Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
• • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
• • 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
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/322—Pigment inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

• the present invention relates to a photocurable composition suitably used for manufacturing electronic circuit boards such as display elements, printed wiring boards, flexible wiring boards, semiconductor package boards and solar cell boards.
• a coating agent that forms a film on the surface of base materials such as various resin plates, glass plates, and metal plates used in the fields of building materials and electricity / electronics to protect the base material from scratches and contamination.
• base materials such as various resin plates, glass plates, and metal plates used in the fields of building materials and electricity / electronics to protect the base material from scratches and contamination.
• Thermosetting resins and photocurable resins are used as coating agents, but when photocurable resins are used, cured products with high surface hardness are often obtained, and they are instantly cured by light irradiation. Due to its high productivity, photocurable resins are often used to protect the surface of organic substrates.
• a cured product using a photocurable resin generally does not have sufficient adhesion to an inorganic substrate. Therefore, various studies have been made to improve the adhesion to the inorganic substrate.
• Patent Document 1 contains a specific monofunctional polymerizable monomer component (A), a polyfunctional polymerizable monomer (B), and a polymerization initiator (C) in predetermined amounts, respectively.
• Inkjet inks are listed. By using the photocurable inkjet ink, it is possible to form a cured product having good adhesion to an inorganic substrate.
• An object of the present invention is to provide a photocurable composition capable of forming a cured product having good reliability in a high temperature and humidity environment, particularly ion migration resistance in a temperature range of 100 ° C. or higher.
• the present inventors have found that a composition capable of forming a cured product having good adhesion to an inorganic substrate and good ion migration resistance by combining specific components. I found it.
• the present invention is based on this finding and has the following configurations.
• the content of the monofunctional acrylic monomer (A) is 40 to 80% by weight with respect to 100% by weight of the composition (X).
• the monofunctional acrylic monomer (A) contains a (meth) acrylate having one or more of the group consisting of a fused ring hydrocarbon group, a polycyclic hydrocarbon group and a monocyclic hydrocarbon group.
• the photocurable composition (Z) according to any one of the above [1] to [11].
• R 1 is hydrogen or methyl
• R 2 is a monovalent with 4 to 30 carbon atoms having a fused ring hydrocarbon group, a polycyclic hydrocarbon group or a monocyclic hydrocarbon group. It is an organic group
• n A is an integer from 0 to 10.
• R 2 is the following formula in (2) to (5) is any one group represented by the photocurable composition according to the [13] (Z) ..
• R 3 is independently hydrogen or an alkyl having 1 to 6 carbon atoms, and * is a bond.
• R 4 is independently hydrogen or methyl
• R 5 has a fused ring hydrocarbon group, a polycyclic hydrocarbon group or a monocyclic hydrocarbon group and has 4 to 30 carbon atoms. It is a divalent organic group
• n B is an independently integer of 0 to 10.
• R 5 is the following formula in (7) - is any one group represented by the (10)
• composition (Z) according to any one of the above [1] to [18], wherein the composition (X) has a hydroxyl value of 5 to 40 mgKOH / g.
• the photocurable composition (Z) of the present invention is a photocurable composition (X) containing a monofunctional acrylic monomer (A) and a polyfunctional acrylic monomer (B) with an ion scavenger (Y) added.
• the composition (Z). By adding the ion scavenger (Y), the generation of cations and anions that cause ion migration can be suppressed, and the problem of ion migration can be fundamentally solved. Further, by adjusting the hydroxyl value of the composition (X), the ion migration resistance of the cured product itself obtained by curing the composition (X) and the adhesion to various substrates can be improved.
• composition (X) includes a monofunctional acrylic monomer (A) (hereinafter, also referred to as “component (A)” or simply “(A)”) and a polyfunctional acrylic monomer (B) (hereinafter, “component (B)”). , Or simply referred to as “(B)”).
• component (A) and (B) are compounds having a hydroxyl value of less than 100 mgKOH / g.
