Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
• • 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
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/28—Applying non-metallic protective coatings

Definitions

• the present invention relates to a curable composition.
• the present invention also relates to a cured product obtained by curing the curable composition and a printed wiring board including the cured product.
• Japanese Unexamined Patent Publication No. 2016-147970 Japanese Unexamined Patent Publication No. 2012-92312 Japanese Unexamined Patent Publication No. 2012-87298
• curable compositions such as those used in Patent Documents 1 to 3 are particularly inferior in adhesion after being left in high temperature and high humidity conditions, and have a problem that it is difficult to secure reliability over a long period of time. rice field. As a result, when an attempt was made to draw a fine pattern, peeling or crushing of the pattern was observed, and the development of a curable composition having excellent both adhesion and resolution was eagerly desired.
• an object of the present invention is to provide a curable composition having excellent flexibility and resolution, and excellent adhesion to copper after being left for a long period of time under high temperature and high humidity conditions.
• Another object of the present invention is to provide a cured product obtained by curing the composition and a printed wiring board provided with the cured product.
• the present inventors have found that the oxidation of the copper surface on which the cured film of the curable composition is formed causes a decrease in adhesion.
• a specific ion scavenger, a photosensitive monomer, and a photopolymerization initiator into the curable composition, the adhesion to copper after the accelerated test is excellent, which greatly affects the improvement in yield.
• the present inventors have surprisingly found that it is possible to provide a cured product having excellent flexibility and resolution in addition to the effect of improving the adhesion to copper, and the present invention has been made. Has been completed.
• the curable composition according to the present invention comprises (A) an ion scavenger containing at least one component selected from the group consisting of zirconium, aluminum, zinc, magnesium, calcium, antimony and bismuth, and (B) photosensitive. It is characterized by containing a sex monomer and (C) a photopolymerization initiator.
• the curable composition further contains (D) a thermosetting component and contains a blocked isocyanate as a thermosetting component.
• the content of the ion scavenger is preferably 0.01 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the curable composition.
• the photosensitive monomer contains a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate.
• the viscosity of the curable composition at 50 ° C. is preferably 50 mPa ⁇ s or less.
• the curable composition is for inkjet printing.
• the cured product according to another aspect of the present invention is characterized by being a cured product obtained by curing the curable composition.
• the printed wiring board according to another aspect of the present invention is characterized by being a printed wiring board provided with the cured product.
• the curable composition according to the present invention it is possible to provide a curable composition having excellent flexibility and resolution, and excellent adhesion to copper after being left for a long period of time under high temperature and high humidity conditions.
• the curable composition according to the present invention is suitable for inkjet printing.
• the curable composition according to the present invention comprises (A) an ion scavenger containing at least one component selected from the group consisting of zirconium, aluminum, zinc, magnesium, calcium, antimony and bismuth, and (B) photosensitive. It contains a sex monomer and (C) a photopolymerization initiator.
• the curable composition according to the present invention preferably further contains (D) a thermosetting component.
• the ion scavenger contained in the curable composition according to the present invention includes an inorganic scavenger that captures cations by ion exchange, an inorganic anion scavenger that captures anions by ion exchange, and cations by ion exchange. Examples thereof include an inorganic amphoteric scavenger that traps both ions and anions, and an inorganic amphoteric scavenger is preferred.
• the ion scavenger contained in the curable composition according to the present invention contains at least one component selected from the group consisting of zirconium, aluminum, zinc, magnesium, calcium, antimony and bismuth.
• two or more oxidative hydrates or hydroxides of these components are preferable, and two or more oxidative hydrates or hydroxides selected from the group consisting of zirconium, magnesium and aluminum are more preferable.
• hydrotalcite which is a three-component oxidative hydrate of magnesium, aluminum and zirconium, bismuth, and a two-component oxidative hydrate of zirconium and a hydroxide containing magnesium and aluminum, is preferable.
• the ion scavenger may be used alone or in combination of two or more.
• Hydrotalcite is represented by the following formula (1).
• n indicates the number of hydration, which is 0 or a positive number, which is preferable. Is 1 to 5.
• one in which a part of Mg is replaced with another divalent metal ion can also be preferably used.
