Classifications

• • 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
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • 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
  • C09D11/30—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
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate

Definitions

• the present invention relates to a curable composition, a cured product, and a printed wiring board.
• Solder resist is used on the surface layer of printed wiring boards and semiconductor package substrates, and plays a role in protecting the circuit patterns formed on the substrates from external shocks and stresses such as heat and moisture.
• Screen printing and other methods have been conventionally known as methods of coating substrates with solder resist.
• In the method of forming a film by screen printing there are many processing steps such as development, and the work is also complicated. It's becoming The inkjet method does not require the production of a screen mesh, a photomask, etc., and can reduce the number of processes compared to the screen printing method, etc., and therefore has a great advantage in terms of cost reduction and takt time reduction.
• the inkjet method in order to stably eject the ink from the inkjet head, it is required that the ink viscosity be somewhat low.
• An inkjet device capable of printing by heating the inkjet head has also been developed, but printing troubles such as nozzle clogging tend to occur due to the drying of the ink in the vicinity of the nozzle due to heating. Diluting the curable resin composition for inkjet with a high boiling point solvent can slightly improve the ejection performance with an inkjet head with a small nozzle size. problems such as thinning of the film.
• the walls of the minute pressure chambers connected to the nozzles are deformed by piezoelectric (piezo) elements to change the volume of the pressure chambers. Ink droplets will be ejected from the For this reason, the viscosity of the curable resin composition of the piezo head is required to be several tens of mPa ⁇ s or less.
• dischargeability such as that the curable resin composition does not solidify in the head, that no precipitates occur, and that fine nozzles do not clog due to drying. Items must be met.
• Patent Document 1 it has a viscosity suitable for application to an inkjet printer, can draw a pattern directly on a substrate for a printed wiring board, cures at a relatively low temperature, and furthermore has excellent adhesion after curing.
• a photocurable thermosetting resin composition having chemical resistance, heat resistance, and insulating properties a photocurable thermosetting resin composition containing a (meth)acryloyl group-containing monomer, a blocked isocyanate, and a photopolymerization initiator A thermosetting resin composition is disclosed.
• the inventors of the present invention have made intensive studies to achieve the above object, and found that the inclusion of three compounds having an isocyanurate skeleton improves the compatibility of the curable composition, resulting in good dischargeability. I found that it gives, and came to complete the present invention.
• the curable composition according to the present invention is characterized by containing three or more compounds having an isocyanurate skeleton.
• Curable compositions according to aspects of the present invention have good compatibility.
• a curable composition having good compatibility is less likely to solidify in the ink head and less likely to generate precipitates, so clogging of nozzles is less likely to occur. Therefore, the curable composition according to the aspect of the present invention has good ejection properties and is suitable as a curable composition for use in inkjet printing.
• At least three compounds having an isocyanurate skeleton among the three or more compounds having an isocyanurate skeleton are (A) a thermosetting compound having an isocyanurate skeleton, and (B) It is preferably at least one selected from the group consisting of (meth)acrylate compounds having an isocyanurate skeleton.
• At least two of the three or more compounds having an isocyanurate skeleton are preferably (A) thermosetting compounds having an isocyanurate skeleton.
• the curable composition according to the aspect of the present invention preferably contains (A) a thermosetting compound having an isocyanurate skeleton and (B) a (meth)acrylate compound having an isocyanurate skeleton.
• the blending ratio of component (A) and component (B) is 5-15:10-20.
• the curable composition according to the aspect of the present invention preferably contains four or more compounds having an isocyanurate skeleton.
• the component (A) is preferably a blocked isocyanate compound having an isocyanurate skeleton.
• the curable composition preferably further contains a photopolymerization initiator, a colorant, or a thermosetting catalyst.
• the viscosity of the curable composition is 1 to 150 mPa ⁇ s at 25°C.
• a curable composition according to aspects of the present invention can be used for inkjet printing.
• a cured product according to another aspect of the present invention is characterized by being obtained by curing the curable composition described above.
• a printed wiring board according to another aspect of the present invention is characterized by comprising the cured product described above.
• a curable composition comprising three or more compounds having an isocyanurate skeleton.
• At least three of the three or more compounds having an isocyanurate skeleton are (A) a thermosetting compound having an isocyanurate skeleton, and (B) a (meth)acrylate compound having an isocyanurate skeleton.
• the curable composition according to [1] which is at least one selected from the group consisting of: [3]
• the curable composition according to [1], wherein at least two of the three or more compounds having an isocyanurate skeleton are (A) a thermosetting compound having an isocyanurate skeleton.
• thermosetting compound having an isocyanurate skeleton (B) a (meth)acrylate compound having an isocyanurate skeleton;
• a curable composition comprising four or more compounds having an isocyanurate skeleton.
