JP6698333B2 - Curable resin composition, dry film, cured product and printed wiring board - Google Patents

Description

  The present invention relates to a curable resin composition, a dry film, a cured product and a printed wiring board.

  A curable resin composition is used as a material for forming a permanent coating film such as a solder resist of a printed wiring board, an interlayer insulating layer, and a coverlay. In recent years, curable resin compositions have been required to have higher workability and higher performance in response to higher densities of printed wiring boards that accompany lighter, thinner, shorter, and smaller electronic devices. For example, as electronic devices have become smaller, lighter, and higher in performance, semiconductor packages have become smaller and more pins have been put into practical use, and mass production is proceeding.

  Corresponding to such high density, instead of IC packages called QFP (Quad Flat Pack Package) and SOP (Small Outline Package), BGA (ball grid array), CSP (chip)・IC packages called scale packages) have appeared. In a printed wiring board having a fine pitch wiring pattern such as such a package substrate, since the wiring patterns are formed in high density and close to each other, a short circuit or crosstalk noise occurs between lines of the wiring pattern. There is a high risk that Therefore, particularly high reliability is required for a permanent coating film such as a solder resist used for such a package substrate.

  Conventionally, a method of blending core-shell rubber particles with a curable resin composition for the purpose of improving reliability has been known. For example, Patent Document 1 describes that a curable resin composition containing core-shell rubber particles has excellent TCT resistance (cooling and thermal shock characteristics). Further, conventionally, it has been known to mix an inorganic filler with a curable resin composition for the purpose of improving properties such as hardness (for example, Patent Document 2).

JP, 2009-192632, A JP-A-8-335767

  As described above, the core-shell rubber particles are components mixed for the purpose of improving reliability such as TCT resistance and tensile elongation, but there is a possibility that the linear expansion coefficient and the tensile strength may be decreased, which may affect the reliability. there were. Therefore, by adding an inorganic filler to the curable resin composition, the linear expansion coefficient has been lowered and the tensile strength has been improved. However, such a curable resin composition could not maintain a satisfactory TCT resistance.

  Therefore, an object of the present invention is to provide a curable resin composition capable of obtaining a cured product having excellent TCT resistance while maintaining thermophysical properties and mechanical properties, a dry film having a resin layer obtained from the composition, and the composition. The object is to provide a cured product of the resin or the resin layer of the dry film, and a printed wiring board having the cured product.

  The present inventors have conducted intensive studies in view of the above, in a curable resin composition containing a core-shell rubber particles and an inorganic filler, the core-shell rubber particles are incorporated into the curing system, and by using a surface-treated inorganic filler The inventors have found that the above problems can be solved and have completed the present invention.

  That is, the curable resin composition of the present invention comprises (A) core-shell rubber particles having a curable reactive group on the surface, (B) a surface-treated inorganic filler, and (C) a curable resin, (A) The curable reactive group of the core-shell rubber particles having a curable reactive group on the surface is a group that reacts with the (C) curable resin.

  In the curable resin composition of the present invention, the (C) curable resin is preferably (C-1) thermosetting resin.

  The curable resin composition of the present invention preferably further contains (C-2) a photocurable resin.

  The curable resin composition of the present invention preferably has a curable reactive group on the surface of which the (B) surface-treated inorganic filler reacts with the (C-2) photocurable resin.

  In the curable resin composition of the present invention, the (B) surface-treated inorganic filler is preferably an inorganic filler surface-treated with a silane coupling agent.

  The curable resin composition of the present invention preferably further contains at least one selected from the group consisting of (D) photopolymerization initiator and (E) photobase generator.

  In the curable resin composition of the present invention, the size of the surface-treated inorganic filler (B) is preferably 2 μm or less in average particle diameter.

  In the curable resin composition of the present invention, the content of the (B) surface-treated inorganic filler is preferably 20 to 80% by mass based on the total amount of solid content in the composition.

  The dry film of the present invention is characterized by having a resin layer obtained by applying the curable resin composition to a film and drying the film.

  The cured product of the present invention is characterized by being obtained by curing the curable resin composition or the resin layer of the dry film.

  The printed wiring board of the present invention is characterized by having the cured product.

  According to the present invention, a curable resin composition capable of obtaining a cured product having excellent TCT resistance while maintaining thermophysical properties and mechanical properties, a dry film having a resin layer obtained from the composition, and the composition Alternatively, a cured product of the resin layer of the dry film and a printed wiring board having the cured product can be provided.

  The curable resin composition of the present invention comprises (A) core-shell rubber particles having a curable reactive group on the surface (hereinafter, also referred to as “(A) core-shell rubber particles”), and (B) surface-treated inorganic filler ( Hereinafter, the curable reactive group of the core-shell rubber particles containing (B) an inorganic filler) and (C) curable resin, and having the (A) curable reactive group on the surface is the (C) curable resin. It is characterized in that it is a group that reacts with. Usually, since components other than the curing component do not participate in the curing reaction, after the curing reaction, they are included in the cured product in a state of being surrounded by the resin having the crosslinked network, and therefore, between the resin having the crosslinked network and the resin. Causes an interface. Although the detailed mechanism is not clear, when the cured product contains the core-shell rubber particles, such an interface becomes a weak point at the time of stress generation, and it is considered that cracks are generated due to this interface. It is considered that by forming a crosslinked network of the resin and the core-shell rubber particles and incorporating them into the curing system, cracks due to such an interface are less likely to occur and the TCT resistance is improved. Moreover, it is considered that the wettability with the resin can be improved by using the surface-treated inorganic filler, the interface with the resin having the crosslinked network is hard to be generated, and the TCT resistance is improved.

  Further, it is preferable that the surface-treated inorganic filler (B) has a curable reactive group that reacts with the curable resin (C). This is because (B) the surface-treated inorganic filler is also taken into the curing system, and cracks are less likely to occur. As the type of surface treatment, silane coupling is preferable because of the ease of surface treatment.

  In the specification of the present application, the curable reactive group means a curable functional group of a curable resin (such as an epoxy group of an epoxy resin which is a thermosetting resin or an acrylic group of an acrylate compound which is a photocurable resin). It means a reactive group, and is a concept including a curable functional group.

  In the curable resin composition of the present invention, the curable resin (C) may be a thermosetting resin or a photocurable resin. For example, when (C) an epoxy resin which is a thermosetting resin is contained as the curable resin, (A) if the core-shell rubber particles have a group capable of undergoing a curing reaction with an epoxy group as a curable reactive group, the curing system is Can be captured. The same applies when the inorganic filler (B) has a curable reactive group.

  As a specific example, the curable resin composition contains (A) core-shell rubber particles having an epoxy group, (B) an inorganic filler having an epoxy group, and (C) a thermosetting resin containing an epoxy resin. In the case of a curable resin, the epoxy group of each component starts a chemical bond by heating, and a cured product in which (A) core-shell rubber particles and (B) inorganic filler are incorporated into the curing system can be obtained.

  The curable resin (C) may have one or more curable reactive groups in addition to the curable functional group. Furthermore, two or more types of (C) curable resin may be contained. As a specific example, the curable resin composition includes (A) core-shell rubber particles having an epoxy group, (B) an inorganic filler having an ethylenically unsaturated bond, and (C) an ethylenically non-curable resin. In the case of containing a carboxyl group-containing resin having a saturated bond and an epoxy resin, the ethylenically unsaturated bond of the inorganic filler (B) and the ethylenically unsaturated bond of the curable resin (C) start a chemical bond by light irradiation, (B) The inorganic filler is incorporated into the curing system. Then, by heating, the epoxy groups of the (A) core-shell rubber particles and the carboxyl groups of the (C) curable resin and the epoxy resin start chemical bonding, and the (A) core-shell rubber particles are incorporated into the curing system.

