorendic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, methylcyclohexenetetracarboxylic anhydride, trimellitic anhydride, and polyazelaic anhydride.
  • thermosetting agents other than acid anhydrides for example, a phenolic compound or a modified polyamine compound such as an amine-epoxy adduct may be used, and other heat curing agents may also be used.
  • Phenol-based compounds include, for example, bis(4-hydroxyphenyl)-2,2-propane, 4,4'-dihydroxybenzophenone, bis(4-hydroxyphenyl)-1,1-ethane, and bis(4-hydroxyphenyl)-1,1-isobutane.
  • Other examples include polyhydric phenols such as bis(4-hydroxy-tert-butyl-phenyl)-2,2-propane, bis(2-hydroxynaphthyl)methane, and 1,5-dihydroxynaphthalene.
  • Other examples include polyfunctional phenols such as phenol novolac resin, bisphenol novolac resin, and cresol novolac resin.
  • Amine compound refers to a compound containing one or more primary, secondary, or tertiary amino groups.
  • amine compounds include aliphatic amines, alicyclic amines, aromatic amines, hydrazides, and guanidine derivatives.
  • adducts such as epoxy compound-added polyamines (reaction products of epoxy compounds and polyamines) and Michael addition polyamines (reaction products of ⁇ , ⁇ -unsaturated ketones and polyamines).
  • adducts such as Mannich addition polyamines (condensation products of polyamines with formalin and phenols), thiourea addition polyamines (reaction products of thiourea and polyamines), and ketone-blocked polyamines (reaction products of ketone compounds and polyamines [ketimines]).
  • thermosetting agents include commercially available acid anhydrides such as “YH306” (methylbutenyltetrahydrophthalic anhydride) manufactured by Mitsubishi Chemical Corporation, "HN-2200” (methyltetrahydrophthalic anhydride), “HN-5500” (methylhexahydrophthalic anhydride) manufactured by Resonac Corporation, “MHAC-P” (methylnadic anhydride) manufactured by the same company, and "RIKACID TH” (tetrahydrophthalic anhydride) and “RIKACID HH” (hexahydrophthalic anhydride) manufactured by New Japan Chemical Co., Ltd.
  • acid anhydrides such as "YH306” (methylbutenyltetrahydrophthalic anhydride) manufactured by Mitsubishi Chemical Corporation, “HN-2200” (methyltetrahydrophthalic anhydride), “HN-5500” (methylhexahydrophthalic anhydride) manufactured by Resonac Corporation, “MHAC-P” (methylna
  • amine heat curing agents include ADEKA's "EH-105L” (aromatic polyamine) and Mitsui Fine Chemicals' “APB-N” (1,3-bis(3-aminophenoxy)benzene).
  • the content of the heat curing agent is preferably in the range of 1 to 60% by mass, more preferably in the range of 5 to 60% by mass, and even more preferably in the range of 5 to 50% by mass, relative to 100% by mass of the B ink according to the present invention.
  • thermosetting agent of the present invention be incorporated as a repeating unit in an appropriate ratio into the polymer chain of the thermosetting compound from the viewpoints of heat resistance, film strength, thermal expansion coefficient, glass transition temperature, and insulating properties.
  • thermosetting compound is an epoxy resin
  • the optimal ratio will vary depending on the compound used, but it is generally preferable to use a molar ratio of 0.1 to 1.5 equivalents of thermosetting agent to the epoxy equivalent, and it is even more preferable to use 0.8 to 1.2 equivalents.
  • the "epoxy equivalent” mentioned above is the molecular weight divided by the number of glycidyl groups.
  • the remaining epoxy resin may be a homopolymer of epoxy resin in which the heat curing agent is not incorporated into the repeating unit.
  • the B ink according to the present invention preferably contains a surface-modified silica filler. This significantly improves the dispersibility and inkjet ejection properties of the ink, and not only improves the accurate mixing of the two-component ink, printing precision, and 3D formability, but also dramatically improves the film properties after ink set curing, such as crack resistance, toughness, film strength capable of withstanding thermal cycles, and thermal expansion coefficient.