• Zn is particularly preferable.
• hydrotalsite are not particularly limited, but for example, Mg 4.5 Al 2 (OH) 13 CO 3 ⁇ nH 2 O, Mg 5 Al 1.5 (OH) 12.5 CO 3 ⁇ nH 2 O, Mg 6 Al 2 (OH) 16 CO 3 ⁇ nH 2 O, Mg 4.2 Al 2 (OH) 12.4 CO 3 ⁇ nH 2 O, Mg 4.3 Al 2 (OH) 12.6 CO 3 ⁇ NH 2 O, Mg 2.5 Zn 2 Al 2 (OH) 13 CO 3 ⁇ nH 2 O, Mg 4.2 Al 2 (OH) 12.4 CO 3 ⁇ nH 2 O, Mg 4.2 Al 2 ( OH) 12.4 CO 3 ⁇ nH 2 O, Mg 4 Al 2 (OH) 12 CO 3 ⁇ nH 2 O, etc. 5), and among them, Mg 4.3 Al 2 (OH) 12.6 CO 3 ⁇ nH 2 O is preferable.
• a / b is preferably 1.5 or more and 5 or less, more preferably 1.7 or more and 3 or less, and 1.8 or more and 2.5. The following is more preferable.
• the average particle size of an ion scavenger containing at least one component selected from the group consisting of zirconium, aluminum, zinc, magnesium, calcium, antimony and bismuth is usually 5 ⁇ m or less, preferably 1 ⁇ m or less.
• the lower limit of the average particle size is not particularly limited, but is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, and further preferably 0.3 ⁇ m or more.
• the average particle size of the ion scavenger can be measured by a dynamic light scattering method.
• the ion scavenger can be measured by creating a particle size distribution of the ion scavenger on a volume basis with a dynamic light scattering type particle size distribution measuring device and using the median diameter (D 50 ) as the average particle size.
• a dynamic light scattering type particle size distribution measuring device As the measurement sample, an ion scavenger dispersed in water by ultrasonic waves can be preferably used.
• the dynamic light scattering type particle size distribution measuring device "Nanotrac Wave II UT151" manufactured by Microtrac Bell can be used.
• a commercially available ion scavenger containing at least one component selected from the group consisting of zirconium, aluminum, zinc, magnesium, calcium, antimony and bismuth may be used, for example, "IXEPLAS-A1” manufactured by Toa Synthetic Co., Ltd. , "IXEPLAS-A2", “IXEPLAS-A3", “IXEPLAS-B1", etc., "DHT-4A”, “DHT-4A-2", “DHT-4C”, etc. manufactured by Kyowa Chemical Industry Co., Ltd. ..
• the content of the ion scavenger containing at least one component selected from the group consisting of zirconium, aluminum, zinc, magnesium, calcium, antimony and bismuth is based on 100 parts by mass of the curable composition in terms of solid content. It is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.02 parts by mass or more and 5 parts by mass or less, and further preferably 0.03 parts by mass or more and 3 parts by mass or less.
• a curable composition having excellent flexibility and resolution and excellent adhesion to copper after being left for a long period of time under high temperature and high humidity conditions can be obtained. be able to.
• the photosensitive monomer is a monomer having an ethylenically unsaturated double bond.
• the photosensitive monomer for example, monofunctional (meth) acrylate and polyfunctional (meth) acrylate can be used.
• As the polyfunctional (meth) acrylate bifunctional (meth) acrylate and trifunctional or higher functional (meth) acrylate can be used.
• (meth) acrylate is a generic term for acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
• the photosensitive monomer may be used alone or in combination of two or more, but it is preferable to use two or more in combination.
• Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and 2-hydroxy.
• Examples thereof include (meth) acrylates such as ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and glycidyl methacrylate, and acryloyl morpholine.
• bifunctional (meth) acrylate examples include diols such as 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and 1,10-decanediol diacrylate.
• trifunctional or higher functional (meth) acrylate examples include trimethylolpropane triacrylate, trimethylolmethane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, and epichlorohydrin-modified trimethylolpropane triacrylate.
