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WO2025192100A1 - Ensemble d'encres à deux composants, procédé de formation de produit durci et produit - Google Patents

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

Info

Publication number
WO2025192100A1
WO2025192100A1 PCT/JP2025/003521 JP2025003521W WO2025192100A1 WO 2025192100 A1 WO2025192100 A1 WO 2025192100A1 JP 2025003521 W JP2025003521 W JP 2025003521W WO 2025192100 A1 WO2025192100 A1 WO 2025192100A1
Authority
WO
WIPO (PCT)
Prior art keywords
ink
compound
thermosetting
component
ink set
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/JP2025/003521
Other languages
English (en)
Japanese (ja)
Inventor
千代子 竹村
厚志 仲島
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 WO2025192100A1 publication Critical patent/WO2025192100A1/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
    • C09D11/52—Electrically conductive inks
    • 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.
  • 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.
  • PCBs that require large currents necessarily require a relatively large copper thickness. This is because thicker copper reduces wiring resistance and makes it possible to reduce the PCB size.
  • 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 one-component inkjet composition disclosed in Patent Document 1 contains a thermosetting catalyst, which causes the reaction of the epoxy resin, a thermosetting compound, to proceed within the inkjet composition, shortening its pot life. Furthermore, there is room for improvement in the ejection stability of the inkjet composition when ejecting it.
  • the two-component inkjet composition in the technology disclosed in Patent Document 2 does not contain a heat curing agent, which is the polymerization unit of the epoxy resin, a thermosetting compound.
  • a heat curing agent which is the polymerization unit of the epoxy resin, a thermosetting compound.
  • Such cured films may not be strong enough to withstand use as insulating materials that require a certain thickness for electrical applications, and are particularly unsuitable for insulating materials that must be durable in harsh environments, such as those used in power electronics.
  • the present invention was made in consideration of the above problems and circumstances, and aims to provide a two-component ink set, a method for forming a cured product, and a product that have a long pot life and excellent film properties.
  • thermosetting agent is added to ink B, which contains a thermosetting compound.
  • thermosetting agent is incorporated as a repeating unit in the polymer chain of the thermosetting compound in an optimal ratio, thereby solving the above-mentioned problems, and led to 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 two-component ink set is characterized in that the B ink contains at least a thermosetting compound and a thermosetting agent.
  • thermosetting compounds contained in the B ink is an epoxy resin having a cyclic structure.
  • a product having a cured resin composition 8.
  • 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, 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 not clear, but is speculated as follows.
  • the two-component ink set of the present invention is a two-component ink set for inkjet printing composed of at least ink A and ink B, characterized in that ink A contains at least a photocurable compound, and ink B contains at least a thermosetting compound and a thermosetting agent.
  • the present invention uses a two-component ink set, which avoids the mixing of highly reactive materials and maintains a separate structure, resulting in a long pot life. Furthermore, because ink A contains a photocurable compound, the pattern precision after application of the ink composition is improved and lamination suitability is excellent. In other words, the film obtained by laminating the ink composition can be made thicker, and it also functions effectively to flatten the conductor wiring when used in various electronic components, etc.
  • thermosetting compound contained in ink B reacts slowly, so if ink A did not contain a photocurable compound, it would not be able to be UV-cured later, causing ink B to become fluid and resulting in poor resolution during image formation. In contrast, by including a photocurable compound in ink A, it can be UV-cured later, resulting in higher resolution during image formation and improved 3D formation precision.
  • thermosetting agent can be incorporated as a repeating unit in the polymer chain of the thermosetting compound at an optimal ratio, resulting in excellent film properties after the ink composition is cured.
  • a cured film can be formed that has a low coefficient of thermal expansion (CTE), a high glass transition temperature (Tg), high insulation resistance, and excellent film toughness.
  • CTE coefficient of thermal expansion
  • Tg glass transition temperature
  • insulation resistance high insulation resistance
  • film toughness e.g
  • such cured films can withstand use as insulating materials that require thickness for electrical materials. They are particularly suitable for insulating materials that require durability in harsh environments, such as those used in power electronics. The following are thought to be the reasons why such excellent film properties can be obtained.
  • ink B contains epoxy resin as a thermosetting compound
  • the ink B also contains a thermosetting agent that becomes the polymerization unit of the epoxy resin. Therefore, before ink A and ink B are mixed together, the polymerization ratio of the epoxy resin and thermosetting agent in ink B is determined and fixed. Therefore, even when ink A and ink B are mixed together after ejection of the ink set, the rigid structure in which the polymerization units of the thermosetting agent are incorporated into the polymerization chains of the epoxy resin is stably maintained.