• the content of the component (A) in the composition (X) is 40 to 80% by weight with respect to 100% by weight of the composition (X), and the content of the component (B) is the composition (X) 100. It is 10 to 50% by weight with respect to% by weight.
• the component (A) and the component (B) in the composition (X) contribute to improving the ejection property and the photocurability when used as an ink jet ink, and also have heat resistance and a substrate, particularly a silicon substrate or a glass. It contributes to improving the adhesion to the substrate and the substrate on which conductors such as metal wiring and electrodes are formed on the substrate.
• the hydroxyl value of the composition (X) itself is further adjusted to 1 to 100 mgKOH / g. This makes it possible to improve the ion migration resistance of the cured product obtained by curing the composition (X) itself and the adhesion to various substrates. From the viewpoint of producing a cured product having excellent ion migration resistance, the hydroxyl value of the composition (X) itself is more preferably 2 to 40 mgKOH / g, further preferably 5 to 40 mgKOH / g.
• either or both of the component (A) and the component (B) have a hydroxyl value of, for example, 1 mgKOH / g or more.
• Ingredients may be used.
• a radically polymerizable compound (C) having a hydroxyl value of 100 to 300 mgKOH / g hereinafter, also referred to as “component (C)” or simply “(C)” may be used as the hydroxyl value adjusting agent.
• a part or all of the component (A) may be the component (C)
• a part or all of the component (B) may be the component (C). It may be, and may contain a component (C) which is a radically polymerizable compound other than the component (A) and the component (B).
• the composition (X) contains a monofunctional acrylic monomer (A).
• the component (A) improves the ejection property when the photocurable composition (Z) is used as an ink.
• the component (A) is also a component having excellent photocurability, and is suitable for forming a cured product having an excellent balance of heat resistance and adhesion to a substrate. From these viewpoints, the content of the component (A) is preferably 40 to 80% by weight, more preferably 50 to 75% by weight, based on 100% by weight of the composition (X).
• the component (A) is a fused cyclic hydrocarbon from the viewpoint of heat resistance and good adhesion to a substrate, particularly a glass substrate, a silicon substrate, or a substrate in which conductors such as metal wiring and electrodes are formed on these substrates. It preferably contains a (meth) acrylate having one or more of the group consisting of hydrogen groups, polycyclic hydrocarbon groups and monocyclic hydrocarbon groups.
• a monofunctional acrylic monomer having a fused ring hydrocarbon group or a polycyclic hydrocarbon group is designated as (a-1)
• a monofunctional polymerizable monomer having a monocyclic hydrocarbon group is designated as (a-2). It is exemplified as.
• (meth) acrylate is used to indicate both acrylate and methacrylate
• (meth) acryloyl is used to indicate both or one of acryloyl and methacryloyl.
• the monofunctional acrylic monomer (a-1) having a fused ring hydrocarbon group or a polycyclic hydrocarbon group is not particularly limited, but has 7 carbon atoms having a fused ring hydrocarbon group or a polycyclic hydrocarbon group. It is preferably a monofunctional acrylic monomer containing up to 50 organic groups, and preferably a monofunctional acrylic monomer containing a fused ring hydrocarbon group or a polycyclic hydrocarbon group having 7 to 30 carbon atoms. More preferred.
• the "monofunctional acrylic monomer” refers to a monomer having one (meth) acryloyl group in one molecule.
• the "condensed ring-type hydrocarbon group” is a hydrocarbon (consisting of a carbon atom and a hydrogen atom) group having two or more rings, and is a carbon that constitutes a certain ring and at the same time constitutes another ring.
• a hydrocarbon group having at least one atom a "polycyclic hydrocarbon group” is a hydrocarbon group having two or more rings, and one ring and another ring have a single bond or the number of carbon atoms.
• the "organic group having 7 to 50 carbon atoms having the fused ring hydrocarbon group or the polycyclic hydrocarbon group” is, for example, the (meth) acryloyl group in the compound represented by the formula (1).