• the curable composition according to any one of [1] to [10] which has a viscosity of 150 mPa ⁇ s or less at 25°C.
• a printed wiring board comprising the cured product of [13].
• the curable composition of the present invention has good compatibility and therefore provides a curable composition with excellent ejection properties.
• the cured product obtained by curing the curable composition of the present invention has good crack resistance, soldering heat resistance and tensile resistance, and is suitable as a solder resist composition for printed wiring boards.
• a curable composition according to one embodiment of the present invention contains three or more compounds having an isocyanurate skeleton.
• a compound having an isocyanurate skeleton improves the compatibility of the curable composition and improves the ejection property.
• a compound having an isocyanurate skeleton (essential component)
• compounds having an isocyanurate skeleton include isocyanate compounds having an isocyanurate skeleton, blocked isocyanate compounds having an isocyanurate skeleton, epoxy compounds having an isocyanurate skeleton, (meth)acrylate compounds having an isocyanurate skeleton, and isocyanurate skeletons.
• the amount of the three or more compounds having an isocyanurate skeleton is 1 to 99% by mass in terms of solid content in the curable composition from the viewpoint of improving the compatibility of the curable composition. Preferably, it is more preferably 20 to 50% by mass.
• At least three compounds having an isocyanurate skeleton among the three or more compounds having an isocyanurate skeleton are (A) a thermosetting compound having an isocyanurate skeleton, and (B) may be at least one selected from the group consisting of (meth)acrylate compounds having an isocyanurate skeleton.
• thermosetting compound having an isocyanurate skeleton (A) a thermosetting compound having an isocyanurate skeleton, (B) a (meth)acrylate having an isocyanurate skeleton Compounds and (C) antioxidants having an isocyanurate skeleton are exemplified, but are not limited to these.
• thermosetting compound having an isocyanurate skeleton used in the curable composition according to the present embodiment is not particularly limited, and a known and commonly used one may be used.
• thermosetting compound having an isocyanurate skeleton excludes (B) a (meth)acrylate having an isocyanurate skeleton, which will be described later.
• the thermosetting compounds having an isocyanurate skeleton may be used alone or in combination of two or more.
• the blending amount is preferably 1 to 20% by mass, preferably 2 to 16% by mass, in terms of solid content in the curable composition. more preferred.
• thermosetting compound having an isocyanurate skeleton used in the curable composition according to the present embodiment, from the viewpoint of improving the compatibility of the curable composition, an isocyanate compound having an isocyanurate skeleton, or an isocyanurate skeleton
• a blocked isocyanate compound having The isocyanate compound having an isocyanurate skeleton or the blocked isocyanate compound having an isocyanurate skeleton may be used alone or in combination of two or more.
• the presence or absence of an isocyanurate skeleton in the isocyanate compound or blocked isocyanate compound can be confirmed by isocyanate titration using a di-n-butylamine solution, gas chromatography, refractive index, viscosity, infrared spectroscopy, and the like.
• An isocyanate compound is a compound having one or more isocyanate groups in one molecule.
• a blocked isocyanate compound is a compound having an isocyanate group blocked with a blocking agent (blocked isocyanate group). The blocked isocyanate compound is obtained by reacting a part or all of the isocyanate groups of the isocyanate compound with a blocking agent, and the protective groups (residues of the blocking agent) are dissociated by heating to generate isocyanate groups.
• the blocking agent used to block (protect) the isocyanate group may be one that reacts with the isocyanate group to protect the isocyanate group and dissociates during heating to generate the isocyanate group, and the type thereof is particularly Not limited.
• blocking agents for isocyanate groups include lactam blocking agents ( ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -propiolactam, etc.), active methylene blocking agents (diethyl malonate, dimethyl malonate, ethyl acetoacetate, acetylacetone, etc.), oxime blocking agents (formaldoxime, acetoaldoxime, acetoxime, methyl ethyl ketone oxime, diacetyl monoxime, cyclohexanone oxime, etc.), pyrazole blocking agents (dimethylpyrazole, etc.), and the like.
• lactam blocking agents ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -propiolactam, etc.
• active methylene blocking agents diethyl malonate, dimethyl malonate, ethyl acetoacetate,
• the isocyanate group blocking agent in the isocyanate compound having an isocyanurate skeleton is preferably an oxime blocking agent, an active methylene blocking agent, a lactam blocking agent, and a pyrazole blocking agent. Blocking agents and pyrazole-based blocking agents are more preferred. An isocyanate group may be protected by one blocking agent, or two or more blocking agents may be used in combination.
• the isocyanurate skeleton can be obtained by cyclotrimerizing isocyanate groups of various aromatic isocyanate compounds, aliphatic isocyanate compounds, alicyclic isocyanate compounds, and the like.