  • the polymerization ratio in the cured film obtained using the two-component ink set can be maintained at an optimum level without being affected by factors that change the polymerization ratio when ink A and ink B are mixed together in the two-component ink set.
  • Factors that may cause the above polymerization ratio to fluctuate include, for example, when ink A and ink B are ejected from separate inkjet heads, differences in the landing position, amount, and landing conditions of ink A and ink B on the component, resulting in non-uniform mixing. It is believed that after ejection of a typical two-component ink set, the ink set will inevitably be affected by these fluctuating factors. As mentioned above, to consistently obtain cured films with excellent film properties, it is extremely important that the film properties, such as the coefficient of thermal expansion (CTE), glass transition temperature (Tg), and film toughness, are highly robust.
  • CTE coefficient of thermal expansion
  • Tg glass transition temperature
  • film toughness film toughness
  • thermosetting compound and a thermosetting agent are ejected from separate nozzles and deposited in the same position, the thermosetting compound and the thermosetting agent are mixed. If active energy rays are irradiated immediately after this, the polymerization ratio of the two is not fixed because the thermosetting compound and the thermosetting agent are not contained in the same ink, and a UV-cured film is formed, so the effects of the above-mentioned variables are thought to be unavoidable.
  • thermosetting compound and the thermosetting agent in ink B before ejecting a two-component ink set containing ink A and ink B, it is thought that the polymerization ratio can be maintained at an optimum level even when the two inks are mixed together.
  • the UV-cured film formed by irradiating the mixed inks with actinic rays or the like maintains an optimal polymerization ratio. Therefore, by subsequently thermally curing the UV-cured film, a rigid and highly cross-linked polymer structure is formed in the UV-cured film. This is thought to result in a cured film with a low coefficient of thermal expansion (CTE), a high glass transition temperature (Tg), high insulation resistance, and excellent film toughness. Furthermore, such cured films are durable enough for use as insulating materials that require thickness for electrical materials. They are 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 use that is composed of at least an A ink and a B ink, and is characterized in that the A ink contains at least a photocurable compound, and the B ink contains at least a thermosetting compound and a thermosetting agent.
  • This feature is a technical feature common to or corresponding to each of the following embodiments (aspects).
  • the A ink and the B ink that make up the two-component ink set are ejected from separate inkjet head nozzles. This extends the pot life of the ink set. Furthermore, the two-component ink set is applied and adhered to an object to form a coating film, and the cured product is formed by irradiating the coating film with active energy rays. This improves the pattern precision of the resulting cured product and provides excellent lamination suitability. In other words, the film obtained by laminating the ink composition can be made thicker, and this method also effectively functions to flatten each component when used in electronic components, etc.
  • the heat curing agent contained in the B ink is an acid anhydride, from the viewpoint of obtaining a cured film with a low coefficient of thermal expansion (CTE), a high glass transition temperature (Tg), high insulation resistance, and good film toughness.
  • the A ink contains a thermosetting catalyst and the B ink does not contain a thermosetting catalyst, as this promotes the curing reaction after the two inks are mixed together and extends the pot life of the B ink.
  • thermosetting compounds contained in the B ink has a cyclic structure. Furthermore, it is preferable that at least one of the thermosetting compounds is an epoxy resin having a cyclic structure, from the viewpoint of obtaining a cured film with a low coefficient of thermal expansion (CTE).
  • CTE coefficient of thermal expansion
  • At least one of the photocurable compounds contained in Ink A is a tri- or higher functional (meth)acrylic monomer, the UV curing speed is improved, which is preferable from the standpoints of printing accuracy and 3D formability.
  • the B ink further contains the photocurable compound, from the viewpoints of reducing the viscosity of the ink composition, improving printing accuracy, and improving 3D formability.
  • the B ink contains a photo- and thermo-reactive compound, from the viewpoint of improving the flexibility, crack resistance, and drill resistance of the ink composition after curing.
  • 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 use that is composed of at least an A ink and a B ink, and is characterized in that the A ink contains at least a photocurable compound, and the B ink contains at least a thermosetting compound and a thermosetting agent.