• the monomer (a-1) it is preferable to use the compound represented by the formula (1) from the viewpoint of obtaining a cured product having excellent heat resistance and adhesion to the substrate.
• R 2 is a monovalent organic group having 4 to 30 carbon atoms having a fused ring hydrocarbon group or a polycyclic hydrocarbon group, and is preferably non-polar and has a fused ring. It is a monovalent organic group having 4 to 30 carbon atoms and having a type hydrocarbon group or a polycyclic hydrocarbon group, and more preferably a group represented by any one of the above formulas (2) to (5). Is. As the n A 0 or 1 is preferred.
• the monomer (a-1) at least one compound selected from the following compound group (I) is preferable.
• the following compounds (11) to (20) are more preferable, and the compounds (11) and (17) are further preferable, considering the adhesion of the obtained cured product to the substrate and heat resistance.
• the monomer (a-1) may be one kind of compound selected from the above-mentioned compounds and the like, or may be a mixture of two or more kinds thereof.
• a mixture of compounds (11) and (17) is preferable, and when both are used in combination, the weight ratio of compound (11): compound (17) is preferably 5:10 to 10: 5, and 7:10 to 10: 7. Is more preferable, and 9:10 to 10: 9 is even more preferable.
• a compound produced by a known method may be used, or dicyclopentanyl acrylate (trade name; funkryl FA-513AS: Hitachi Kasei Kogyo Co., Ltd.), di. Cyclopentanyl methacrylate (trade name; funcryl FA-513M: Hitachi Kasei Kogyo Co., Ltd.), dicyclopentenyl acrylate (trade name; funcryl FA-511AS: Hitachi Kasei Kogyo Co., Ltd.), dicyclopentenyl methacrylate (trade name; Name; Funkryl FA-511M: Hitachi Kasei Kogyo Co., Ltd., Dicyclopentenyloxyethyl acrylate (trade name; Funkrill FA-512AS: Hitachi Kasei Kogyo Co., Ltd.), Dicyclopentenyloxyethyl methacrylate (trade name; Funkril FA-512M: Hitachi Kasei Kogyo Co., Ltd., I
• the "monocyclic hydrocarbon group” refers to a hydrocarbon group having one ring (including an aromatic ring).
• a compound produced by a known method may be used, or benzyl acrylate, cyclohexyl acrylate (trade name; V # 155: Osaka Organic Chemical Industry Co., Ltd.), cyclohexyl methacrylate.
• Commercially available products such as (trade name; light ester CH: Kyoeisha Chemical Co., Ltd.) may be used.
• the composition (X) contains a polyfunctional acrylic monomer (B).
• the "polyfunctional acrylic monomer” refers to a monomer having two or more (meth) acryloyl groups in one molecule.
• 10 to 50% by weight of the component (B) can be used with respect to 100% by weight of the entire composition (X).
• component (B) examples include tricyclodecanedimethanol di (meth) acrylate, bisphenol F ethylene oxide-modified di (meth) acrylate, bisphenol A ethylene oxide-modified di (meth) acrylate, and isocyanurate ethylene oxide-modified di (meth).
• Acrylate polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, trimethylolpropane di.
• any one of the formulas (6) R 5 is the equation in (7) - (10)
• the compound represented by the group is preferable, and the group represented by the above formula (7) is more preferable. Further, 0 or 1 is preferable as n B.
• the component (B) may be one kind of compound selected from the above-mentioned compounds and the like, or may be a mixture of two or more kinds thereof.
• the component (B) improves the photocurability of the composition (X).
• the component (B) is also suitable for forming a cured product having an excellent balance of heat resistance and adhesion to a substrate. From these viewpoints, the content of the component (B) is preferably 10 to 50% by weight, more preferably 13 to 30% by weight, still more preferably 15 to 25% by weight, based on 100% by weight of the composition (X). ..