  • the A ink described above contains a surface-modified silica filler.
  • the B ink according to the present invention may also contain a filler other than a surface-modified silica filler. Commercially available products may be used as the surface-modified silica filler.
  • the surface-modified silica filler and fillers other than said silica filler that can be contained in the ink B according to the present invention are the same as the surface-modified silica filler and fillers other than said silica filler that can be contained in the ink A described above.
  • the B ink according to the present invention preferably contains a surface-modified silica filler.
  • the A ink described above contains a surface-modified silica filler.
  • the surface modifier is not particularly limited, but is preferably a surface modifier having a polymerizable functional group B.
  • the B ink according to the present invention contains a surface-modified silica filler
  • the surface-modified silica filler it is preferable that the surface-modified silica filler have a polymerizable functional group, from the viewpoint of improving film properties such as film strength and thermal expansion coefficient after ink set curing.
  • the surface-modified silica filler contained in the B ink according to the present invention has a polymerizable functional group, and it is preferable that the polymerizable functional group is a glycidyl group, from the viewpoint of improving film properties such as film strength and thermal expansion coefficient after the ink set is cured. It is also preferable that the polymerizable functional group is a (meth)acrylic group, from the viewpoint of improving film properties such as film strength and thermal expansion coefficient after the ink set is cured.
  • the polymerizable functional group possessed by the surface-modified silica filler contained in the ink B according to the present invention is a glycidyl group, and that the polymerizable functional group possessed by the surface-modified silica filler contained in the ink A described above is a (meth)acrylic group. This improves the dispersibility and inkjet ejection properties of the ink.
  • the B ink according to the present invention contains a photothermally reactive compound from the viewpoints of film toughness after curing of the ink composition, crack resistance, drill resistance, adhesion, and durability in a heat cycle test.
  • the reason for improved film toughness is that having a photocurable functional group and a thermosetting functional group in the same molecule allows the photocurable compound and the thermosetting compound to be bonded together.
  • a "photo-thermally reactive compound” refers to a compound having at least one photo-curable functional group and at least one thermo-curable functional group.
  • the photothermally reactive compound preferably has one or more (meth)acryloyl groups and one or more epoxy groups. Only one of the photothermally reactive compounds may be used, or two or more may be used in combination.
  • the cured product of the resin composition formed from the two-component ink set of the present invention has a low thermal expansion coefficient, a high glass transition temperature, and excellent film toughness, insulation resistance, and heat resistance, making it suitable for insulating film pattern formation processes that require thickness control. It can also be used favorably as a planarizing material for the insulating film between wiring on thick copper PCBs, which is increasingly required for power electronics PCBs. Furthermore, it can be used not only to planarize the inner layer thick copper circuits of such laminated PCBs, but also to provide insulating protection for the outer layer copper wiring of PCBs.
  • the thicker cured film i.e., the cured product of the resin composition
  • the physical properties of the cured product are strongly affected by the thermal expansion coefficient and glass transition temperature, which can lead to problems such as cracks and reduced adhesion to thick copper substrates.
  • the cured product of the components of Ink A and Ink B that make up the inkjet-ejectable two-component ink set of the present invention has a thermal expansion coefficient that is significantly smaller than that of cured products of conventional inkjet-ejectable resin compositions, a high glass transition temperature, and excellent 3D formability. For this reason, it is suitable for flattening thick copper surfaces of 210 ⁇ m or more, particularly 300 ⁇ m or more, and can be used favorably in products such as electronic components.
  • the ink components in Table I are as follows. The amounts of each component in Table I are expressed in mass %.
  • SPJ Phenyl surface-treated silica (manufactured by Admatechs Co., Ltd.). Although “SPJ” is listed in Table I, it is actually the product name “SC2500-SPJ” (particle size 0.5 ⁇ m).