  • the ink set of the present invention is a two-component type, and therefore the ink A and ink B according to the present invention do not mix until they are ejected, for example, by an inkjet head. Therefore, there is an advantage that the pot life of ink A or ink B alone is longer than that of a one-component ink set.
  • Ink A of the present invention contains at least a photocurable compound, and ink B contains at least a thermosetting compound.
  • ink B contains a thermosetting agent in addition to the thermosetting compound.
  • thermosetting agent which contains a thermosetting compound as mentioned above, already contains the optimal ratio of thermosetting agent. This allows the thermosetting agent to be incorporated as a repeating unit in the polymer chain of the thermosetting compound in the optimal ratio.
  • ink A and ink B can be mixed while maintaining the polymerization ratio between the thermosetting compound and the thermosetting agent, regardless of factors that may cause fluctuations in the polymerization ratio when the two-component ink set is applied. This allows for the stable formation of a cured film with a rigid structure.
  • Ink A contains at least a photocurable compound.
  • ink A may also contain a thermosetting catalyst, a photopolymerization initiator, a reactive diluent, a filler, and other components.
  • a thermosetting catalyst e.g., a thermosetting catalyst
  • a photopolymerization initiator e.g., a photopolymerization initiator
  • a reactive diluent e.g., a filler, and other components.
  • Photocurable Compound A “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 rays or electron beams. If a photocurable compound with a lower viscosity is used in the B ink according to the present invention, which will be described later, the viscosity of the B ink will be lower. If a photocurable compound with a higher glass transition temperature is used in the photocurable compounds, 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 radical 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.
  • Trifunctional or higher (meth)acrylic monomers When at least one of the photocurable compounds contained in the ink A is a tri- or higher functional (meth)acrylic monomer, the UV curing speed is improved, which is preferable from the viewpoints of printing precision and 3D formability.
  • 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.
  • trifunctional products include, for example, Miwon's Miramer M300 (trimethylolpropane triacrylate) and Kyoeisha Chemical's Light Acrylate PE-3A (pentaerythritol triacrylate).
  • commercially available tetrafunctional products include, for example, Miwon's Miramer M410 (ditrimethylolpropane tetraacrylate) and Kyoeisha Chemical's Light Acrylate PE-4A (pentaerythritol tetraacrylate).
  • pentafunctional products include, for example, Shin-Nakamura Chemical's A-DPH (dipentaerythritol polyacrylate).
  • commercially available hexafunctional products include, for example, Kyoeisha Chemical's Light Acrylate DPE-6A (dipentaerythritol hexaacrylate).
  • Thermosetting catalyst refers to a catalyst for controlling the heat-accelerated curing speed and curing temperature.
  • the amount contained in the A ink according to the present invention is 0.1 to 2.0 mass % relative to the epoxy resin, calculated after mixing the two liquids.
  • the thermosetting catalyst does not form the main skeleton, and does not have a significant effect on the physical properties of the cured film.
  • the A ink contains a thermosetting catalyst and the B ink does not contain a thermosetting catalyst, as this promotes the curing reaction after the two inks are mixed together 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 include, for example, DBU (1,8-diazabicyclo(5,4,0)-undecene-7), DBN (1,5-diazabicyclo(4,3,0)-nonene-5), and organic acid salts of DBU or DBN.
  • Other examples include 2,4,6-tris(dimethylaminomethyl)phenol, piperidine, N,N-dimethylpiperazine, triethylenediamine, benzyldimethylamine, and 2-(dimethylaminomethyl)phenol.
  • Imidazole derivatives include, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole. Also included are 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, those classified as DBN, those classified as phosphine compounds or phosphonium salts, and those classified as imidazoles.
  • 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.
  • phosphine compounds or phosphonium salts include, for example, TCI's "T0519” (triphenylphosphine), “T1329” (tetraphenylphosphonium tetraphenylborate), and “T2008” (tetra-n-butylphosphonium tetraphenylborate), as well as San-Apro's "U-CAT 5003” (benzyltriphenylphosphonium bromide) and "U-CAT 5050” (ethyltriphenylphosphonium methanesulfonate).
  • 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.
  • the fluidity quickly decreases after light irradiation, resulting in good 3D formability when forming a thick film of insulating material, so it is preferable to use a photocurable compound 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 preferably contains a filler. This improves the physical properties of the cured film formed by applying and curing an ink set containing the ink A and the ink B.
  • the filler can be any known filler without limitation.