  In order to further improve the crack resistance, it is preferable that the particle diameters of the (A) core-shell rubber particles and the (B) inorganic filler be as close as possible to the primary particle diameter.

  Next, each component of the curable resin composition of the present invention will be described. In addition, in this specification, (meth)acrylate is a general term for acrylates, methacrylates, and mixtures thereof, and the same applies to other similar expressions.

[(A) Core-shell rubber particles having curable reactive group on the surface]
The core-shell rubber particles refer to a rubber material having a multi-layer structure composed of a core layer having a different composition and one or more shell layers covering the core layer. As described below, as the core-shell rubber particles, the core layer is made of a material having excellent flexibility, and the shell layer is made of a material having an excellent affinity for other components. The dispersibility is improved while achieving high efficiency.

  A material having excellent flexibility is used as a constituent material of the core layer. Specific examples include silicone elastomers, butadiene elastomers, styrene elastomers, acrylic elastomers, polyolefin elastomers, and silicone/acrylic composite elastomers.

  On the other hand, as a constituent material of the shell layer, a material having an excellent affinity for other components is used. For example, when the curable resin composition contains an epoxy resin, it is preferable to use core-shell rubber particles having a shell layer made of a material having an excellent affinity for the epoxy resin. Acrylic resin and epoxy resin are more preferable.

  The curable reactive group on the surface of the (A) core-shell rubber particle is not particularly limited as long as it is a group that undergoes a curing reaction with the (C) curable resin, and even a thermosetting reactive group is a photocurable reactive group. May be. Further, the (A) core-shell rubber particles may have two or more kinds of curable reactive groups.

  Examples of the thermosetting reactive group include a hydroxyl group, a carboxyl group, an isocyanate group, an imino group, an epoxy group, an oxetanyl group, a mercapto group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, and an oxazoline group. .. More preferably, it is an epoxy group.

  Examples of the photocurable reactive group include a vinyl group, a styryl group, a methacryl group, and an acryl group. A methacryl group or an acryl group is preferable because the reactivity becomes appropriate even when the filler content is large.

  The method for introducing the curable reactive group (A) on the surface of the core-shell rubber particles is not particularly limited, and a known and commonly used method may be used. For example, when forming a shell layer around the core layer, by polymerizing a material having a curable reactive group different from a functional group for a polymerization reaction with the core layer into the core layer as a constituent material of the shell layer, Can be introduced.

  Examples of commercially available (A) core-shell rubber particles include Paraloid ELX2655 manufactured by Rohm and Haas Co., XER-91 manufactured by Japan Synthetic Rubber Co., Ltd., and the like.

  In the curable resin composition of the present invention, it is preferable that the core-shell rubber particles (A) have an average particle diameter of 2 μm or less because crack resistance is excellent. More preferably, it is 0.01 to 1 μm. In the present specification, the average particle size is a value of D50 measured using a Microtrac particle size analyzer manufactured by Nikkiso Co., Ltd.

  In the curable resin composition of the present invention, the content of the (A) core-shell rubber particles is preferably 1 to 30 mass% with respect to the organic component in the solid content of the composition. When it is 1% by mass or more, crack resistance is more excellent, which is preferable. On the other hand, when it is 30% by mass or less, it is preferable in terms of excellent printability and developability. More preferably, it is 3 to 20 mass %. Further, the curable resin composition of the present invention may contain core-shell rubber particles having no curable reactive group, as long as the effects of the invention are not impaired. In addition, an organic component means here all solid components other than inorganic components, such as a filler.

[(B) Surface-treated inorganic filler]
The surface treatment of the inorganic filler (B) is not particularly limited, and a surface treatment capable of introducing a curable reactive group onto the surface of the inorganic filler is preferable.

  The inorganic filler is not particularly limited, and known conventional fillers such as silica, crystalline silica, Neuburg silica, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, Inorganic fillers such as aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate and zinc white can be used. Among them, silica is preferable, and spherical silica is more preferable because it has a small surface area and the stress is dispersed all over, so that it is less likely to be a starting point of cracks.

  The inorganic filler (B) preferably has a curable reactive group that reacts with the curable resin (C) on its surface. The curable reactive group may be a thermosetting reactive group or a photo-curable reactive group, and examples thereof include the curable reactive group mentioned in the above (A) core-shell rubber particles. Among them, the photocurable reactive group is preferably a methacrylic group, an acrylic group or a vinyl group, and the thermosetting reactive group is preferably an epoxy group. Further, the inorganic filler (B) may have two or more curable reactive groups.

  The method for introducing the curable reactive group to the surface of the inorganic filler (B) is not particularly limited, and may be introduced by a known and commonly used method. For example, a surface treating agent having a curable reactive group, for example, a curable reactive group may be introduced. The surface of the inorganic filler may be treated with a coupling agent having an organic group.

  The surface treatment of the inorganic filler (B) is preferably a surface treatment with a coupling agent. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent or the like can be used. Of these, a silane coupling agent is preferable.

  As the silane coupling agent, a silane coupling agent capable of introducing a curing reactive group into the inorganic filler (B) is preferable. The silane coupling agent capable of introducing a thermosetting reactive group, as the organic group, a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having a mercapto group, an isocyanate group The silane coupling agent which has is mentioned, Especially, the silane coupling agent which has an epoxy group is more preferable. As the silane coupling agent capable of introducing a photocurable reactive group, as the organic group, a silane coupling agent having a vinyl group, a silane coupling agent having a styryl group, a silane coupling agent having a methacryl group, an acrylic group The silane coupling agent having is preferable, and the silane coupling agent having a methacryl group is more preferable.

  Further, as the inorganic filler (B) having no curable reactive group, for example, an alumina surface-treated inorganic filler and the like can be mentioned.

  The inorganic filler (B) may be added to the curable resin composition of the present invention in a surface-treated state. In the composition, the surface-untreated inorganic filler and the surface-treating agent are separately added. The inorganic filler may be surface-treated, but it is preferable to add an inorganic filler that has been surface-treated in advance. By blending the inorganic fillers that have been surface-treated in advance, it is possible to prevent a decrease in crack resistance and the like due to the surface-treating agent which is not consumed in the surface treatment and may remain when they are blended separately. When the surface treatment is carried out in advance, it is preferable to add a preliminary dispersion liquid in which the inorganic filler (B) is pre-dispersed, and the surface-treated inorganic filler is pre-dispersed in the solvent, and the preliminary dispersion liquid is added to the composition. Alternatively, it is more preferable that after the surface-untreated inorganic filler is sufficiently dispersed in the solvent, the surface treatment is sufficiently performed and then the preliminary dispersion liquid is added to the composition.

  In the curable resin composition of the present invention, it is preferable that the inorganic filler (B) has an average particle size of 2 μm or less because it is more excellent in crack resistance. More preferably, it is 1 μm or less.

  The curable resin composition of the present invention can contain an inorganic filler which is not surface-treated, in addition to the inorganic filler (B). In that case, the amount of the inorganic filler (B) is preferably 30% by mass or more, more preferably 50% by mass or more, and 70% by mass based on the total amount of the inorganic filler (B) and the inorganic filler not surface-treated. % Or more is more preferable. Further, the inorganic filler not surface-treated is preferably spherical silica.