• the isocyanate compound having an isocyanurate skeleton or the blocked isocyanate compound having an isocyanurate skeleton those obtained by cyclotrimerizing the isocyanate groups of various diisocyanate compounds or triisocyanate compounds are preferred.
• Diisocyanate compounds include, for example, 1,4-tetramethylene diisocyanate, ethyl (2,6-diisocyanate) hexanoate, 1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2,4- or 2, Aliphatic diisocyanate compounds such as 4,4-trimethylhexamethylene diisocyanate; 1,3- or 1,4-bis(isocyanatomethylcyclohexane), 1,3- or 1,4-diisocyanatocyclohexane, 3-isocyanato-methyl-3 , 5,5-trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4′-diisocyanate, 2,5- or 2,6-diisocyanatomethylnorbornane and other aliphatic diisocyanate compounds; m- or p-phenylene diisocyanate, tolylene-2, 4-
• triisocyanate compounds include aliphatic triisocyanate compounds such as 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, and 2-isocyanatoethyl (2,6-diisocyanate) hexanoate.
• alicyclic triisocyanate compounds such as 2,5- or 2,6-diisocyanatomethyl-2-isocyanatopropyl norbornane; aromatic triisocyanate compounds such as triphenylmethane triisocyanate and tris(isocyanatophenyl)thiophosphate; mentioned.
• Examples of commercially available isocyanate compounds having an isocyanurate skeleton or blocked isocyanate compounds having an isocyanurate skeleton include Duranate TPA-100, TKA-100, MFA-75B, MHG-80B, TUL-100, and TLA-100. , TSA-100, TSS-100, TSE-100 (manufactured by Asahi Kasei Corporation), BI-7951, BI-7982, BI-7992, DP9C/437 (manufactured by GSI Creos Co., Ltd.) and the like.
• Epoxy compound having an isocyanurate skeleton As the thermosetting compound having an isocyanurate skeleton used in the curable composition according to this embodiment, an epoxy compound having an isocyanurate skeleton can be suitably used. As the epoxy compound having an isocyanurate skeleton, one having two or more epoxy groups per isocyanurate skeleton is preferred. Epoxy compounds having an isocyanurate skeleton may be used alone or in combination of two or more.
• epoxy compounds having an isocyanurate skeleton include 1,3,5-triglycidyl isocyanurate, tris(2,3-epoxypropyl) isocyanurate, tris( ⁇ -methylglycidyl) isocyanurate, tris(1-methyl -2,3-epoxypropyl)isocyanurate, 1,3,5-tris(2,3-epoxypropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(3,4-epoxybutyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(5,6 -epoxybutyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, tris ⁇ 2,2-bis[(oxiran-2-ylmethoxy)methyl]butyl ⁇ -3, 3′,3
• TEPIC-G TEPIC-S, TEPIC-SP, TEPIC-HP, TEPIC-L, TEPIC-PAS, TEPIC-VL, TEPIC-FL, TEPIC-UC (Nissan manufactured by Kagaku Kogyo Co., Ltd.) and the like.
• (B) (Meth)acrylate compound having an isocyanurate skeleton As used herein, "(meth)acrylic acid” means “acrylic acid” or “methacrylic acid”, “(meth)acrylate” means “acrylate” or “methacrylate”, and "( A meth)acryloyl group” means an “acryloyl group” or a “methacryloyl group”.
• a (meth)acrylate compound having an isocyanurate skeleton can be suitably used from the viewpoint of improving compatibility.
• a (meth)acrylate compound having an isocyanurate skeleton has an isocyanurate skeleton and a (meth)acryloyl group in its unit structure.
• a (meth)acrylate compound having an isocyanurate skeleton may be used alone or in combination of two or more.
• the blending amount is 2 to 40 in terms of solid content in the curable composition from the viewpoint of improving the compatibility of the curable resin composition. % by mass is preferable, and 3 to 30% by mass is more preferable.
• (Meth)acrylate compounds having an isocyanurate skeleton include, for example, tris(2-acryloyloxyethyl) isocyanurate, bis(2-acryloyloxyethyl)-2-hydroxyethyl isocyanurate, ⁇ -caprolactone-modified tris-(2 -acryloxyethyl) isocyanurate and the like.
• tris(2-acryloyloxyethyl) isocyanurate and bis(2-acryloyloxyethyl)-2-hydroxyethyl isocyanurate are preferred from the viewpoint of excellent storage stability. preferable.