  • examples of fillers include silica, hollow silica, alumina, titanium oxide, aluminum hydroxide, zinc oxide, zirconium oxide, magnesium oxide, mica, and bismuth oxychloride.
  • Other examples include talc, kaolin, barium sulfate, silicic acid anhydride, calcium carbonate, magnesium carbonate, magnesium silicate, aluminum silicate, magnesium aluminum silicate, silicon carbide, silicon nitride, boron nitride, glass powder, metal oxides, and metal powders.
  • These fillers can be used alone or in combination of two or more.
  • 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 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, the ejection stability, such as the landing accuracy of the ejected ink, will deteriorate, 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).
  • commercially available surface-modified silica can be used, and examples thereof include “SC2500-SEJ” (Admafine 0.5 ⁇ m, epoxy treatment) manufactured by Admatechs Co., Ltd., "SC2300-SVJ” (Admafine 0.5 ⁇ m, vinyl treatment) manufactured by the same company, “SC2500-SXJ” (Admafine 0.5 ⁇ m, phenylamine treatment) manufactured by the same company, “SC2500-SMJ” (Admafine 0.5 ⁇ m, methacrylic treatment) manufactured by the same company, and “SC2500-SPJ” (Admafine 0.5 ⁇ m, phenyl treatment) manufactured by the same company.
  • SC2500-SEJ Admafine 0.5 ⁇ m, epoxy treatment
  • SC2300-SVJ Admafine 0.5 ⁇ m, vinyl treatment
  • SC2500-SXJ Admafine 0.5 ⁇ m, phenylamine treatment
  • SC2500-SMJ Admafine 0.5 ⁇ m
  • 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.
  • the organic solvent contained in Ink A according to the present invention is not particularly limited and can be any known organic solvent.
  • the organic solvent content is preferably kept to 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, relative to 100% by mass of Ink A.
  • the B ink according to the present invention contains at least a thermosetting compound and a thermosetting agent.
  • the B ink may also contain a photo- and thermo-reactive compound, a photopolymerization initiator, a reactive diluent, a filler, and other components. Note that the "reactivity" in “reactive diluent” includes both photo-reactivity and heat-reactivity.
  • thermosetting compound refers to a compound having a curable functional group, which polymerizes (cures) when heat is applied.
  • thermosetting compound an epoxy resin is preferably used. At least one of the thermosetting compounds contained in the B ink according to the present invention preferably has a cyclic structure. Furthermore, from the viewpoint of obtaining a cured film with a low coefficient of thermal expansion (CTE), it is preferable that at least one of the thermosetting compounds is an epoxy resin having a cyclic structure.
  • One type of such thermosetting compound may be used alone, or two or more types may be used in combination.
  • a cured film can be formed by curing the ink set of the present invention using the curing of the epoxy resin, but a cured film can also be formed by using the curing reaction caused by adding a thermal radical polymerization initiator to an acrylic resin as a thermosetting compound.
  • thermosetting epoxy resins examples include bisphenol A epoxy resins, bisphenol F epoxy resins, phenol novolac epoxy resins, and cresol novolac epoxy resins.
  • Other examples include biphenyl epoxy resins, aliphatic epoxy resins, and glycidylamine epoxy resins. From the standpoint of heat resistance, it is particularly preferable for the thermosetting epoxy resin to be an epoxy resin with a cyclic structure other than an aliphatic type.
  • thermosetting epoxy resins that have aromatic rings such as bisphenol A epoxy resin, phenol novolac epoxy resin, and cresol novolac epoxy resin, are more preferred from the standpoints of insulation properties and film strength. They are also more preferred from the standpoints of coefficient of thermal expansion (CTE), glass transition temperature (Tg), etc.
  • CTE coefficient of thermal expansion
  • Tg glass transition temperature
  • thermosetting epoxy resin when using the above-mentioned thermosetting epoxy resin in combination with a photocurable compound such as (meth)acrylate, it is preferable to reproducibly obtain the desired film properties described above. Furthermore, it is preferable that the thermosetting epoxy resin be a novolac type or a bisphenol type.
  • novolac-type epoxy compound examples include phenol novolac epoxy compounds, cresol novolac epoxy compounds, biphenyl novolac epoxy compounds, and trisphenol novolac epoxy compounds. Also included are dicyclopentadiene novolac epoxy compounds.
  • bisphenol-type epoxy compound examples include bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, and 2,2'-diallyl bisphenol A-type epoxy compounds. Other examples include hydrogenated bisphenol-type epoxy compounds and polyoxypropylene bisphenol A-type epoxy compounds.