• Examples thereof include polyfunctional acrylates typified by sesquioxane-modified products, metaacrylate monomers corresponding thereto, and ⁇ caprolactone-modified trimethyloloxyethyl isocyanurate.
• the blending amount of the photosensitive monomer is preferably 30 parts by mass or more and 95 parts by mass or less, and more preferably 30 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the curable composition in terms of solid content. ..
• the blending amount of the photosensitive monomer is within the above numerical range, a curable composition having excellent flexibility and resolution and excellent adhesion to copper after being left for a long period of time under high temperature and high humidity conditions can be obtained. be able to.
• the photopolymerization initiator is for reacting the (B) photosensitive monomer by exposure. Any known photopolymerization initiator can be used. As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination.
• photopolymerization initiator examples include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis.
• Ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethyl benzoate, p-dimethylbenzoic acid ethyl ester; 1,2 -Octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] Oxim esters such as-, 1- (O-acetyloxime); bis ( ⁇ 5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) ) Phenyl) Titanium, bis (cyclopentadienyl) -bis [2,
• Examples of commercially available ⁇ -aminoacetophenone-based photopolymerization initiators include Omnirad 907, 369, 369E, 379 manufactured by IGM Resins.
• Examples of commercially available acylphosphine oxide-based photopolymerization initiators include Omnirad TPO H and 819 manufactured by IGM Resins.
• Commercially available products of oxime ester-based photopolymerization initiators include Irgacure OXE01 and OXE02 manufactured by BASF Japan Ltd., N-1919 manufactured by ADEKA Corporation, ADEKA Arkuru's NCI-831, NCI-831E, and Changzhou Powerful Electronics New Materials Co., Ltd. TR-PBG-304 and the like can be mentioned.
• the amount of the photopolymerization initiator to be blended is not particularly limited, but is preferably 0.2 parts by mass or more and 25 parts by mass or less, more preferably 0 parts by mass, based on 100 parts by mass of the curable composition in terms of solid content. It is 5 parts by mass or more and 20 parts by mass or less.
• a photoinitiator or sensitizer may be used in combination with the above-mentioned (C) photopolymerization initiator.
• the photoinitiator aid or sensitizer include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, xanthone compounds and the like.
• thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone.
• the deep curability can be improved.
• these compounds may be used as a photopolymerization initiator, they are preferably used in combination with a photopolymerization initiator.
• one type of photoinitiator aid or sensitizer may be used alone, or two or more types may be used in combination.
• thermosetting component Any known thermosetting component (D) can be used. Since the curable composition contains a thermosetting component, the heat resistance of the cured film can be improved.
• the heat-curable component include amino resins such as melamine resin, benzoguanamine resin, melamine derivative, and benzoguanamine derivative, isocyanate compounds, blocked isocyanate compounds, cyclocarbonate compounds, epoxy compounds, oxetane compounds, episulfide resins, bismaleimide, and carbodiimide resins.
• Known thermocuring components can be used.
• thermosetting component having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.
• cyclic (thio) ether groups cyclic (thio) ether groups
• one type may be used alone or two or more types may be used in combination.
• the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is a compound having a plurality of 3, 4, or 5-membered cyclic (thio) ether groups in the molecule, and is, for example, a plurality of compounds in the molecule.
• examples thereof include a compound having an epoxy group, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, and a compound having a plurality of thioether groups in the molecule, that is, an episulfide resin.
• epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, and phenol novolac type epoxy resin.
• examples thereof include cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, and triphenylmethane type epoxy resin.
• Epoxy urethane acrylate compounds obtained by reacting a half urethane compound may also be mentioned.
• Examples of commercially available epoxy resins include jER 828, 806, 807, YX8000, YX8034, 834 manufactured by Mitsubishi Chemical Corporation, YD-128, YDF-170, ZX-1059 manufactured by Nittetsu Chemical & Materials Co., Ltd. Examples thereof include ST-3000, EPICLON 830, 835, 840, 850, N-730A, N-695 manufactured by DIC Corporation, and RE-306 manufactured by Nippon Kayaku Corporation.
• polyfunctional oxetane compound examples include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, and 1,4-bis [(3-3-oxythenylmethoxy) methyl] ether.