• (meth)acrylate compounds having an isocyanurate skeleton include, for example, Aronix M-215, M-313, M-315 (manufactured by Toagosei Co., Ltd.), FA-731A (manufactured by Showa Denko Materials Co., Ltd.). , A-9300, A-9200YN, A-9300-1CL, A-9300-3CL (manufactured by Shin-Nakamura Chemical Co., Ltd.), Photomer 4356 (manufactured by IGM Resins), TEICA (GX-8430) (Daiichi Kogyo Seiyaku Co., Ltd.) manufactured by the company).
• Aronix M-215, M-313, M-315 manufactured by Toagosei Co., Ltd.
• FA-731A manufactured by Showa Denko Materials Co., Ltd.
• A-9300, A-9200YN, A-9300-1CL, A-9300-3CL manufactured by Shin-Nakamura Chemical Co., Ltd.
• the antioxidant used in the curable composition according to the present embodiment is an antioxidant having an isocyanurate skeleton from the viewpoint of improving the crack resistance of the cured product obtained by curing the curable composition. is preferred, and a hindered phenolic antioxidant having an isocyanurate skeleton is more preferred.
• an antioxidant having an isocyanurate skeleton is included in the compounds having three or more isocyanurate skeletons, the long-term reliability (crack resistance A) after the reflow process is remarkably improved while maintaining compatibility. Therefore, it is more preferable.
• the antioxidants having an isocyanurate skeleton may be used alone or in combination of two or more.
• the blending amount is 0.1 to 10 mass in terms of solid content in the curable composition from the viewpoint of improving the compatibility of the curable composition. %, preferably 0.3 to 6% by mass.
• Antioxidants having an isocyanurate skeleton include, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenyl)isocyanurate, 1,3,5-tris(3,5 -di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris[3(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 1,3 , 5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid and the like.
• antioxidants having an isocyanurate skeleton include, for example, Irganox 3114 (manufactured by BASF Japan Ltd.), Cyanox CY-1790 and CY-2777 (manufactured by Sun Chemical Co., Ltd.).
• the blending ratio is the phase of the curable composition
• the component (A): component (B) 5 or more on a mass basis in terms of solid content. It is preferably 15:10-20, more preferably 8-12:12-18.
• the curable composition contains (A) a thermosetting compound having an isocyanurate skeleton, (B) a (meth)acrylate compound having an isocyanurate skeleton, and (C) an antioxidant having an isocyanurate skeleton ,
• thermosetting compounds (meth)acrylate compounds, antioxidants, photopolymerization initiators, colorants, thermosetting catalysts, organic solvents, and other additive components are described below.
• thermosetting compound used in the curable composition according to the present embodiment is not particularly limited, and known and commonly used compounds may be used. Examples include isocyanate compounds, blocked isocyanate compounds, epoxy compounds, oxetane compounds, melamine compounds, A phenol compound etc. are mentioned.
• a thermosetting compound may be used individually by 1 type, and may be used in combination of 2 or more type.
• the content of the thermosetting compound is preferably 1 to 20% by mass, more preferably 2 to 16% by mass in terms of solid content in the curable composition.
• An isocyanate compound is a compound having one or more isocyanate groups in one molecule.
• a blocked isocyanate compound is a compound having an isocyanate group blocked with a blocking agent (blocked isocyanate group).
• the blocked isocyanate compound is obtained by reacting a part or all of the isocyanate groups of the isocyanate compound with a blocking agent, and the protective groups (residues of the blocking agent) are dissociated by heating to generate isocyanate groups.
• curability and toughness of the cured product can be improved.
• the isocyanate compound or blocked isocyanate compound may be used singly or in combination of two or more.
• an aromatic isocyanate compound an aromatic isocyanate compound, an aliphatic isocyanate compound, or an alicyclic isocyanate compound may be used.
• aromatic isocyanate compounds include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4 -diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-4''- and triphenylmethane triisocyanate.
• aliphatic isocyanate compounds include tetramethylene diisocyanate, hexamethylene diisocyanate, ethylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate), and the like.
• alicyclic isocyanate compounds include isophorone diisocyanate, bicycloheptane triisocyanate, dicyclohexylmethane-4,4'-diisocyanate and the like.
• isocyanate compounds include adducts, burettes, and isocyanurates of the above isocyanate compounds.
• the blocking agent used to block (protect) the isocyanate group may be one that reacts with the isocyanate group to protect the isocyanate group and dissociates during heating to generate the isocyanate group, and the type thereof is particularly Not limited.
• Isocyanate group blocking agents include, for example, phenolic blocking agents (phenol, cresol, xylenol, chlorophenol, ethylphenol, etc.), lactam blocking agents ( ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -pro piolactam, etc.), active methylene-based blocking agents (e.g., diethyl malonate, dimethyl malonate, ethyl acetoacetate, acetylacetone, etc.), alcohol-based blocking agents (methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl alcohol, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate, ethyl lactate, etc
• oxime blocking agents active methylene blocking agents, alcohol blocking agents and pyrazole blocking agents are preferred, and oxime blocking agents and pyrazole blocking agents are more preferred.