  • thermosetting compounds examples include “Epogose 2EH” (2-ethylhexyl glycidyl ether) and “Epogose OCR” (glycidyl (2-methylphenyl) ether), both manufactured by Yokkaichi Chemical Co., Ltd. These can also be used as reactive diluents.
  • 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.
  • 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 that has high heat resistance, a low coefficient of thermal expansion, a high glass transition temperature, and excellent film strength and insulating properties, a heat curing agent that can be heated to high temperatures 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, or other heat curing agents may 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]).
  • heat curing agents include commercially available acid anhydrides such as “YH306” (methylbutenyltetrahydrophthalic anhydride) manufactured by Mitsubishi Chemical Corporation and "HN-2200” (methyltetrahydrophthalic anhydride) manufactured by Resonac Corporation.
  • Other examples include “HN-5500” (methylhexahydrophthalic anhydride) and “MHAC-P” (methylnadic anhydride) manufactured by the same company.
  • Other examples include “RIKACID TH” (tetrahydrophthalic anhydride) and “RIKACID HH” (hexahydrophthalic anhydride) manufactured by New Japan Chemical Co., Ltd.
  • 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 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 photocurable compound and thermosetting compound according to the present invention are preferably contained as components different from the photo- and thermo-reactive compound.
  • photothermally reactive compounds include compounds having a (meth)acryloyl group and an epoxy group, partially (meth)acrylated epoxy compounds, and urethane-modified (meth)acrylic epoxy compounds.
  • Compound having a (meth)acryloyl group and an epoxy group examples include glycidyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether.
  • epoxy compounds that can be used for the partially (meth)acrylated epoxy compound include novolac-type epoxy compounds and bisphenol-type epoxy compounds.
  • the partially (meth)acrylated epoxy compound can be obtained, for example, by reacting an epoxy compound with (meth)acrylic acid in the presence of a catalyst according to a conventional method.
  • the urethane-modified (meth)acrylic epoxy compound can be obtained, for example, by the following method.
  • a polyol is reacted with a difunctional or higher isocyanate, and then the remaining isocyanate groups are reacted with a (meth)acrylic monomer having an acid group and glycidol.
  • a difunctional or higher isocyanate may be reacted with a (meth)acrylic monomer having a hydroxyl group and glycidol without using a polyol.
  • the above urethane-modified (meth)acrylic epoxy compound can also be obtained by reacting a (meth)acrylate monomer having an isocyanate group with glycidol.
  • Polyols are not particularly limited, but examples include ethylene glycol, glycerin, sorbitol, trimethylolpropane, and (poly)propylene glycol.
  • the isocyanate is not particularly limited as long as it is difunctional or higher, and examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl)thiophosphate, tetramethylxylene diisocyanate, and 1,6,10-undecane triisocyanate.
  • MDI diphenylmethane-4,4'-diiso
  • the photothermally reactive compound preferably includes glycidyl acrylate, glycidyl methacrylate, or 4-hydroxybutyl acrylate glycidyl ether. From the viewpoint of reactivity, 4-hydroxybutyl acrylate glycidyl ether is more preferred.
  • the content of the photothermally reactive compound is preferably 0.5% by mass or more relative to 100% by mass of the B ink according to the present invention, in order to further improve the physical properties of the cured film, particularly film toughness and crack resistance. It is more preferably in the range of 1 to 30% by mass.
  • the content of the photothermally reactive compound is too low, the effect will not be obtained, and if the content of the photothermally reactive compound is too high, the flexibility will be too high, the thermal expansion coefficient will increase, and the glass transition temperature will decrease, which is undesirable.
  • photothermally reactive compounds include, for example, "4HBAGE” (4-hydroxybutyl acrylate glycidyl ether) manufactured by Mitsubishi Chemical Corporation and "G0497” (glycidyl acrylate) manufactured by TCI.
  • Other examples include “M0590” (glycidyl methacrylate) manufactured by the same company and “EA-1010LC” (bisphenol A skeleton glycidyl ether-containing epoxy acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Other examples include "EBECRYL 3605" (epoxy resin half acrylate) manufactured by Daicel Allnex Corporation.
  • Photopolymerization Initiator As the photopolymerization initiator contained in the B ink according to the present invention, the same photopolymerization initiator as that contained in the A ink described above can be used.