  The content of the inorganic filler (B) is preferably 20 to 80% by mass, more preferably 30 to 60% by mass, and more preferably 35 to 60% by mass based on the total amount of the solid content of the curable resin composition. It is more preferable that there is.

[(C) Curable resin]
The (C) curable resin may be (C-1) a thermosetting resin or (C-2) a photocurable resin. The curable resin (C) may be used alone or in combination of two or more.

  The thermosetting resin (C-1) may be any resin that is cured by heating and exhibits electrical insulation, and examples thereof include an epoxy compound, an oxetane compound, a melamine resin, and a silicone resin. Particularly, in the present invention, an epoxy compound and an oxetane compound can be preferably used, and these may be used in combination.

  As the epoxy compound, a known and commonly used compound having one or more epoxy groups can be used, and among them, a compound having two or more epoxy groups is preferable. For example, monoepoxy compounds such as monoepoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, glycidyl (meth)acrylate, bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, Cresol novolac 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 in one molecule such as ethylene glycol or propylene glycol diglycidyl ether, sorbitol polyglycidyl ether, tris(2,3-epoxypropyl)isocyanurate, triglycidyl tris(2-hydroxyethyl)isocyanurate, etc. And a compound having These may be used alone or in combination of two or more according to the required characteristics.

Specific examples of the compound having two or more epoxy groups include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Co., Ltd., Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, and Nippon Steel & Sumikin Chemical Co., Ltd. Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Dow Chemical Japan Co., Ltd. E. R. 317, D.I. E. R. 331, D.I. E. R. 661, D.I. E. R. 664, Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Co., Ltd., A.E. manufactured by Asahi Kasei E-materials Corporation. E. R. 330, A. E. R. 331, A.A. E. R. 661, A.D. E. R. Bisphenol A type epoxy resin such as 664; jERYL903 manufactured by Mitsubishi Chemical Co., Epicron 152, Epicron 165 manufactured by DIC Co., Ltd., Epototo YDB-400, YDB-500 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., D.C. E. R. 542, Sumi-Epoxy ESB-400 and ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.E. manufactured by Asahi Kasei E-Materials. E. R. 711, A. E. R. Brominated epoxy resin such as 714; jER152, jER154 manufactured by Mitsubishi Chemical Co., D.C. manufactured by Dow Chemical Japan. E. N. 431, D.I. E. N. 438, DIC's Epicron N-730, Epicron N-770, Epicron N-865, Nippon Steel & Sumikin Chemical's Epotote YDCN-701, YDCN-704, Nippon Kayaku's EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumi-epoxy ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Co., A. manufactured by Asahi Kasei E-materials Co., Ltd. E. R. ECN-235, ECN-299, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704 YDCN-704A manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. , Novolac type epoxy resin such as Epicron N-680, N-690, N-695 (all trade names) manufactured by DIC; Epicron 830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical, Epototo manufactured by Nippon Steel & Sumikin Chemical Bisphenol F type epoxy resins such as YDF-170, YDF-175 and YDF-2004; hydrogenated bisphenol A type epoxy resins such as Epototo ST-2004, ST-2007 and ST-3000 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; Mitsubishi Chemical Corporation JER604 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epotote YH-434 manufactured by Sumitomo Chemical Co., Ltd., glycidylamine type epoxy resin such as Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd., hydantoin type epoxy resin; Epoxy resin: YL-933 manufactured by Mitsubishi Chemical Co., Ltd., T.L. manufactured by Dow Chemical Japan Co., Ltd. E. N. , EPPN-501, EPPN-502 and other trihydroxyphenylmethane type epoxy resins; Mitsubishi Chemical's YL-6056, YX-4000, YL-6121 and other bixylenol type or biphenol type epoxy resins or mixtures thereof; Japan. Bisphenol S type epoxy resin such as EBPS-200 manufactured by Kayaku Co., EPX-30 manufactured by ADEKA, EXA-1514 manufactured by DIC; Bisphenol A novolac type epoxy resin such as jER157S manufactured by Mitsubishi Chemical; Mitsubishi Chemical Tetraphenylolethane type epoxy resin such as jERYL-931; Heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industries; Diglycidyl phthalate resin such as Bremmer DGT manufactured by NOF CORPORATION; ZX-1063 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Naphthalene group-containing epoxy resins such as ESN-190, ESN-360 manufactured by Nippon Steel & Sumitomo Metal Corporation, HP-4032 manufactured by DIC, EXA-4750, and EXA-4700; HP-7200 manufactured by DIC. , HP-7200H and other epoxy resins having a dicyclopentadiene skeleton; NOF CORPORATION CP-50S, CP-50M and other glycidyl methacrylate copolymer epoxy resins; and cyclohexyl maleimide and glycidyl methacrylate copolymer epoxy resins; Examples thereof include CTBN-modified epoxy resin (for example, YR-102 and YR-450 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), but are not limited thereto. Among these, a bisphenol A type epoxy resin, a heterocyclic epoxy resin, or a mixture thereof is preferable because it is particularly excellent in discoloration resistance.
These epoxy resins may be used alone or in combination of two or more.

（式中、Ｒ^１は、水素原子または炭素数１〜６のアルキル基を示す）により表されるオキセタン環を含有するオキセタン化合物の具体例としては、３−エチル−３−ヒドロキシメチルオキセタン（東亞合成社製ＯＸＴ−１０１）、３−エチル−３−（フェノキシメチル）オキセタン（東亞合成社製ＯＸＴ−２１１）、３−エチル−３−（２−エチルヘキシロキシメチル）オキセタン（東亞合成社製ＯＸＴ−２１２）、１，４−ビス｛［（３−エチル−３−オキセタニル）メトキシ］メチル｝ベンゼン（東亞合成社製ＯＸＴ−１２１）、ビス（３−エチル−３−オキセタニルメチル）エーテル（東亞合成社製ＯＸＴ−２２１）などが挙げられる。さらに、フェノールノボラックタイプのオキセタン化合物なども挙げられる。これらオキセタン化合物は、上記エポキシ化合物と併用してもよく、また、単独で使用してもよい。 Next, the oxetane compound will be described. The following general formula (I),

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and specific examples of the oxetane compound having an oxetane ring include 3-ethyl-3-hydroxymethyloxetane (Toago OXT-101 manufactured by Synthetic Co., Ltd., 3-ethyl-3-(phenoxymethyl)oxetane (OXT-211 manufactured by Toagosei Co., Ltd.), 3-Ethyl-3-(2-ethylhexyloxymethyl)oxetane (OXT manufactured by Toagosei Co., Ltd.) -212), 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (TOA Gosei Co., Ltd. OXT-121), bis(3-ethyl-3-oxetanylmethyl) ether (Toago Gosei) OXT-221) manufactured by the same company can be mentioned. Further, a phenol novolac type oxetane compound and the like are also included. These oxetane compounds may be used in combination with the above epoxy compound or may be used alone.

  The (C-2) photocurable resin may be a resin that is cured by irradiation with active energy rays and exhibits electrical insulation properties. In particular, in the present invention, one or more ethylenically unsaturated bonds are present in the molecule. Compounds having are preferably used. As the compound having an ethylenically unsaturated bond, a photopolymerizable oligomer, a photopolymerizable vinyl monomer or the like, which is a known and commonly used photosensitive monomer, can be used. Further, as the photocurable resin, a polymer such as a carboxyl group-containing resin having an ethylenically unsaturated bond as described below can be used.