• the composition (X) preferably has a hydroxyl value adjusted to 1 to 100 mgKOH / g from the viewpoint of improving the ion migration resistance of the cured product itself and the adhesion to various substrates.
• a radically polymerizable compound (C) having a hydroxyl value of 100 to 300 mgKOH / g can be used.
• part or all of the component (A) may be the component (C)
• part or all of the component (B) may be the component (C).
• a component (C) which is a radically polymerizable compound other than the component (A) and the component (B) may be contained.
• the component (C) may be used as one kind or a mixture of two or more kinds.
• the component (C) which is a radically polymerizable compound other than the component (A) and the component (B), is used, the component (C) functions as a hydroxyl value adjusting agent and serves as the component (A) or the component (B).
• a compound having a hydroxyl value lower than that of the component (C) can be used, or a compound having no hydroxyl group can also be used.
• a monofunctional acrylic monomer having no hydroxyl group can be selected as the component (A), or a polyfunctional acrylic monomer having no hydroxyl group as the component (B).
• a radically polymerizable compound that can be selected and has a hydroxyl group as the component (C) is blended to adjust the hydroxyl value of the entire composition (X).
• the content of the component (C) is preferably 0.1 to 30% by weight, preferably 0.3% by weight, based on 100% by weight of the composition (X). It is more preferably from 25% by weight, still more preferably from 0.5 to 20% by weight.
• the hydroxyl value of the component (C) is preferably 100 to 300 mgKOH / g, more preferably 150 to 200 mgKOH / g.
• the component (C) contains an acrylic oligomer.
• the weight average molecular weight of the component (C) is preferably 100 to 5,000, more preferably 300 to 3,000, and even more preferably 500 to 1,500.
• the glass transition point (Tg) of the radically polymerizable compound (C) is preferably 85 ° C. or higher, more preferably 90 ° C. or higher.
• the composition (X) may further contain a photopolymerization initiator (D).
• the photopolymerization initiator may be any compound that can initiate polymerization of the monomer component contained in the composition (X) and that generates radicals by irradiation with ultraviolet rays, visible light, electromagnetic waves, or the like, and generally used compounds can be used. ..
• photopolymerization initiator examples include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-.
• the photopolymerization initiator (D) is preferably 5 to 15% by weight, more preferably 7 to 12% by weight, based on 100% by weight of the composition (X), from the viewpoint of forming a cured product having good ion migration resistance.
• the photopolymerization initiator (D) may be one kind of compound or a mixture of two or more kinds of compounds.
• an ion scavenger (Y) is further added to the composition (X) to obtain a photocurable composition (Z).
• the ion scavenger (Y) used in addition to the composition (X) has at least one selected from the group consisting of Zr (zirconium), Bi (bismuth), Mg (magnesium) and Al (aluminum).
• the "ion scavenger” is not particularly limited as long as it can capture ions and has a function of capturing at least one of a cation and an anion.
• the ions captured in the present invention are incorporated into a photocurable composition (Z) that reacts by irradiation with light, an electron beam, or the like and whose solubility in a solvent changes, for example, sodium ion (Na + ), chloride ion (). It is an ion such as Cl ⁇ ), bromine ion (Br ⁇ ), copper ion (Cu + , Cu 2+ ), and by capturing these ions, electrical insulation and electrolytic corrosion resistance are improved.
• a photocurable composition (Z) that reacts by irradiation with light, an electron beam, or the like and whose solubility in a solvent changes, for example, sodium ion (Na + ), chloride ion (). It is an ion such as Cl ⁇ ), bromine ion (Br ⁇ ), copper ion (Cu + , Cu 2+ ), and by capturing these ions, electrical insulation and electrolytic corrosion resistance are improved.
• Examples of the ion scavenger that captures such ions include a cation scavenger that captures cations, an anion scavenger that captures anions, and both cation and anion scavengers.
• cation trapping agent for capturing cations
• examples of the cation trapping agent for capturing cations include zirconium phosphate, zirconium tungstate, zirconium molybdate, zirconium antimonate, zirconium selenate, zirconite terlate, zirconium silicate, zirconium phosphate, zirconium polyphosphate and the like.