• An isocyanate group may be protected by one blocking agent, or two or more blocking agents may be used in combination.
• An epoxy compound is a compound having an epoxy group. By adding an epoxy compound to the curable composition of the present embodiment, the crosslink density of the cured product of the curable composition can be increased.
• An epoxy compound may be used individually by 1 type, and may be used in combination of 2 or more type.
• epoxy compound a known and commonly used compound having one or more epoxy groups can be used, and an epoxy compound having two or more epoxy groups is preferably used.
• epoxy compounds include monoepoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, glycidyl (meth)acrylate, bisphenol A type epoxy resins, bisphenol S type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolak type epoxy resin, alicyclic epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6-hexanediol diglycidyl ether, Two or more epoxy groups per molecule such as diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris(2,3-e
• epoxy compounds include, for example, JER 828, 806, 807, YX8000, YX8034, 834 (manufactured by Mitsubishi Chemical Corporation), YD-128, YDF-170, ZX-1059, ST-3000 (Nippon Steel Chemical & Materials Co., Ltd.), EPICLON 830, 835, 840, 850, N-730A, N-695 (manufactured by DIC Corporation), RE-306 (manufactured by Nippon Kayaku Co., Ltd.), and the like.
• a (meth)acrylate compound having a hydroxyl group, a polyfunctional (meth)acrylate compound, or the like can be preferably used from the viewpoint of improving curability.
• polyfunctional it is possible to form a cured product with a high cross-linking density, and as a result, it is possible to obtain a cured product excellent in adhesion and the like.
• One of the above (meth)acrylate compounds may be used alone, or two or more thereof may be used in combination.
• the amount of the (meth)acrylate compound is, in terms of the solid content in the curable composition, from the viewpoint of improving the balance between the initial curing speed of the curable composition, the initial adhesion and the subsequent adhesion, It is preferably 50 to 90% by mass, more preferably 60 to 90% by mass.
• the (meth)acrylate compound having a hydroxyl group may be monofunctional or polyfunctional, such as 2-hydroxy-3-acryloyloxypropyl acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-hydroxy-3-phenoxyethyl acrylate, 2-hydroxy-3-phenoxyethyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, 1,4-cyclohexanedimethanol monomethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol mono
• Examples of commercially available (meth)acrylate compounds having a hydroxyl group include Aronix M-5700 (manufactured by Toagosei Co., Ltd.), 4-HBA (manufactured by Shinryo Corporation), CHDMMA (manufactured by Mitsubishi Chemical Corporation), BHEA, and HPA. , HEMA, HPMA (manufactured by Nippon Shokubai Co., Ltd.), light ester HO, light ester HOP, light ester HOA (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.
• polyfunctional (meth)acrylate compound examples include diols such as 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and 1,10-decanediol diacrylate.
• diacrylate ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol Diacrylates, diol diacrylates obtained by adding at least one of ethylene oxide and propylene oxide to neopentyl glycol, glycol diacrylates such as caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate, bisphenol A EO ( Ethylene oxide) adduct diacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, tricyclodecanedimethanol diacrylate, hydrogenated dicyclopentadienyl diacrylate, cyclohexyl diacrylate, and other diacrylate compounds having a cyclic structure and polyfunctional methacrylates having no
• polyfunctional (meth)acrylate compounds include, for example, light acrylate 1,6HX-A, 1,9ND-A, 3EG-A, 4EG-A (manufactured by Kyoeisha Chemical Co., Ltd.), HDDA, DPGDA, TPGDA.
• the curable composition according to the present embodiment may optionally contain an antioxidant.
• Antioxidants used in the curable composition according to the present embodiment include, for example, hindered phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, thioether antioxidants, vitamin antioxidants, Examples include lactone antioxidants, amine antioxidants, and the like.
• hindered phenol-based antioxidants are preferably used from the viewpoint of heat resistance and yellowing resistance.
• An antioxidant may be used individually by 1 type, and may be used in combination of 2 or more type.
• the content of the antioxidant is preferably 0.1 to 10% by mass, preferably 0.3 to 6% by mass, in terms of solid content in the curable composition.
• Hindered Phenolic Antioxidant refers to a compound containing a structure (hindered phenol structure) in which at least one, preferably both ortho-positions of a phenol are substituted with bulky substituents.
• Bulky substituents include, for example, branched or cyclic alkyl groups, preferably t-butyl groups.