• Methyl-3-oxetanylmethoxy) methyl] benzene 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-3) Oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and polyfunctional oxetane such as their oligomers or copolymers, as well as oxetane alcohols and novolak resins.
• Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin and the like. Further, using the same synthesis method, an episulfide resin or the like in which the oxygen atom of the epoxy group of the novolak type epoxy resin is replaced with a sulfur atom can also be used.
• amino resins such as melamine derivatives and benzoguanamine derivatives include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycol uryl compounds and methylol urea compounds.
• polyisocyanate compound a polyisocyanate compound can be blended.
• Polyisocyanate compounds include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and Aromatic polyisocyanates such as 2,4-tolyrene dimer; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; bicyclo Alicyclic polyisocyanates such as heptanthriisocyanate; and adducts, burettes, and isocyanurates
• an addition reaction product of the isocyanate compound and the isocyanate blocking agent can be used.
• the isocyanate compound capable of reacting with the isocyanate blocking agent include the above-mentioned polyisocyanate compound and the like.
• the isocyanate blocking agent include a phenol-based blocking agent; a lactam-based blocking agent; an active methylene-based blocking agent; an alcohol-based blocking agent; an oxime-based blocking agent; a mercaptan-based blocking agent; an acid amide-based blocking agent; an imide-based blocking agent; Amine-based blocking agents; imidazole-based blocking agents; imine-based blocking agents and the like can be mentioned.
• the amount of the thermosetting component (D) to be blended is not particularly limited, but is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 5 parts by mass, with respect to 100 parts by mass of the curable composition in terms of solid content. It is 25 parts by mass or less.
• the curable composition of the present invention may contain (E) a colorant.
• the colorant is not particularly limited, and known colorants such as red, blue, green, and yellow can be used, and any of pigments, dyes, and pigments may be used, but it may reduce the environmental load and affect the human body. It is preferable that the colorant does not contain halogen from the viewpoint of less.
• red colorants examples include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridone, etc.
• -Index CI; The Society of Dyers and Colorists (issued by The Society of Dyersand Colorists)) numbered ones can be mentioned.
• Pigment Red 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114, 146,147,151,170,184,187,188,193,210,245,253,258,266,267,268,269 and the like can be mentioned.
• Examples of the disazo-based red colorant include Pigment Red 37, 38, 41 and the like.
• Examples of the benzimidazolone-based red colorant include Pigment Red 171, 175, 176, 185, 208 and the like.
• Examples of the perylene-based red colorant include Solvent Red 135,179, Pigment Red 123,149,166,178,179,190,194,224 and the like.
• Examples of the diketopyrrolopyrrole-based red colorant include Pigment Red 254, 255, 264, 270, 272 and the like.
• Examples of the condensed azo red colorant include Pigment Red 220, 144, 166, 214, 220, 211, 242 and the like.
• Examples of the anthraquinone-based red colorant include Pigment Red 168, 177, 216 and Solvent Red 149, 150, 52, 207.
• Examples of the quinacridone-based red colorant include Pigment Red 122, 202, 206, 207, 209 and the like.
• blue colorant examples include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds include compounds classified as Pigment.
• Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70 and the like can be used.
• metal-substituted or unsubstituted phthalocyanine compounds can also be used.
• yellow colorant examples include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, etc.
• the anthraquinone yellow colorant includes Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202 and the like can be mentioned.
• the isoindolinone-based yellow colorant examples include Pigment Yellow 110, 109, 139, 179, 185 and the like.
• Pigment Yellow as a condensed azo yellow colorant 93, 94, 95, 128, 155, 166, 180 and the like can be mentioned.
• Examples of the benzimidazolone-based yellow colorant include Pigment Yellow 120, 151, 154, 156, 175, 181 and the like.
• Pigment Yellow 1,2,3,4,5,6,9,10,12,61,62,62: 1,65,73,74,75,97,100, 104, 105, 111, 116, 167, 168, 169, 182, 183 and the like can be mentioned.
• Examples of the disazo-based yellow colorant include Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198 and the like. Can be mentioned.
• colorants such as purple, orange, brown, black, and white may be added.