  • SVJ vinyl surface-treated silica (manufactured by Admatechs Co., Ltd.). Note that although “SVJ” is listed in Table I, it is actually the product name "SC2300-SVJ” (particle size 0.5 ⁇ m).
  • SEJ Epoxy surface-treated silica (manufactured by Admatechs Co., Ltd.).
  • the ink components in Table II are as follows. The amounts of each component in Table II are expressed in mass %.
  • SPJ Phenyl surface-treated silica (manufactured by Admatechs Co., Ltd.). Although “SPJ” is listed in Table II, it is actually the product name "SC2500-SPJ” (particle size 0.5 ⁇ m).
  • SVJ vinyl surface-treated silica (manufactured by Admatechs Co., Ltd.). Note that although “SVJ” is listed in Table II, it is actually the product name “SC2300-SVJ” (particle size 0.5 ⁇ m).
  • SEJ Epoxy surface-treated silica (manufactured by Admatechs Co., Ltd.). Note that although “SEJ” is listed in Table II, it is actually the product name “SC2500-SEJ” (particle size 0.5 ⁇ m).
  • SJ Methacrylic surface-treated silica (manufactured by Admatechs Co., Ltd.).
  • the ink components in Table III are as follows. The amounts of each component in Table III are expressed in mass %.
  • SR833 Tricyclodecane dimethanol diacrylate (manufactured by Sartomer)
  • A0144 2-ethylhexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • 4300E Bisphenol A type epoxy resin (manufactured by ADEKA Corporation) In Table III, “4300E” is written, but the product name is "EP-4300E”.
  • FIG. 1 shows an example of the configuration of a printing machine. Printing was performed using a serial printing type inkjet printer equipped with two inkjet heads in the layout shown in Figure 1.
  • PS refers to the printer stage
  • S refers to the substrate
  • C refers to the carriage
  • UV lamp refers to a UV-LED irradiator manufactured by Phoseon Technology.
  • H1 refers to inkjet head H1
  • H2 refers to inkjet head H2.
  • Phoseon 365nm UV-LED irradiators were mounted on both sides of carriage C, and inkjet heads H1 and H2 were Konica Minolta KM1024i series (nozzle pitch 360npi, 1024 nozzles, standard droplet size 30pL).
  • Ink was supplied from ink tanks (not shown) connected to inkjet heads H1 and H2.
  • the flow path including the ink tanks was pressure-controlled (not shown) to form an appropriate meniscus.
  • printing is performed by scanning a carriage bidirectionally over the substrate, and after ink is ejected, a UV irradiator follows, allowing UV curing for each round trip scan.
  • inkjet head H1 and inkjet head H2 were 4 cm, and the distance between each inkjet head and the UV-LED irradiator was 10 cm.
  • Inkjet head H1 which was connected to an ink cartridge filled with ink as shown in Figure 1, was filled with ink A, and inkjet head H2 was filled with ink B. At this time, the temperature, voltage, and drive waveform of the inkjet head were appropriately adjusted so that the droplet size of both ink A and ink B was 30 pL.
  • a 5cm x 5cm solid image was used to evaluate the physical properties of the printed material.
  • the solid image was printed so that the ratio of the coverage rate of ink A to the coverage rate of ink B was 1:5, and the coverage rates of ink A and ink B were set so that when scanned four times (two round trips), i.e., four passes, a 1440 x 1440 dpi image was formed, resulting in a thickness of 100 ⁇ m.
  • the coverage ratios of ink A and ink B were set so that when a 1440 x 1440 dpi image was formed using 8 (4 round trips), 12 (6 round trips), or 24 (12 round trips) scans, i.e., 8, 12, or 24 passes, the resulting thicknesses were 200 ⁇ m, 300 ⁇ m, or 400 ⁇ m.
  • Ink B was ejected immediately after ink A was ejected, mixing the two inks, and then the material was temporarily cured by UV exposure.
  • the head scanning speed was 300 mm/s, and the UV exposure amount per scan at this speed was 300 mJ/cm 2 .
  • FIG. 1 is an example of a schematic diagram of the evaluation sample obtained by curing the ink.