• Hindered phenol antioxidants include, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,1,3-tri(4-hydroxy- 2-methyl-5-t-butylphenyl)butane, 1,1-bis(3-t-butyl-6-methyl-4-hydroxyphenyl)butane, 3,5-bis(1,1-dimethylethyl)- 4-hydroxy-benzenepropanoic acid, pentaerythrityl tetrakis(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3-(1,1-dimethylethyl)-4-hydroxy-5-methyl - benzenepropanoic acid, 3,9-bis[1,1-dimethyl-2-[(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8 , 10-tetraoxaspiro[5.5]
• antioxidants examples include Irganox 1010, 1076, 1330 (manufactured by BASF Japan Ltd.), Adekastab AO-20, AO-50, AO-60, AO-30, AO-330 (stock manufactured by the company ADEKA), and the like.
• the photopolymerization initiator used in the curable composition according to the present embodiment is not particularly limited, and known and commonly used ones can be used.
• a photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.
• photopolymerization initiators include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis -(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide , bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2, bisacylphosphine oxides such as 4,6-trimethylbenzoyl)-phenylphosphine oxide; 2,6-dimeth
• the amount of the photopolymerization initiator compounded in the curable composition according to the present embodiment is 1 to 10 parts by weight with respect to 100 parts by weight of the curable composition, excluding the oxime ester photopolymerization initiator. is preferred.
• the amount is 1 part by mass or more, the photocurability of the curable composition is improved, the film is difficult to peel off, and the film properties such as chemical resistance are improved.
• the content is 10 parts by mass or less, the effect of reducing outgassing is obtained, the light absorption on the surface of the solder resist coating film is improved, and the deep-part curability is less likely to deteriorate. More preferably 5 to 10 parts by mass.
• the amount of the oxime ester photopolymerization initiator to be blended is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable composition.
• the amount is 0.1 part by mass or more, the photocurability of the curable composition is improved, and film properties such as heat resistance and chemical resistance are also improved.
• the amount is 5 parts by mass or less, the light absorption of the solder resist film is improved, and the deep part curability is less likely to deteriorate. More preferably, it is 0.5 to 3 parts by mass.
• the curable composition according to this embodiment may contain a colorant.
• the colorant is not particularly limited as long as it can be dispersed in the curable composition, and known and commonly used colorants such as red, blue, green, yellow, white and black can be used. , dyes, and pigments.
• Red colorants include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone.
• Blue colorants include phthalocyanine-based, anthraquinone-based, and the like, and pigment-based compounds classified as pigments can be used. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.
• Green coloring agents include phthalocyanines, anthraquinones, and perylenes. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.
• Yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone colorants.
• white colorants include rutile-type and anatase-type titanium oxide.
• Black colorants include carbon black, graphite, iron oxide, titanium black, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, aniline, and sulfide. Molybdenum, bismuth sulfide, etc.
• coloring agents such as purple, orange, and brown may be added for the purpose of adjusting the color tone.
• thermosetting catalyst can be blended in the curable composition according to the present embodiment.
• thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazole derivatives such as (2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzyl amines, amine compounds such as 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenyl
• commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (manufactured by Shikoku Chemical Industry Co., Ltd., U-CAT 3513N, DBU, DBN, U-CAT SA 102 (San-Apro Co., Ltd.
• it is not limited to these, but is a thermosetting catalyst for epoxy resins and oxetane compounds, or promotes the reaction between at least one of an epoxy group and an oxetanyl group and a carboxyl group.
• S-triazine derivatives such as S-triazine derivatives can also be used, and these compounds that also function as adhesiveness-imparting agents are preferably used in combination with thermosetting catalysts.
• the curable composition according to the present embodiment may contain an organic solvent for the purpose of preparing the curable composition and adjusting the viscosity when applied to a substrate or film, as long as the properties are not impaired.
• organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether; , dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbito
• Volatilization drying of organic solvents is carried out by using a hot air circulating drying furnace, IR furnace, hot plate, convection oven, etc. (equipped with a heat source that heats the air using steam), and a method in which the hot air in the dryer is brought into contact with the counter current and supported by a nozzle. method of spraying on the body) can be used.
• the amount of the organic solvent in the curable composition is preferably changed as appropriate according to the material constituting the curable composition, for example, 0 to 30 parts by mass with respect to 100 parts by mass of the curable composition. be able to.
• the curable composition according to the present embodiment may optionally further contain a photoinitiation aid, an elastomer, a mercapto compound, a curing catalyst, a thixotropic agent, an adhesion promoter, a block copolymer, a chain transfer agent, and a polymerization inhibitor.
• a silane coupling agent such as a thiazole-based or triazole-based silane coupling agent, a flame retardant such as a phosphinate, a phosphoric acid ester derivative, a phosphorus compound such as a phosphazene compound, or the like can be blended.