• Inorganic ion exchangers such as metal oxides of the above can be mentioned.
• these cation scavengers are IXE-100 (Zr-containing compound) and IXE-150 (Zr-containing compound) marketed by Toagosei Corporation. Etc. can be used.
• anion scavenger examples include inorganic ion exchangers such as bismuth oxide hydrate and hydrotalcites. Further, these anion scavengers (also referred to as "inorganic ion exchangers") are IXE-500 (Bi-containing compound) and IXE-530 (Bi-containing compound) marketed by Toa Synthetic Co., Ltd.
• IXE-550 (Bi-containing compound), IXE-700 (Mg, Al-containing compound), IXE-700F (Mg, Al-containing compound), IXE-770D (Mg, Al-containing compound), IXE-702 (Al-containing compound) ), IXE-800 (Zr-containing compound) and the like can be used.
• amphoteric scavenger examples include inorganic ion exchangers such as metal hydrous oxides such as aluminum oxide hydrate and zirconium oxide hydrate.
• inorganic ion exchangers such as metal hydrous oxides such as aluminum oxide hydrate and zirconium oxide hydrate.
• these two ion scavengers are IXE-1320 (Mg, Al-containing compound) and IXE-600 (Bi-containing) marketed by Toa Synthetic Co., Ltd.
• IXE-633 (Bi-containing compound), IXE-680 (Bi-containing compound), IXE-6107 (Zr, Bi-containing compound), IXE-6136 (Zr, Bi-containing compound), IXEPLAS-A1 (Zr, Mg). , Al-containing compound), IXEPLAS-A2 (Zr, Mg, Al-containing compound), IXEPLAS-B1 (Zr, Bi-containing compound) can also be used.
• the component (Y) can use the above-mentioned cation scavenger, anion scavenger, and both ion scavengers alone or in combination of two or more.
• cation scavenger anion scavenger
• ion scavengers both ion scavengers alone or in combination of two or more.
• an amphoteric scavenger that functions independently.
• the amount of the ion scavenger (Y) added is preferably 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the composition (X) from the viewpoint of improving electrical insulation and electrolytic corrosion resistance. Parts are more preferable, and 0.5 to 2 parts by weight are even more preferable.
• the dispersant may be further added to the composition (X) and used.
• the dispersant that can be used is not limited, and can be appropriately selected in consideration of the influence of the dispersibility of the ion scavenger (Y) and the adhesion of the photocurable composition (Z) to the substrate.
• the amount added is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, when the weight of the ion scavenger (Y) is 100 parts by weight.
• 0.1 part by weight is preferable, and from the viewpoint of sufficiently exerting the ion-capturing function of the ion scavenger (Y), 100 It is preferably parts by weight or less.
• the viscosity at 25 ° C. is preferably 1 to 150 mPa ⁇ s, preferably 3 to 70 mPa ⁇ s, from the viewpoint of improving the ejection property. Is more preferable.
• the present invention can also be carried out as an inkjet ink composition containing the photocurable composition (Z) of the present invention, or as an active energy ray-curable ink composition containing an inkjet ink composition.
• the active energy ray means an energy ray capable of decomposing a compound that generates an active species to generate an active species. Examples of such active energy rays include light energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, ⁇ rays, ⁇ rays, ⁇ rays, and electron rays.
• the photocurable composition (Z) of the present invention has a flame retardant, a resin containing a phenolic hydroxyl group, a melamine resin, an epoxy compound, an oxetane compound, a curing agent, a surfactant, and a coloring agent in order to improve various properties.
• a flame retardant a resin containing a phenolic hydroxyl group
• a melamine resin an epoxy compound, an oxetane compound, a curing agent, a surfactant, and a coloring agent
• Polymerization inhibitors and other components such as solvents may be included as long as the effects of the present invention are not impaired.