• the amount of the colorant (E) to be blended is not particularly limited, but is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0, with respect to 100 parts by mass of the curable composition in terms of solid content. It is 0.05 parts by mass or more and 10 parts by mass or less, and more preferably 0.1 parts by mass or more and 5 parts by mass or less.
• the curable composition of the present invention further includes an organic solvent, a photoinitiator, a cyanate compound, an elastomer, a mercapto compound, a urethanization catalyst, a thixotropic agent, an adhesion accelerator, a block copolymer, and a chain.
• Transfer agents polymerization inhibitors, antioxidants, surface tension modifiers, rust preventives, fine powder silica, organic bentonite, thickeners such as montmorillonite, silicone-based, fluorine-based, polymer-based defoaming agents and / or Ingredients such as leveling agents, silane coupling agents such as imidazole, thiazole, and triazole, flame retardants such as phosphinates, phosphoric acid ester derivatives, and phosphorus compounds such as phosphazene compounds can be blended. As these, those known in the field of electronic materials can be used.
• the curable composition of the present invention preferably has a viscosity suitable for the printing method to be used in consideration of workability, and more preferably has a viscosity suitable for inkjet printing.
• the viscosity of the curable composition at 50 ° C. is preferably 50 mPa ⁇ s or less, more preferably 20 mPa ⁇ s or less.
• the viscosity of the curable composition shall be 50 ° C., 100 rpm, 30 seconds value according to 10 "Conical-Viscosity measurement method by flat plate type rotational viscometer" of JIS Z 8803: 2011, and 1 ° 34'x as a cone rotor. It can be measured using a cone plate type viscometer (TVE-33H, manufactured by Toki Sangyo Co., Ltd.) using R24.
• TVE-33H manufactured by Toki Sangyo Co., Ltd.
• the curable composition according to the present invention is useful for forming a pattern layer as a permanent coating of a printed wiring board such as a solder resist, a coverlay, and an interlayer insulating layer, and is particularly useful for forming a solder resist. Further, since the curable composition of the present invention can form a cured product having excellent film strength even with a thin film, a pattern on a printed wiring board, for example, a package substrate (printed wiring board used for a semiconductor package), which is required to be thinned. It can also be suitably used for forming a layer. Further, the cured product obtained from the curable composition of the present invention is excellent in flexibility and can be suitably used for a flexible printed wiring board.
• the curable composition according to the present invention can be used not only for forming a pattern layer of a cured film but also for an application not forming a pattern layer, for example, a molding application (sealing application).
• the cured product of the present invention is obtained by curing the above-mentioned curable composition of the present invention.
• the cured product of the present invention is preferably obtained by curing the above-mentioned curable composition of the present invention by inkjet printing using an inkjet printer.
• the cured product of the present invention can be obtained by irradiating the curable composition immediately after printing with light and photo-curing it.
• Light irradiation is performed by irradiation with active energy rays such as ultraviolet rays, electron beams, and chemical rays, preferably by ultraviolet irradiation.
• Ultraviolet irradiation in an inkjet printer can be performed, for example, by attaching a light source such as a high-pressure mercury lamp, a metal halide lamp, or an ultraviolet LED to the side surface of the print head, and scanning by moving the print head or the base material. In this case, printing and ultraviolet irradiation can be performed almost at the same time.
• the inkjet printer can be performed by appropriately adjusting conventionally known conditions, and either the piezo method or the thermal method can be used, but the piezo method is preferable.
• the cured product of the present invention can be suitably used for printed wiring boards, electrical and electronic parts, and the like. Since the cured product of the present invention has excellent flexibility, it can be particularly preferably used for a flexible printed wiring board.
• the printed wiring board of the present invention comprises a cured product obtained by curing the curable composition of the present invention.
• the base material includes a printed wiring board and a flexible printed wiring board whose circuit is formed of copper or the like in advance, as well as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, and glass cloth / paper epoxy.
• Synthetic fiber epoxy, fluororesin / polyethylene / polyimideene ether, polyphenylene oxide / cyanate, etc. are used for high-frequency circuit copper-clad laminates, etc., and all grades (FR-4, etc.) of copper-clad laminates are used.