  Examples of the photopolymerizable oligomer include unsaturated polyester-based oligomers and (meth)acrylate-based oligomers. Examples of (meth)acrylate-based oligomers include epoxy (meth)acrylates such as phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, and bisphenol type epoxy (meth)acrylate, urethane (meth)acrylate, epoxy urethane (meth). ) Acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polybutadiene modified (meth)acrylate and the like.

  As the photopolymerizable vinyl monomer, known conventional ones, for example, styrene derivatives such as styrene, chlorostyrene and α-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- Vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether and triethylene glycol monomethyl vinyl ether; acrylamide, (Meth)acrylamides such as methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide; triallyl isocyanurate, diallyl phthalate, Allyl compounds such as diallyl isophthalate; 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc. Of (meth)acrylic acid ester; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate; methoxyethyl (meth)acrylate, ethoxyethyl Alkoxyalkylene glycol mono(meth)acrylates such as (meth)acrylate; ethylene glycol di(meth)acrylate, butanediol di(meth)acrylates, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di( Alkylene polyols poly(meth)acrylates such as (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate; diethylene glycol di(meth)acrylate, triethylene glycol di Polyoxyalkylene glycol poly(meth)acrylates such as (meth)acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri(meth)acrylate A) acrylates; poly(meth)acrylates such as hydroxypivalic acid neopentyl glycol ester di(meth)acrylate; isocyanurate-type poly(meth)acrylates such as tris[(meth)acryloxyethyl]isocyanurate. Can be mentioned. These may be used alone or in combination of two or more according to the required characteristics.

  The (C) curable resin may have one or more curable reactive groups in addition to the curable functional group, and for example, a carboxyl group-containing resin having an ethylenically unsaturated group or the like may be used. it can. Such a carboxyl group-containing resin is preferable because it has alkali solubility and the curable resin composition of the present invention can be used as an alkali developing type photocurable resin composition.

Specific examples of the carboxyl group-containing resin having an ethylenically unsaturated bond include compounds (both oligomers and polymers) listed below.
(1) An unsaturated carboxylic acid such as (meth)acrylic acid, an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, and isobutylene, and a photosensitive monomer as described above. A carboxyl group-containing resin having an ethylenically unsaturated group, which is obtained by copolymerization. The lower alkyl refers to an alkyl group having 1 to 5 carbon atoms.
(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, and carboxy group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate-based polyols and polyether-based polyols Of a carboxyl group-containing urethane resin by polyaddition reaction of a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic-based polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, etc. During the synthesis, a compound having one hydroxyl group and one or more (meth)acryloyl group in the molecule such as hydroxyalkyl (meth)acrylate was added, and the terminal (meth)acrylated carboxyl having an ethylenically unsaturated group was added. Group-containing polyurethane resin.
(3) Diisocyanate compound such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate, and polycarbonate-based polyol, polyether-based polyol, polyester-based polyol, polyolefin-based polyol, acrylic-based polyol, bisphenol A-based During the synthesis of a urethane resin containing a terminal carboxyl group obtained by reacting an acid anhydride with the end of a urethane resin by polyaddition reaction of an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and a compound having an alcoholic hydroxyl group, etc. A carboxyl group-containing polyurethane having an ethylenically unsaturated group, which is obtained by adding a compound having one hydroxyl group and one or more (meth)acryloyl group in a molecule such as hydroxyalkyl (meth)acrylate and terminal (meth)acrylated. resin.
(4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing polyurethane resin having an ethylenically unsaturated group obtained by a polyaddition reaction of (meth)acrylate or a partial acid anhydride modified product thereof, a carboxyl group-containing dialcohol compound and a diol compound.
(5) A compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule such as hydroxyalkyl (meth)acrylate is added during the synthesis of the resin of (4) above to obtain a terminal (meth)acrylate. And a carboxyl group-containing polyurethane resin having an ethylenically unsaturated group.
(6) During the synthesis of the resin of (2) or (4), one isocyanate group and one or more (meth)acryloyl group are added to the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. A carboxyl group-containing polyurethane resin having an ethylenically unsaturated group, which is obtained by adding a compound having the above and is (meth)acrylate-terminated.
(7) A polyfunctional epoxy resin as described above is reacted with (meth)acrylic acid, and a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is added to the hydroxyl group present in the side chain. And a carboxyl group-containing resin having an ethylenically unsaturated group. Here, the polyfunctional epoxy resin is preferably solid.
(8) An ethylenic compound obtained by reacting a (meth)acrylic acid with a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional epoxy resin with epichlorohydrin and adding a dibasic acid anhydride to the generated hydroxyl group. A carboxyl group-containing resin having a saturated group. Here, the bifunctional epoxy resin is preferably solid.
(9) A carboxyl group-containing resin having an ethylenically unsaturated group, which is obtained by reacting the above difunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
(10) Reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid A carboxyl group-containing resin having an ethylenically unsaturated group, which is obtained by reacting a product with a polybasic acid anhydride.
(11) Obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate and propylene carbonate with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing resin having an ethylenically unsaturated group, which is obtained by reacting a reaction product with a polybasic acid anhydride.
(12) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, (meth) A maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine is reacted with the alcoholic hydroxyl group of the reaction product obtained by reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid. A carboxyl group-containing resin having an ethylenically unsaturated group, which is obtained by reacting a polybasic acid anhydride such as an acid.
(13) In addition to the resin according to any one of (1) to (12), one epoxy group and one or more (meth)acryloyl in a molecule such as glycidyl (meth)acrylate and α-methylglycidyl (meth)acrylate. A carboxyl group-containing resin having an ethylenically unsaturated group, which is obtained by adding a compound having a group.

  Among the carboxyl group-containing resins having an ethylenically unsaturated group, a carboxyl group-containing resin that does not use an epoxy resin as a starting material can be preferably used. Therefore, among the specific examples of the carboxyl group-containing resin described above, the carboxyl group-containing resin having an ethylenically unsaturated group of any one or more of (2), (3), (10) and (11) is preferably used. Can be used. Above all, it is particularly preferable to use the carboxyl group-containing resin (10) having an ethylenically unsaturated group.

  Thus, by not using the epoxy resin as the starting material, the chlorine ion impurity amount can be suppressed to a very small value of, for example, 100 ppm or less. The content of chlorine ion impurities in the carboxyl group-containing resin having an ethylenically unsaturated group preferably used in the present invention is preferably 0 to 100 ppm, more preferably 0 to 50 ppm, and further preferably 0 to 30 ppm.

  Since the carboxyl group-containing resin having an ethylenically unsaturated group as described above has a large number of carboxyl groups in the side chain of the backbone polymer, it can be developed with an aqueous alkaline solution.

  The acid value of the carboxyl group-containing resin having an ethylenically unsaturated group is preferably in the range of 20 to 200 mgKOH/g, more preferably 40 to 150 mgKOH/g. When the acid value of the carboxyl group-containing resin having an ethylenically unsaturated group is 20 mgKOH/g or more, the adhesion of the coating film becomes good and the alkali developability becomes good. On the other hand, when the acid value is 200 mgKOH/g or less, the surface curability is excellent, and the development damage of the exposed area due to the developer can be reduced.