• the cured product of the present invention can be obtained by photo-curing the photocurable composition (Z) of the present invention.
• a cured product can be produced by a method including the following steps 1 and 2.
• Step 1 Step of applying the photocurable composition (Z) of the present invention onto a substrate by an inkjet method to form a coating film
• Step 2 Step of applying the photocurable composition (Z) of the present invention onto a substrate by an inkjet method to form a coating film
• Step 2 The coating film obtained in Step 1 is coated with light.
• the inkjet method is not particularly limited, and a known inkjet method can be used.
• the substrate is not particularly limited as long as it can be applied with the ink of the present invention, and its shape is not limited to a flat plate shape, and may be a curved surface shape or the like.
• the substrate is not particularly limited, but is, for example, a polyester resin substrate made of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc .; a polyolefin resin substrate made of polyethylene, polypropylene, or the like; polyvinyl chloride, fluororesin.
• Organic polymer film composed of acrylic resin, polyamide, polycarbonate, polyimide, etc .; cellophane; metal foil; laminated film of polyimide and metal foil; glassin paper, parchment paper, polyethylene, clay binder, polyvinyl alcohol having a sealing effect.
• the ink of the present invention can be easily applied in a predetermined pattern, and a uniform pattern can be formed on a large substrate.
• the temperature at the time of ejection by the inkjet coating device is preferably 10 to 120 ° C.
• the viscosity of the ink of the present invention at the temperature is preferably 1 to 30 mPa ⁇ s, more preferably 2 to 25 mPa ⁇ s, and even more preferably 3 to 20 mPa ⁇ s.
• heating the inkjet head to lower the viscosity of the ink at the time of ejection enables more stable ejection.
• the heating temperature is preferably 40 to 120 ° C.
• the thickness of the obtained coating film may be appropriately selected according to the desired application, but is preferably 1 to 20 ⁇ m, more preferably 5 to 15 ⁇ m.
• the amount of exposure to be irradiated may be appropriately adjusted according to the composition of the photocurable composition (Z) of the present invention, but a UV monitor manufactured by Opsystec (“UV-Pad”” , wavelength: when measured using a UV-a (315-400nm)), preferably about 100 ⁇ 10,000mJ / cm 2, more preferably about 150 ⁇ 5,000mJ / cm 2, 180 ⁇ 3,000mJ / About cm 2 is more preferable, and about 200 to 2,000 mJ / cm 2 is particularly preferable.
• the wavelength of ultraviolet rays, visible light, etc. to be irradiated is preferably 200 to 500 nm, more preferably 300 to 450 nm.
• An exposure machine may be used when irradiating light, and the exposure machine is equipped with a UV-LED lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a halogen lamp, a black light lamp, or the like.
• a device that irradiates ultraviolet rays, visible light, or the like in the range of 200 to 500 nm is preferable.
• the cured product cured by irradiation with light may be further heated and fired.
• a stronger cured product can be obtained by heating and baking at 80 to 250 ° C. for 10 to 60 minutes.
• the thickness of the cured product of the present invention may be appropriately selected according to the desired application, but is preferably 1 to 20 ⁇ m, more preferably 5 to 15 ⁇ m.
• the cured product of the present invention has a glass transition temperature of preferably 85 ° C. or higher measured using DMS6000 (Hitachi High-Technologies Corporation) from the viewpoint of manufacturing a highly reliable electronic circuit substrate or the like. More preferably, it is 90 to 150 ° C.
• a voltage application insulation resistance test (hereinafter referred to as an ion migration resistance test) under a constant temperature and humidity constant environment may be carried out.
• ion migration resistance test a specific voltage is applied for a specific time under a specific constant temperature and humidity constant environment, and the presence or absence of an abnormality in the resistance value at that time is confirmed.
• evaluation is often performed at a high temperature of 85 to 130 ° C. Therefore, in order to obtain a highly reliable electronic circuit substrate or the like, it is desirable that the glass transition temperature of the cured product is within the above range. ..