• Examples thereof include a plate, a metal substrate, a polyimide film, a polyethylene terephthalate film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, a wafer plate, and the like.
• a plate a metal substrate, a polyimide film, a polyethylene terephthalate film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, a wafer plate, and the like.
• PEN polyethylene naphthalate
• ⁇ Viscosity measurement of curable composition The viscosities of the curable compositions of Examples 1 to 6 and Comparative Examples 1 and 2 are 50 ° C., 100 rpm, and 30 seconds according to 10 "Conical-Viscosity measurement method using a flat plate type rotational viscometer" of JIS Z 8803: 2011. The value was measured using a cone plate type viscometer (TVE-33H, manufactured by Toki Sangyo Co., Ltd.) using 1 ° 34'x R24 as the cone rotor. As a result, the curable compositions of Examples 1 to 6 and Comparative Examples 1 and 2 all had a viscosity of 50 mPas ⁇ s or less, and were suitable for inkjet use.
• Inkjet printing was performed using a droplet amount of 6 pL, a number of nozzles of 2 ⁇ 1024, and a head temperature of 50 ° C.) so that a solid portion could be formed.
• the coated flexible printed wiring board was temporarily cured under the condition of 300 mJ / cm 2 using an LED (SGHUV-UN-L042-B, manufactured by Microcraft Co., Ltd., wavelength 365 nm) as a light source.
• LED SGHUV-UN-L042-B, manufactured by Microcraft Co., Ltd., wavelength 365 nm
• it was heated at 150 ° C. for 60 minutes in a hot air circulation type drying oven (manufactured by Yamato Scientific Co., Ltd., DF610) to form a cured coating film having a thickness of 20 ⁇ m.
• the evaluation criteria are as follows. The obtained evaluation results are shown in Table 1. (Evaluation criteria for flexibility) ⁇ : MIT resistance was 150 times or more. ⁇ : MIT resistance was 100 times or more and 149 times or less. ⁇ : MIT resistance was 50 times or more and 99 times or less. X: MIT resistance was 49 times or less.
• Inkjet printing was performed using CP56151 (manufactured by Microcraft) and an array of KM1024iSHE (manufactured by Microcraft, coating droplet amount 6 pL, number of nozzles 2 ⁇ 1024, head temperature 50 ° C.). Subsequently, the coated flexible printed wiring board was temporarily cured under the condition of 300 mJ / cm 2 using an LED (SGHUV-UN-L042-B, manufactured by Microcraft Co., Ltd., wavelength 365 nm) as a light source. Subsequently, it was heated at 150 ° C.
• the obtained solid cured coating film was exposed to the obtained cured coating film at a temperature of 85 ° C. and a humidity of 85% for 500 hours, left at room temperature for 24 hours, and then cross-cut using each of the prepared wiring boards.
• a tape peel test was conducted.
• the 100 squares formed were peeled off with cellophane tape (adhesion strength of 10 ⁇ 1N per 25 mm width), and the number of remaining squares was counted.
• the evaluation criteria are as follows.
• the obtained evaluation results are shown in Table 1. (Evaluation criteria for adhesion) ⁇ : The number of remaining squares was 100/100. ⁇ : The number of remaining cells was 90/100 or more and 99/100 or less. X: The number of remaining cells was 89/100 or less.
• -IXEPLAS-A1 Zr-Mg-Al system (manufactured by Toagosei Co., Ltd.)
• -DHT-4A Mg 4.3 Al 2 (OH) 12.6 CO 3 ⁇ nH 2 O (n indicates the number of hydration and is 0 or a positive number) (manufactured by Kyowa Chemical Industry Co., Ltd.)
• IBXA Isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
• 4HBA 4-Hydroxybutyl acrylate (manufactured by Nihon Kasei Co., Ltd.)
• -A-TMPT Trimethylolpropane triacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
• 1,9-NDA 1,9-nonanediol diacrylate (manufactured by Dai-
• the curable composition of the examples of the present application was able to obtain a cured coating film having excellent flexibility and resolution and excellent adhesion to copper.
• such a curable composition was suitable for inkjet printing.

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