  Although the weight average molecular weight of the carboxyl group-containing resin having an ethylenically unsaturated group varies depending on the resin skeleton, it is generally preferably 2,000 to 150,000. When the weight average molecular weight is 2,000 or more, a dry coating film excellent in dryness to the touch can be obtained. On the other hand, when the weight average molecular weight is 150,000 or less, the alkali developability becomes good and the storage stability becomes good. More preferably, it is 5,000 to 100,000.

((D) Photopolymerization initiator)
When the curable resin composition of the present invention contains (C-2) a photocurable resin as the (C) curable resin, it preferably contains (D) a photopolymerization initiator. As the photopolymerization initiator (D), any photopolymerization initiator known as a photopolymerization initiator or a photoradical generator can be used.

  Examples of the photopolymerization initiator (D) include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide and 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-(2,4 ,6-Trimethylbenzoyl)-phenylphosphine oxide (IRGACURE819 manufactured by BASF Japan Ltd.) and the like; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2 , 4,6-Trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF Japan Ltd.) IRGACURE TPO) and other monoacylphosphine oxides; 1-hydroxy-cyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one , 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1- Hydroxyacetophenones such as phenylpropan-1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; benzoin alkyl ethers; benzophenone, Benzophenones such as p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone; acetophenone, 2,2- Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino -1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl)-1-[ Acetophenones such as 4-(4-morpholinyl)phenyl]-1-butanone and N,N-dimethylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethyl. Thioxanthones such as thioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, Anthraquinones such as 2-aminoanthraquinone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate and p-dimethylbenzoic acid ethyl ester 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-, 1-(O-acetyloxime) and other oxime esters; bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H- Titanocenes such as pyrrol-1-yl)phenyl)titanium and bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyr-1-yl)ethyl)phenyl]titanium; Examples thereof include phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide and the like. As the photopolymerization initiator (D), one type may be used alone, or two or more types may be used in combination. Among them, monoacylphosphine oxides and oxime esters are preferable, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3. -Yl]-,1-(O-acetyloxime) is more preferred.

  The compounding amount of the (D) photopolymerization initiator is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the solid content of the (C-2) photocurable resin. When it is 5 parts by mass or more, the surface curability becomes good, and when it is 20 parts by mass or less, halation hardly occurs and good resolution is obtained.

((E) Photobase generator)
The curable resin composition of the present invention may contain (E) a photobase generator.
(E) The photobase generator is one or more basic substances capable of functioning as a catalyst for a thermosetting reaction by changing the molecular structure or cleaving the molecule upon irradiation with light such as ultraviolet rays or visible light. Is a compound that produces. Examples of the basic substance include secondary amines and tertiary amines.

  (E) Examples of photobase generators include α-aminoacetophenone compounds, oxime ester compounds, acyloxyimino groups, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzylcarbamate groups, and alcohols. Examples thereof include compounds having a substituent such as an oxybenzyl carbamate group. Of these, oxime ester compounds and α-aminoacetophenone compounds are preferable, oxime ester compounds are more preferable, and ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) is more preferred. As the α-aminoacetophenone compound, those having two or more nitrogen atoms are particularly preferable. As the photobase generator (E), one type may be used alone, or two or more types may be used in combination.

  Besides, examples of the photobase generator include carbamate derivatives, quaternary ammonium salts and the like.

  As other photobase generators, WPBG-018 (trade name: 9-anthrylmethyl N, N'-diethylcarbamate), WPBG-027 (trade name: (E)-1-[3-(2-hydroxyphenyl)-2- WPBG-082 (trade name: guanidinium2-(3-benzoylphenyl)propionate), WPBG-140 (trade name: 1-(anthraquinon-2-yl)ethyl imidazoleate etc.) can also be used.

  Further, some substances of the above-mentioned photopolymerization initiator also function as a photobase generator. Examples of the photopolymerization initiator that also functions as a photobase generator include oxime ester-based photopolymerization initiators having an oxime ester group, α-aminoacetophenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and titanocene-based photopolymerization initiators. Polymerization initiators are preferred. In addition, a photopolymerization initiator having a substituent such as an acyloxyimino group, an N-formylated aromatic amino group, an N-acylated aromatic amino group, a nitrobenzylcarbamate group, and an alcooxybenzylcarbamate group is also a photobase generator. Can also be used as

  The compounding amount of the (E) photobase generator is preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the solid content of the (C-2) photocurable resin. When the amount is 0.5 parts by mass or more, the surface curability is good, and when the amount is 5 parts by mass or less, halation hardly occurs and good resolution is obtained.

(Curing agent and thermosetting catalyst)
The curable resin composition of the present invention may contain at least one of a curing agent and a thermosetting catalyst.

  Examples of the curing agent include polyfunctional phenol compounds, polycarboxylic acids and acid anhydrides thereof, aliphatic or aromatic primary or secondary amines, polyamide resins, isocyanate compounds, polymercapto compounds, and the like. Among these, polyfunctional phenol compounds, polycarboxylic acids and acid anhydrides thereof are preferably used from the viewpoints of workability and insulating properties.

  The thermosetting catalyst is a compound that can be a thermosetting catalyst in the reaction between a thermosetting resin such as an epoxy compound and an oxetane compound and a curing agent, or a compound that is a polymerization catalyst when the curing agent is not used. Specific examples of the curing catalyst include tertiary amines, tertiary amine salts, quaternary onium salts, tertiary phosphines, crown ether complexes, and phosphonium ylides. Or two or more types can be used in combination.

(Organic solvent)
The curable resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition and adjusting the viscosity when applied to a substrate or a carrier film. Examples of the organic solvent 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. , Glycol ethers such as 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, carbitol acetate, butyl carbyl Esters such as tall acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, solvent naphtha, etc. Conventional organic solvents can be used. These organic solvents can be used alone or in combination of two or more.

(Other optional ingredients)
Further, the curable resin composition of the present invention may be blended with other additives known and commonly used in the field of electronic materials. Other additives include thermal polymerization inhibitors, UV absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial and antifungal agents, antifoaming agents, leveling agents, thickening agents. Agents, adhesion promoters, thixotropic agents, colorants, photoinitiating aids, sensitizers, thermoplastic resins, organic fillers, release agents, surface treatment agents, dispersants, dispersion aids, surface modifiers , Stabilizers, phosphors and the like.

  The curable resin composition of the present invention is preferably one selected from a thermosetting resin composition, a photocurable resin composition, and an alkali-developing photosensitive thermosetting resin composition.

  When the curable resin composition of the present invention is a thermosetting resin composition, it contains (C-1) thermosetting resin as (C) curable resin, and (A) core-shell rubber particles and (B) It is preferable that the surface-treated inorganic filler has a thermosetting reactive group. The (C-1) thermosetting resin is more preferably an epoxy resin, and the (A) core-shell rubber particles and (B) the surface-treated inorganic filler are used as the thermosetting reactive group, an epoxy group and oxetanyl. It preferably has a group, a mercapto group, or an isocyanate group. More preferably, it is an epoxy group.

  When the curable resin composition of the present invention is a photocurable resin composition, it contains (C-2) a photocurable resin as (C) a curable resin and further contains (D) a photopolymerization initiator. To do. The (A) core-shell rubber particles preferably have a methacrylic group, an acrylic group, or a vinyl group as a photocurable reactive group. More preferably, it is a methacrylic group or an acrylic group. The surface-treated inorganic filler (B) preferably has a photocurable reactive group, and preferably has a methacrylic group, an acrylic group, or a vinyl group as the photocurable reactive group. More preferably, it is a methacrylic group or an acrylic group.