• a thiazole-based or triazole-based silane coupling agent such as a thiazole-based or triazole-based silane coupling agent, a flame retardant such as a phosphinate, a phosphoric acid ester derivative, a phosphorus compound such as a phosphazene compound, or the like can be blended.
• a flame retardant such as a phosphinate, a phosphoric acid ester derivative, a phosphorus compound such as a phosphazene compound, or the like can be blended.
• those known in the field of electronic materials can be used.
• the method for producing the curable composition according to the present embodiment is not particularly limited.
• kneading means such as a three-roll mill, a ball mill, a bead mill, and a sand mill at room temperature, or , a super mixer, a planetary mixer, or the like by kneading or mixing.
• pre-kneading or pre-mixing may be carried out, if necessary.
• the viscosity of the curable composition according to the present embodiment at room temperature is preferably 150 mPa ⁇ s or less.
• the curable composition can be applied onto a substrate with good ejection properties by an inkjet method.
• the upper limit of the viscosity of the curable composition at room temperature is not particularly limited, it is preferably 100 mPa ⁇ s or less, more preferably 50 mPa ⁇ s or less.
• the lower limit of the viscosity of the curable composition at room temperature is not particularly limited, but from the viewpoint of maintaining the shape of the coating film and controlling the thickness of the coating film, for example, it is preferably 1 mPa s or more.
• viscosity refers to a viscosity measurement method using a 10 cone-plate rotary viscometer of JIS Z8803:2011, at 25°C, 100 rpm, 30 seconds, and 1°34′ as a cone rotor. Refers to the viscosity measured using a cone-plate viscometer (TVE-33H, manufactured by Toki Sangyo Co., Ltd.) using ⁇ R24.
• the curable composition according to the present embodiment is used for forming cured coatings, particularly permanent coatings, and is suitably used as an insulating material.
• insulating materials include solder resists, interlayer insulating materials, coverlays, and solder dam forming materials.
• the curable composition according to this embodiment may be used to form a protective film for semiconductor wafers.
• the curable composition according to this embodiment is obtained by applying the curable composition described above and curing the coating film, and is produced by the following procedure.
• an organic solvent is used to adjust the viscosity to be suitable for the coating method, and the substrate is coated with an inkjet method, a dip coating method, a flow coating method, There are methods such as roll coating, bar coating, screen printing, and curtain coating, which are not particularly limited.
• An ink-jet method is preferred in which a liquid composition is ejected and adhered to a desired position on a substrate. Therefore, the curable composition according to this embodiment is preferably used for inkjet printing.
• a base material in addition to printed wiring boards and flexible printed wiring boards on which circuits are formed in advance with copper, etc., paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven fabric epoxy, glass cloth/paper epoxy, synthetic Materials such as copper-clad laminates for high-frequency circuits using fiber epoxy, fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc. Copper-clad laminates of all grades (FR-4, etc.), In addition, metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates and the like can be used.
• PEN polyethylene naphthalate
• a cured product can be obtained by, for example, irradiating the coating film with an active energy ray or heating it to a temperature of 100°C to 250°C.
• Active energy ray irradiation in an inkjet printer can be performed by, for example, attaching a light source such as a high-pressure mercury lamp, a metal halide lamp, or an ultraviolet LED to the side of the print head and scanning by moving the print head or substrate. In this case, printing and active energy ray irradiation can be performed almost simultaneously.
• a light source such as a high-pressure mercury lamp, a metal halide lamp, or an ultraviolet LED
• Suitable light sources for active energy ray irradiation include LEDs, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and metal halide lamps.
• electron beams, ⁇ -rays, ⁇ -rays, ⁇ -rays, X-rays, neutron beams, etc. can also be used.
• the irradiation light source may be one or two or more, and in the case of two or more, it is possible to use a combination of light sources with different wavelengths.
• the amount of active energy ray irradiation varies depending on the thickness of the coating film, but is generally in the range of 10 to 10,000 mJ/cm 2 , preferably 20 to 2,000 mJ/cm 2 , more preferably 100 to 2,000 mJ/cm 2 . can do.
• Heating is carried out by using a hot air circulating drying furnace, IR furnace, hot plate, convection oven, or the like, which is equipped with a steam air heating heat source, and bringing the hot air in the dryer into countercurrent contact with the support. It can be carried out using a method of spraying on.
• a printed wiring board according to the present embodiment includes a cured product obtained from the curable composition described above.
• a printed wiring board having a cured product having excellent properties such as crack resistance, soldering heat resistance, and tensile resistance is produced. be able to.
• thermosetting compound an epoxy compound, a (meth)acrylate compound, an antioxidant, and a photopolymerization initiator in amounts shown in Tables 1 and 2 (unit: parts by mass). were mixed and kneaded in a bead mill in a container filled with argon gas, and then the mixture was filtered through a glass filter having a pore size of 1 ⁇ m to obtain the curable compositions of Examples 1 to 11 and Comparative Examples 1 to 4. got In addition, the value of the compounding amount in Tables 1 and 2 indicates parts by mass unless otherwise specified.