• the cured product of the present invention is a cured product having excellent heat resistance, adhesion to a substrate, and ion migration resistance, display elements such as liquid crystal display elements or EL display elements, printed wiring boards, flexible wiring boards, and semiconductor packages It is suitably used as a protective film and an insulating film in an electronic circuit board such as a substrate and a solar cell substrate. Further, the cured product of the present invention is suitably used for metal wiring forming a predetermined circuit pattern, a coverlay film for protecting conductors such as electrodes, solder resist and the like.
• the electronic component of the present invention contains the cured product of the present invention and is produced by a method including the steps 1 and 2. Since the cured product of the present invention is excellent in heat resistance, adhesion to a substrate, ion migration resistance, etc., the electronic component of the present invention is an electronic component excellent in electrical characteristics, long-term reliability, and the like.
• IXEPLAS-A1 amphoteric scavenger (trade name; IXEPLAS-A1, Toagosei Co., Ltd., Zr, Mg, Al-containing compound)
• IXEPLAS-A2 amphoteric scavenger (trade name; IXEPLAS-A2, Toagosei Co., Ltd., Zr, Mg, Al-containing compound)
• UV-Pad photocured by irradiating with UV-A (315-400 nm)), and heated and baked at 200 ° C for 60 minutes in a clean oven DT-610 (manufactured by Yamato Kagaku Co., Ltd.). By doing so, a substrate 1 on which a cured product having a thickness of 16 ⁇ m was formed was obtained. The film thickness of the cured product on the facing comb electrode was measured with a laser microscope VK-X100 (manufactured by KEYENCE CORPORATION).
• Examples 2 to 4 Comparative Example 1> Each component of Example 1 was changed to the component shown in Table 1, and compositions 2 to 5 were prepared by the same method as in Example 1. Using the obtained compositions 2 to 5, substrates 2 to 5 were prepared in the same manner as in Example 1.
• the ion migration resistance (IMG resistance) of the substrates (1 to 5) obtained above was evaluated by the following method.
• the obtained substrate and the ion migration tester MIG-87 (manufactured by IMV Co., Ltd.) are connected by wiring, installed in the advanced accelerated life test device EHS-411 (manufactured by ESPEC Co., Ltd.), and then 130 ° C. ⁇ 100.
• a DC voltage of 100 V was applied to the facing comb-shaped electrode pattern for 96 hours under the environment of%.
• IMG resistance Resistance value of opposed comb-shaped electrode pattern after 96 hours ⁇ : Resistance value indicates 1 ⁇ 10 6 ⁇ or more ⁇ : Resistance value indicates less than 1 ⁇ 10 6 ⁇ Electrode discoloration: Electrode after 96 hours The presence or absence of discoloration was observed with a laser microscope VK-X100 (manufactured by KEYENCE CORPORATION). ⁇ : No discoloration of the electrode ⁇ : Discoloration of the electrode
• the Tg of the cured product was calculated from the Fox formula based on the weight ratio of each component.
• the hydroxyl value of the composition (X) was calculated based on the hydroxyl value of each component.
• the viscosity of the photocurable composition (Z) was measured at 25 ° C. using an E-type viscometer (TV-22, Toki Sangyo Co., Ltd., the same applies hereinafter).
• the ion migration resistance of the cured product in the temperature range of 100 ° C. or higher (hereinafter, appropriately referred to as “IMG resistance”) was improved. From this result, it can be said that it is effective for the ion scavenger (Y) to capture ions that reduce IMG resistance in order to improve IMG resistance.
• the low IMG resistance in Comparative Example 1 containing no ion scavenger (Y) indicates that it was not possible to capture the ions that reduce the IMG resistance.
• the photocurable composition of the present invention can form a cured product having excellent reliability in a high temperature and humidity environment, particularly ion migration resistance in a temperature range of 100 ° C. or higher, for example, a display element or a printed wiring board.
• a display element or a printed wiring board.

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• 2021
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