  • Reactive Diluent is a colorless, low-viscosity liquid that is added to a substance to reduce its viscosity and make it easier to handle.
  • the B ink according to the present invention preferably contains a reactive diluent, which can reduce the viscosity of the B ink.
  • 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 above. 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.
  • a photocurable compound as the reactive diluent for the B ink is even more preferable, as it suppresses bleeding during printing, resulting in higher resolution and better 3D formability when laminating thick films.
  • the amount of reactive diluent contained is determined by the amount that adjusts the viscosity of the ink to approximately 100 cp at 25°C. Since the function of the reactive diluent is to lower the viscosity of the ink, it is preferable that the viscosity of the B ink be 30 cp or less, more preferably 15 cp or less, and even more preferably 10 cp or less.
  • the reactive diluent content is 1% by mass or more relative to 100% by mass of the B ink according to the present invention, the viscosity-lowering effect is enhanced, and when it is 70% by mass or less, the content of the main ingredients, epoxy resin and thermosetting agent, can be ensured to be above a certain level. This allows for the desired film properties (thermal expansion coefficient, glass transition temperature, film strength, heat resistance, etc.). Therefore, the reactive diluent content in the B ink is preferably within the range of 1 to 70% by mass.
  • the B ink according to the present invention preferably contains a filler. This improves the physical properties of the cured film formed by applying and curing an ink set containing the B ink and the A ink.
  • the filler can be any conventionally known filler without any restrictions, and the same fillers as those used in Ink A described above can be used. One type can be used alone, or two or more types can be mixed together.
  • 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 B ink according to the present invention. This improves the ejection properties of the B ink. It is preferable that as much filler as possible be contained in the B ink, but if there is too much, the viscosity of the ink will become too high and it will not be possible to eject it in an inkjet manner. 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 A ink according to the present invention.
  • the average particle size of the filler, its measurement method, and commercially available products are the same as those for the filler that can be contained in Ink A described above.
  • the B ink 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 B ink according to the present invention may also contain a thermosetting catalyst, and may contain the same substances as those that can be contained in the A ink according to the present invention described above. However, since the pot life is longer when, for example, the epoxy resin, thermosetting catalyst, and thermosetting agent are not present in the same liquid, it is preferable that the B ink does not contain a thermosetting catalyst.
  • the ink A according to the present invention contains a thermosetting catalyst while the ink B does not, in order to promote the curing reaction after the two inks are mixed together and to extend the pot life of the ink B.
  • the water contained in the B ink 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 the B ink.
  • the organic solvent contained in the B ink according to the present invention is not particularly limited and can be any known organic solvent.
  • the organic solvent content is preferably kept to 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, relative to 100% by mass of the B ink.
  • Method for forming a cured product using a two-component ink set In the method for forming a cured product of the present invention, the A ink and the B ink constituting the two-component ink set are ejected from separate inkjet head nozzles, thereby extending the pot life of the two-component ink set.
  • Extending the pot life improves ejection stability.
  • the reason for improved ejection stability is that the ink's liquid properties are stable, which reduces fluctuations in ejection speed and suppresses the occurrence of nozzle gaps, bending, and satellites.
  • High ink ejection stability prevents deterioration in ink landing accuracy during image formation, which in turn maintains the mixing of the two liquids, ensuring stable film properties for the cured film formed in subsequent processes.
  • 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, wherein the cured product is a cured product consisting of the components of the ink A and ink B that constitute the two-component ink set of the present invention.
  • the two-component ink set of the present invention has excellent 3D formability and is therefore suitable for forming thick insulating films, and can be used, for example, as an insulating material between electrodes in thick copper PCBs (printed circuit boards).
  • 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 thickness of the typical copper substrate used in conventional electronic components and other products is expected to be 70 ⁇ m or less.
  • a hardened film that acts as an insulating resin layer, such as solder resist on the metal wiring surface of such electronic components, the load on the electronic components, such as current, can be reduced.
  • the thickness of the copper substrate used in such electronic components is different from normal thicknesses and is expected to be, for example, 140 ⁇ m or thicker. For this reason, the thickness of the hardened film formed on a normal copper substrate will be thicker.
  • 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 an extremely small thermal expansion coefficient compared to cured products of conventional inkjet-ejectable resin compositions. It also has a high glass transition temperature and excellent 3D formability. Therefore, it is suitable for flattening thick copper of 210 ⁇ m or more, particularly 300 ⁇ m or more, and can be used favorably in products such as electronic components.