• Base material FR-4 copper clad laminate (150 mm x 95 mm x thickness 1.6 mm) Polishing: Buff polishing (Scotch brite SF (#600 equivalent) and UEF (#1000 equivalent))
• Crack occurrence rate (%) (Numerical aperture where cracks occurred/Numerical aperture observed) x 100 ⁇ : Crack incidence rate is 3% or less ⁇ : Crack incidence rate is greater than 3% and 10% or less ⁇ : Crack incidence rate is greater than 10% and 50% or less ⁇ : Crack incidence rate is greater than 50%
• Each of the curable compositions is enclosed in a 50 mL light-shielding bottle, stored in a constant temperature bath at 50 ° C. for 5 weeks, and then returned to room temperature. method, and the viscosity increase rate relative to the initial viscosity was obtained.
• the 50°C storage stability was evaluated according to the following criteria. ⁇ : viscosity increase rate is 20% or less ⁇ : viscosity increase rate is greater than 20% and 50% or less ⁇ : viscosity increase rate is greater than 50% and 100% or less ⁇ : gelation occurs
• crack resistance B Reliability at high temperatures (crack resistance B) was evaluated according to the following criteria based on the crack occurrence rate (%) shown in the following formula.
• the number of lands observed was 100.
• Crack incidence rate (%) (number of cracked lands/number of lands observed) x 100 ⁇ : Crack incidence rate is 1% or less ⁇ : Crack incidence rate is greater than 1% and 5% or less ⁇ : Crack incidence rate is greater than 5%
• the curable compositions of Examples 1 to 8 containing three or more compounds having an isocyanurate skeleton exhibited good compatibility and excellent ejection properties.
• the curable compositions of Examples 1 to 8 containing three or more compounds having an isocyanurate skeleton when cured, have good long-term reliability (crack resistance A), solder heat resistance, and tensile resistance. showed good results.
• the curable composition of Comparative Example 1 which contains only one compound having an isocyanurate skeleton, had good compatibility and jettability, but exhibited poor long-term reliability (crack resistance A) when cured. and showed poor results in tensile resistance.
• the curable composition of Comparative Example 2 which contains only two kinds of compounds having an isocyanurate skeleton, has poor compatibility and ejection properties, exhibits poor tensile resistance when cured, and exhibits long-term reliability (crack resistance A) and Soldering heat resistance was inferior to the cured products of Examples 1-8.
• thermosetting compound having an isocyanurate skeleton, a (meth) acrylate compound having an isocyanurate skeleton, and a curable composition containing an antioxidant having an isocyanurate skeleton It can be seen that the cured product obtained by curing , has good long-term reliability (crack resistance A). Further, a curable composition containing four kinds of compounds having an isocyanurate skeleton as in Examples 6 and 10 and a curable composition containing five kinds of compounds having an isocyanurate skeleton as in Example 9 were cured. The resulting cured product tended to give good results in both long-term reliability (crack resistance A) and high temperature reliability (crack resistance B). It is considered that this is because the compatibility of the curable composition is improved due to the large number of types of compounds having an isocyanurate skeleton.
• the curable composition of Example 1 has improved compatibility and ejection properties compared to the curable composition of Comparative Example 2. Comparing the components of the curable compositions of Example 1 and Comparative Example 2 in Tables 1 and 2, in addition to the antioxidant Irganox 3114 having an isocyanurate skeleton, the curable composition of Example 1 further contains two (thermosetting compound BI-7982 with isocyanurate skeleton and NK ester A-9300 with isocyanurate skeleton). On the other hand, the curable composition of Comparative Example 2 contains only the thermosetting compound BI-7982 having an isocyanurate skeleton.
• the curable composition of Example 1 contains three kinds of compounds having an isocyanurate skeleton, thereby making the curable composition of Comparative Example 2, which contains only two kinds of compounds having an isocyanurate skeleton, It is thought that this gives good compatibility and jettability compared to the other.
• thermosetting compound (A) having an isocyanurate skeleton the more the type of thermosetting compound (A) having an isocyanurate skeleton, the better the storage stability at 50°C. It is considered that this is because (A) there are many kinds of thermosetting compounds having an isocyanurate skeleton, and thus the compatibility is improved.
• the curable compositions of Examples 6 and 9 to 11 in Table 1 contain four or more compounds having an isocyanurate skeleton, and have compatibility, jettability, and long-term reliability (crack resistance A). and high temperature reliability (crack resistance B), solder heat resistance, elongation in tensile measurement, and 50° C. storage stability.

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