  • Evaluation samples [G2] to [G9] were prepared in the same manner as evaluation sample [G1], except that the heating temperature, voltage, and printing ratio of the inkjet head were adjusted so that the laminate film thickness would be 100 ⁇ m, 200 ⁇ m, 300 ⁇ m, or 400 ⁇ m. Evaluation samples [G2] to [G9] were also prepared for film thicknesses of 100 ⁇ m, 200 ⁇ m, 300 ⁇ m, and 400 ⁇ m.
  • the image boundary was found to extend beyond the design value by more than 300 ⁇ m for a 5 cm x 5 cm size due to a deterioration in the landing accuracy of the ejected ink. This phenomenon worsened with each printing cycle.
  • (Evaluation criteria) 4 No cracks were observed in any of the evaluation samples having thicknesses of 100 ⁇ m, 200 ⁇ m, 300 ⁇ m, and 400 ⁇ m.
  • 3 No cracks were observed in the evaluation samples with film thicknesses of 100 ⁇ m, 200 ⁇ m, and 300 ⁇ m, but cracks were observed in the sample with a film thickness of 400 ⁇ m.
  • 2 No cracks were observed in the evaluation samples with film thicknesses of 100 ⁇ m and 200 ⁇ m, but cracks were observed in the evaluation samples with film thicknesses of 300 ⁇ m and 400 ⁇ m.
  • 1 No cracks were observed in the evaluation sample with a film thickness of 100 ⁇ m, but cracks were observed in the samples with film thicknesses of 200 ⁇ m, 300 ⁇ m, and 400 ⁇ m.
  • CTE coefficient of thermal expansion
  • (Evaluation criteria) 4 The coefficient of thermal expansion (CTE) is less than 61 ppm/°C. 3: The coefficient of thermal expansion (CTE) is 61 ppm/°C or more and less than 71 ppm/°C. 2: The coefficient of thermal expansion (CTE) is 71 ppm/°C or more and less than 81 ppm/°C. 1: The coefficient of thermal expansion (CTE) is 81 ppm/°C or more.
  • the glass transition temperature (Tg) is 130°C or higher.
  • the glass transition temperature (Tg) is 110°C or higher and lower than 130°C.
  • the glass transition temperature (Tg) is 90°C or higher and lower than 110°C. 1: The glass transition temperature (Tg) is less than 90°C.

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Abstract

La présente invention aborde le problème consistant à fournir : un ensemble d'encre à deux composants qui a une longue durée de vie en pot et peut fournir d'excellentes propriétés physiques de film en tant qu'isolant utilisé pour un composant électronique ; un procédé de formation d'un produit durci ; et un produit.　Cet ensemble d'encre à deux composants pour jet d'encre est composé d'au moins une encre A et une encre B, l'ensemble d'encre à deux composants étant caractérisé en ce que l'encre A contient au moins un composé photodurcissable, l'encre B contient au moins un composé thermodurcissable, au moins l'une des encres parmi l'encre A et l'encre B contient une charge de silice, et la charge de silice est modifiée en surface.
PCT/JP2025/003393 2024-03-15 2025-02-03 Ensemble d'encre à deux composants, procédé de formation de produit durci et produit Pending WO2025192095A1 (fr)

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JP2011225867A (ja) * 2010-03-31 2011-11-10 Dic Corp 水性顔料分散液の製造方法
JP2018203912A (ja) * 2017-06-06 2018-12-27 太陽インキ製造株式会社 インクジェット用硬化性組成物セット、硬化物、その製造方法、プリント配線板およびファンアウト型のウェハレベルパッケージ
JP2021147581A (ja) * 2020-03-23 2021-09-27 株式会社リコー インクジェット用活性エネルギー線硬化型組成物、立体造形物の製造方法、及び立体造形物の製造装置
JP2022155890A (ja) * 2021-03-31 2022-10-14 日本化薬株式会社 インク、インクメディアセット及び耐擦性の向上方法

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