  • ink components in Table I are as follows. The amount of each component in Table I is expressed in mass %. Ink [A8] in Table I contains "YH30", which is originally a heat curing agent. 6" was added in a catalytic amount.
  • SR833 Tricyclodecane dimethanol diacrylate (manufactured by Sartomer)
  • M222 Dipropylene glycol diacrylate (manufactured by Miwon)
  • M300 Trimethylolpropane triacrylate (manufactured by Miwon)
  • A-HD-N 1,6-hexanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • the ink components in Table II are as follows. The amounts of each component in Table II are expressed in mass %.
  • 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)
  • M222 Dipropylene glycol diacrylate (manufactured by Miwon)
  • M300 Trimethylolpropane triacrylate (manufactured by Miwon)
  • A0144 2-ethylhexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • A-NPG Neopentyl glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • ⁇ Thermosetting compound> "4300E” Bisphenol A type epoxy resin (manufactured by ADEKA Corporation). Although “4300E” is listed in the table, the product name is “EP-4300E.”
  • SA102 DBU compound (thermal latent base generator, manufactured by San-Apro Co., Ltd.)
  • SA102 DBU compound (thermal latent base generator, manufactured by San-Apro Co., Ltd.)
  • the product name is "U-CAT SA102”
  • 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 [G8] 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 [G8] were also prepared for film thicknesses of 100 ⁇ m, 200 ⁇ m, 300 ⁇ m, and 400 ⁇ m.
  • evaluation sample [G9] The ink A and ink B constituting the ink set were changed to obtain the ink set combination shown in Table VII, and a solid image was printed so that the ratio of the coverage of ink A to the coverage of ink B was 1:1.
  • Evaluation sample [G9] was prepared in the same manner as evaluation sample [G1], except that the heating temperature, voltage, and coverage of the inkjet head were adjusted so that the evaluation samples would be 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.
  • Cured film [ ⁇ ] was isolated from each of the Teflon (registered trademark) plate samples [Tef1] to [Tef9], and the cured film [ ⁇ ] was cut into a length of 20 mm and a width of 2 mm to prepare cured film sample pieces for evaluation [T1] to [T9].
  • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

La présente invention aborde le problème consistant à fournir : un ensemble d'encres à deux composants qui a une longue durée de vie en pot et avec lequel d'excellentes propriétés physiques de film peuvent être obtenues ; un procédé de formation d'un produit durci ; et un produit.　L'ensemble d'encres pour jet d'encre à deux composants comprend au moins une encre A et une encre B, l'encre A contenant au moins un composé photodurcissable, et l'encre B contenant au moins un composé thermodurcissable et un agent thermodurcissable.
PCT/JP2025/003521 2024-03-15 2025-02-04 Ensemble d'encres à deux composants, procédé de formation de produit durci et produit Pending WO2025192100A1 (fr)

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JP2024-041525 2024-03-15

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WO2025192100A1 true WO2025192100A1 (fr) 2025-09-18

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006159746A (ja) * 2004-12-09 2006-06-22 Konica Minolta Medical & Graphic Inc 光硬化型インクジェット記録方法
JP2013142130A (ja) * 2012-01-11 2013-07-22 Seiko Epson Corp 光硬化型インク組成物及び記録方法
JP2016204453A (ja) * 2015-04-17 2016-12-08 積水化学工業株式会社 インクジェット用組成物、半導体装置の製造方法、電子部品及び電子部品の製造方法
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
WO2023127797A1 (fr) * 2021-12-28 2023-07-06 太陽ホールディングス株式会社 Composition de résine photodurcissable, produit durci de celle-ci, et carte de circuit électronique pourvue dudit produit durci

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006159746A (ja) * 2004-12-09 2006-06-22 Konica Minolta Medical & Graphic Inc 光硬化型インクジェット記録方法
JP2013142130A (ja) * 2012-01-11 2013-07-22 Seiko Epson Corp 光硬化型インク組成物及び記録方法
JP2016204453A (ja) * 2015-04-17 2016-12-08 積水化学工業株式会社 インクジェット用組成物、半導体装置の製造方法、電子部品及び電子部品の製造方法
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
WO2023127797A1 (fr) * 2021-12-28 2023-07-06 太陽ホールディングス株式会社 Composition de résine photodurcissable, produit durci de celle-ci, et carte de circuit électronique pourvue dudit produit durci

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