  When the curable resin composition of the present invention is an alkali-developable photosensitive thermosetting resin composition, it contains (C-1) thermosetting resin as (C) curable resin, and further contains (C- 2) It is preferable to contain a photocurable resin and (D) a photopolymerization initiator. The thermosetting resin (C-1) is preferably an epoxy resin, and the photocurable resin (C-2) is preferably an alkali-soluble resin. It is preferable that the core-shell rubber particles (A) have an epoxy group, an oxetanyl group, a mercapto group, or an isocyanate group as a thermosetting reactive group. More preferably, it is an epoxy group. The surface-treated inorganic filler (B) preferably has a photocurable reactive group, and preferably has a methacrylic group, an acrylic group, or a vinyl group as the photocurable reactive group. More preferably, it is a methacrylic group or an acrylic group.

  The curable resin composition of the present invention may be used as a dry film or used as a liquid. When it is used as a liquid, it may be one-part or two-part or more.

  Next, the dry film of the present invention has a resin layer obtained by applying the curable resin composition of the present invention onto a carrier film and drying it. When forming a dry film, first, the curable resin composition of the present invention is diluted with the above organic solvent to adjust the viscosity to a suitable value, and then a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater. , A reverse coater, a transfer roll coater, a gravure coater, a spray coater, etc. to apply a uniform thickness on the carrier film. After that, the applied composition is usually dried at a temperature of 40 to 130° C. for 1 to 30 minutes to form a resin layer. The coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected within the range of 5 to 150 μm, preferably 15 to 60 μm.

  A plastic film is used as the carrier film, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used. The thickness of the carrier film is not particularly limited, but generally, it is appropriately selected within the range of 10 to 150 μm. More preferably, it is in the range of 15 to 130 μm.

  After forming a resin layer composed of the curable resin composition of the present invention on a carrier film, for the purpose of preventing dust from adhering to the surface of the film, a peelable cover film is further provided on the surface of the film. It is preferable to stack them. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. Any cover film may be used as long as it has a smaller adhesive force between the resin layer and the carrier film when the cover film is peeled off.

  In the present invention, a resin layer may be formed by coating the curable resin composition of the present invention on the cover film and drying it, and then laminating a carrier film on the surface thereof. That is, as the film to which the curable resin composition of the present invention is applied when producing the dry film in the present invention, either a carrier film or a cover film may be used.

  Further, the curable resin composition of the present invention is adjusted to have a viscosity suitable for a coating method using the above organic solvent, and then the dip coating method, the flow coating method, the roll coating method, and the bar coater are applied on a substrate. Method, screen printing method, curtain coating method, etc., and then the organic solvent contained in the composition is volatilized (temporarily dried) at a temperature of 60 to 100° C. to form a tack-free resin layer. can do. Further, in the case of a dry film in which the above composition is applied onto a carrier film or a cover film, dried and wound as a film, the composition of the present invention is laminated on the substrate by a laminator or the like. The resin layer can be formed by peeling off the carrier film after bonding to.

  Examples of the base material include a printed wiring board and a flexible printed wiring board on which circuits have been previously formed of copper, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy. , Synthetic fiber epoxy, fluororesin/polyethylene/polyphenylene ether, polyphenylene oxide/cyanate, etc. copper clad laminates for high frequency circuits. Copper grade clad laminates of all grades (FR-4 etc.) Plates and the like, metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates and the like can be mentioned.

  Volatile drying performed after applying the curable resin composition of the present invention, hot-air circulation type drying furnace, IR furnace, hot plate, convection oven, etc. (using a heat source of air heating system by steam It is possible to use a method of bringing hot air into countercurrent contact and a method of spraying hot air to a support from a nozzle).

  When the curable resin composition of the present invention is thermosetting, for example, it is heated to a temperature of 100 to 220° C. to be thermoset, whereby heat resistance, chemical resistance, moisture absorption resistance, adhesiveness, and electrical characteristics are obtained. It is possible to form a cured film (cured product) excellent in various properties such as.

  When the curable resin composition of the present invention is photocurable, the curable resin composition of the present invention is applied, and the resin layer obtained after volatilizing and drying the solvent is subjected to exposure (light irradiation). As a result, the exposed portion (the portion irradiated with light) is cured. When the curable resin composition of the present invention is a photosensitive thermosetting resin and contains a photobase generator, it is exposed to heat by activating the base in the exposed portion (light-irradiated portion). Part to deepen. Specifically, by a contact method or a non-contact method, a pattern-formed photomask is used for selective exposure with active energy rays or direct pattern exposure with a laser direct exposure machine. A resist pattern can be formed by developing the unexposed area with a dilute alkaline aqueous solution (for example, 0.3 to 3 mass% sodium carbonate aqueous solution).

The exposure machine used for irradiation with the active energy rays may be a high-pressure mercury lamp lamp, an ultra-high-pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, or any other device that irradiates ultraviolet rays in the range of 350 to 450 nm. Further, a direct drawing device (for example, a laser direct imaging device that draws an image directly with a laser using CAD data from a computer) can also be used. A lamp light source or a laser light source for a direct drawing machine may have a maximum wavelength in the range of 350 to 410 nm. The exposure amount for image formation varies depending on the film thickness and the like, but it can be generally in the range of 10 to 1000 mJ/cm ² , and preferably 20 to 800 mJ/cm ² .

  The developing method may be a dipping method, a shower method, a spray method, a brush method, or the like, and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Aqueous alkaline solutions such as ammonia and amines can be used.

  The curable resin composition of the present invention is preferably used for forming a cured film on a printed wiring board, more preferably used for forming a permanent film, and more preferably a solder resist, Used to form an interlevel dielectric layer, coverlay. Further, according to the curable resin composition of the present invention, since a cured product having excellent crack resistance can be obtained, a printed wiring board having a fine-pitch wiring pattern having a large influence of defects due to crack generation, for example, a package substrate. It can be suitably used for forming a permanent coating film such as a solder resist used for.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. In the following, “part” and “%” are based on mass unless otherwise specified.

[Synthesis Example of Photocurable Resin (Varnish C-2-1)]
In an autoclave equipped with a thermometer, a nitrogen introducing device and an alkylene oxide introducing device, and a stirrer, 119.4 parts of novolac-type cresol resin (Showa Denko KK, Shonor CRG951, OH equivalent: 119.4), potassium hydroxide 1.19 parts and toluene 119.4 parts were charged, the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 parts of propylene oxide was gradually added dropwise and reacted at 125 to 132° C. and 0 to 4.8 kg/cm ² for 16 hours. Then, it was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with this reaction solution to neutralize potassium hydroxide, and the nonvolatile content was 62.1% and the hydroxyl value was 182.2 g/eq. A propylene oxide reaction solution of the novolac type cresol resin was obtained. This was an average of 1.08 mol of alkylene oxide added per equivalent of the phenolic hydroxyl group.

  293.0 parts of the alkylene oxide reaction solution of the obtained novolac type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone and 252.9 parts of toluene were stirred with a temperature of a stirrer. A reactor equipped with a meter and an air blowing tube was charged, air was blown at a rate of 10 ml/min, and the reaction was performed at 110° C. for 12 hours while stirring. The water produced by the reaction was an azeotropic mixture with toluene, and 12.6 parts of water was distilled out. Then, it was cooled to room temperature, the resulting reaction solution was neutralized with 35.35 parts of a 15% sodium hydroxide aqueous solution, and then washed with water. Then, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate (carbitol acetate) with an evaporator to obtain a novolac type acrylate resin solution.

  Next, 332.5 parts of the obtained novolac type acrylate resin solution and 1.22 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was supplied at a rate of 10 ml/min. While blowing and stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added, reacted at 95 to 101° C. for 6 hours, and after cooling, the solid acid value was 88 mgKOH/g and the solid content was 65.8% carboxyl. A group-containing resin solution was obtained. Hereinafter referred to as Varnish C-2-1.

[Synthesis Example of Photocurable Resin (Varnish C-2-2)]
A flask equipped with a cooling tube and a stirrer was charged with 456 parts of bisphenol A, 228 parts of water and 649 parts of 37% formalin, kept at a temperature of 40° C. or lower, and added 228 parts of 25% aqueous sodium hydroxide solution. The reaction was carried out at 50°C for 10 hours. After completion of the reaction, the mixture was cooled to 40°C and neutralized to pH 4 with a 37.5% phosphoric acid aqueous solution while keeping the temperature at 40°C or lower. Then, the mixture was allowed to stand and the aqueous layer was separated. After separation, 300 parts of methyl isobutyl ketone was added and uniformly dissolved, and then washed with 500 parts of distilled water three times, and water, solvent and the like were removed under reduced pressure at a temperature of 50° C. or lower. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanol solution of the polymethylol compound. When a part of the obtained methanol solution of the polymethylol compound was dried at room temperature in a vacuum dryer, the solid content was 55.2%.

  500 parts of a methanol solution of the obtained polymethylol compound and 440 parts of 2,6-xylenol were charged and uniformly dissolved at 50°C. After uniform dissolution, methanol was removed under reduced pressure at a temperature of 50°C or lower. Thereafter, 8 parts of oxalic acid was added, and the mixture was reacted at 100°C for 10 hours. After the reaction was completed, the distillate was removed under reduced pressure of 180° C. and 50 mmHg to obtain 550 parts of novolac resin A.

Furthermore, 130 parts of the above novolak resin A, 2.6 parts of 50% sodium hydroxide aqueous solution, toluene/methyl isobutyl ketone (mass ratio) were placed in an autoclave equipped with a thermometer, a nitrogen introducing device/alkylene oxide introducing device, and a stirring device. = 2/1) 100 parts was charged, the system was replaced with nitrogen while stirring, and then the temperature was raised by heating, and 45 parts of ethylene oxide was gradually introduced and reacted at 150° C. and 8 kg/cm ² . The reaction was continued for about 4 hours until the gauge pressure reached 0.0 kg/cm ^2, and then cooled to room temperature. To this reaction solution, 3.3 parts of 36% aqueous hydrochloric acid solution was added and mixed to neutralize sodium hydroxide. This neutralization reaction product was diluted with toluene, washed three times with water, and desolvated with an evaporator to give a hydroxyl value of 175 g/eq. An ethylene oxide adduct of novolak resin A was obtained. This was an average of 1 mol of ethylene oxide added per equivalent of the phenolic hydroxyl group.

  175 parts of the ethylene oxide adduct of the novolac resin A thus obtained, 50 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 part of hydroquinone monomethyl ether, 130 parts of toluene, a stirrer, a thermometer, air After charging in a reactor equipped with a blowing tube, stirring while blowing air, and raising the temperature to 115° C., and distilling off the water produced by the reaction as an azeotropic mixture with toluene, after reacting for another 4 hours, Cooled to room temperature. The obtained reaction solution was washed with 5% NaCl aqueous solution and distilled under reduced pressure to remove toluene, and then diethylene glycol monoethyl ether acetate was added to obtain an acrylate resin solution having a solid content of 68%.

  Next, into a four-necked flask equipped with a stirrer and a reflux condenser, 312 parts of the obtained acrylate resin solution, 0.1 part of hydroquinone monomethyl ether and 0.3 part of triphenylphosphine were charged, and this mixture was heated at 110°C. Then, 45 parts of tetrahydrophthalic anhydride was added and reacted for 4 hours. After cooling, a carboxyl group-containing resin solution having a solid content of 70% and a solid content acid value of 65 mgKOH/g was obtained. Hereinafter referred to as Varnish C-2-2.

[Synthesis Example of Photocurable Resin (Varnish C-2-3)]
Cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, epoxy equivalent 220 g/eq) 220 parts (1 equivalent), carbitol acetate 140.1 parts, and solvent naphtha 60.3 parts were charged in a flask, and 90 The mixture was heated to ℃ and stirred to dissolve. The solution obtained was once cooled to 60° C., 72 parts (1 mol) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine were added, and the mixture was heated to 100° C. and reacted for about 12 hours to obtain an acid value. Of 0.2 mg KOH/g was obtained. To this, 80.6 parts (0.53 mol) of tetrahydrophthalic anhydride was added, heated to 90° C. and reacted for about 6 hours. The solid content acid value was 85 mgKOH/g and the solid content was 65.8%. A carboxyl group-containing resin solution having a saturated bond was obtained. Hereinafter referred to as Varnish C-2-3.

[Preparation of surface-treated silica (B-1)]
70 g of spherical silica (SFP-20M manufactured by Denki Kagaku Kogyo Co., Ltd.), 28 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 2 g of KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd. as a silane coupling agent are uniformly dispersed. Thus, a silica solvent dispersion B-1 was obtained.

[Preparation of surface-treated silica (B-2)]
70 g of spherical silica (SFP-20M manufactured by Denki Kagaku Kogyo Co., Ltd.), 28 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 2 g of KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd. as a silane coupling agent are uniformly dispersed. Thus, a silica solvent dispersion B-2 was obtained.

[Preparation of surface-treated silica (B-3)]
70 g of spherical silica (SFP-20M manufactured by Denki Kagaku Kogyo KK), 28 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 2 g of silane coupling agent (KBM-402 manufactured by Shin-Etsu Chemical Co., Ltd.) are homogeneous. By dispersing, a silica solvent dispersion B-3 was obtained.

[Preparation of surface-treated barium sulfate (B-4)]
70 g of barium sulfate (Sakai Chemical Industry B-30 (alumina surface-treated barium sulfate)), PMA (propylene glycol monomethyl ether acetate) 28 g as a solvent, and Shin-Etsu Chemical Co., Ltd. KBM-503 as a silane coupling agent. And 2 g were evenly dispersed to obtain a barium sulfate solvent-dispersed product B-4.

[Preparation of surface-treated barium sulfate (B-5)]
70 g of barium sulfate (B-30 (aluminum surface treated barium sulfate) manufactured by Sakai Chemical Industry Co., Ltd.), 28 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 2 g of BYK-made BYK-111 as a dispersant. After uniform dispersion, barium sulfate solvent dispersion B-5 was obtained.

[Preparation of untreated silica]
70 g of spherical silica (SFP-20M manufactured by Denki Kagaku Kogyo KK), 28 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 2 g of BYK-111 manufactured by BYK as a dispersant are uniformly dispersed to obtain silica. A solvent dispersion was obtained.

[Preparation of Epoxy Dispersion Product A-1 in which core-shell rubber particles having a curable reactive group on the surface are dispersed in an epoxy resin]
(Preparation of core-shell rubber particles having a curable reactive group on the surface)
1300 g of rubber latex and 440 g of pure water were charged into a 3 liter glass reactor, and this mixture was heated to 70° C. with stirring while introducing nitrogen. This rubber latex contains 480 g of polybutadiene particles having an average particle diameter of 0.1 μm, and 1.5% by mass of sodium dodecylbenzenesulfonate with 100% by mass of this polybutadiene. After 1.2 g of azoisobutyronitrile was added thereto, a mixture of 36 g of styrene, 48 g of methyl methacrylate, 24 g of acrylonitrile, and 12 g of glycidyl methacrylate was added over 3 hours. Then, the mixture was further stirred for 2 hours to obtain core-shell rubber particles (latex (L)). The solid content of the latex (L) was 32%. The gel fraction of the core-shell copolymer in the latex (L) was 98%. The rubber particle size in the latex (L) was 0.5 μm.

(Preparation of epoxy dispersion)
340 g of methyl ethyl ketone (MEK) was charged into a 1-liter tank, and 273 g of the latex (L) obtained above was added at 25°C. After mixing well, 126 g of pure water was added, and 30 g of a 5 mass% sodium sulfate aqueous solution was added with stirring. When the stirring was stopped, the water phase and the MEK phase were separated. After removing the aqueous phase and adding 90 g of MEK to the remaining MEK phase, 302 g of pure water was added with stirring, and further 30 g of a 5 mass% sodium sulfate aqueous solution was added. When the stirring was stopped, the water phase and the MEK phase were separated. The aqueous phase was removed, and the remaining MEK phase was mixed with 204 g of a bisphenol A type epoxy resin (jER828: manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 189) as an epoxy resin. The MEK was removed from this mixture on a rotary evaporator. Thus, a dispersion in which the core-shell copolymer was dispersed in the bisphenol A type epoxy resin was obtained. 100% by weight of this dispersion consists of 60% by weight of epoxy resin and 40% by weight of core-shell copolymer. The epoxy equivalent of the dispersion was 266. Hereinafter, it will be referred to as an epoxy dispersion product A-1.

  In order to examine the degree of dispersion of rubber particles, piperidine was added to this dispersion and cured at 120° C. for 16 hours. The appearance of the obtained cured product was transparent. From this, it is understood that the crosslinked rubber particles are completely primary-dispersed in the epoxy resin.

[Preparation of Epoxy Dispersion Product A-2 in which core-shell rubber particles having a curable reactive group on the surface are dispersed in an epoxy resin]
(Preparation of core-shell rubber particles having a curable reactive group on the surface)
1300 g of rubber latex and 440 g of pure water were charged into a 3 liter glass reactor, and this mixture was heated to 70° C. with stirring while introducing nitrogen. This rubber latex contains 480 g of polybutadiene particles having an average particle diameter of 0.1 μm, and 1.5% by mass of sodium dodecylbenzenesulfonate with 100% by mass of this polybutadiene. After 1.2 g of azoisobutyronitrile was added thereto, a mixture of 36 g of styrene, 48 g of methyl methacrylate, 24 g of acrylonitrile, and 12 g of glycidyl methacrylate was added over 3 hours. Then, the mixture was further stirred for 2 hours to obtain core-shell rubber particles (latex (L)). The solid content of the latex (L) was 32%. The gel fraction of the core-shell copolymer in the latex (L) was 98%. The rubber particle size in the latex (L) was 0.5 μm.

(Preparation of epoxy dispersion)
340 g of methyl ethyl ketone (MEK) was charged into a 1-liter tank, and 273 g of the latex (L) obtained above was added at 25°C. After mixing well, 126 g of pure water was added, and 30 g of a 5 mass% sodium sulfate aqueous solution was added with stirring. When the stirring was stopped, the water phase and the MEK phase were separated. After removing the aqueous phase and adding 90 g of MEK to the remaining MEK phase, 302 g of pure water was added with stirring, and further 30 g of a 5 mass% sodium sulfate aqueous solution was added. When the stirring was stopped, the water phase and the MEK phase were separated. The aqueous phase was removed, and the remaining MEK phase was mixed with 204 g of a bisphenol F type epoxy resin (jER806: manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 165) as an epoxy resin. The MEK was removed from this mixture on a rotary evaporator. Thus, a dispersion in which the core-shell copolymer was dispersed in the bisphenol A type epoxy resin was obtained. 100% by weight of this dispersion consists of 75% by weight of epoxy resin and 25% by weight of core-shell copolymer. The epoxy equivalent of the dispersion was 266. Hereinafter, it will be referred to as an epoxy dispersion product A-2.

  In order to examine the degree of dispersion of rubber particles, piperidine was added to this dispersion and cured at 120° C. for 16 hours. The appearance of the obtained cured product was transparent. From this, it is understood that the crosslinked rubber particles are completely primary-dispersed in the epoxy resin.

[Epoxy Dispersion Product R-1 in which core-shell rubber particles having no curable reactive group on the surface are dispersed in an epoxy resin]
(Preparation of core-shell rubber particle size)
1300 g of rubber latex and 440 g of pure water were charged into a 3 liter glass reactor, and this mixture was heated to 70° C. with stirring while introducing nitrogen. This rubber latex contains 480 g of polybutadiene particles having an average particle diameter of 0.1 μm, and 1.5% by mass of sodium dodecylbenzenesulfonate with 100% by mass of this polybutadiene. After 1.2 g of azoisobutyronitrile was added thereto, a mixture of 36 g of styrene, 48 g of methyl methacrylate, and 24 g of acrylonitrile was added over 3 hours. Then, the mixture was further stirred for 2 hours to obtain core-shell rubber particles (latex (L)). The solid content of the latex (L) was 32%. The gel fraction of the core-shell copolymer in the latex (L) was 98%. The rubber particle size in the latex (L) was 0.5 μm.

(Preparation of epoxy dispersion)
340 g of methyl ethyl ketone (MEK) was charged into a 1-liter tank, and 273 g of the latex (L) obtained above was added at 25°C. After mixing well, 126 g of pure water was added, and 30 g of a 5 mass% sodium sulfate aqueous solution was added with stirring. When the stirring was stopped, the water phase and the MEK phase were separated. After removing the aqueous phase and adding 90 g of MEK to the remaining MEK phase, 302 g of pure water was added with stirring, and further 30 g of a 5 mass% sodium sulfate aqueous solution was added. When the stirring was stopped, the water phase and the MEK phase were separated. The aqueous phase was removed, and the remaining MEK phase was mixed with 204 g of a bisphenol F type epoxy resin (jER806: manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 165) as an epoxy resin. The MEK was removed from this mixture on a rotary evaporator. Thus, a dispersion in which the core-shell copolymer was dispersed in the bisphenol A type epoxy resin was obtained. 100% by weight of this dispersion consisted of 75% by weight of epoxy resin and 25% by weight of core-shell copolymer. The epoxy equivalent of the dispersion was 266. Hereinafter, it will be referred to as epoxy dispersion R-1.

  In order to examine the degree of dispersion of rubber particles, piperidine was added to this dispersion and cured at 120° C. for 16 hours. The appearance of the obtained cured product was transparent. From this, it is understood that the crosslinked rubber particles are completely primary-dispersed in the epoxy resin.

[ Reference Examples 1 and 2, Examples 3 to 22, Comparative Examples 1 to 6]
The above resin solution (varnish) was blended together with the various components shown in Table 1 at the ratio (parts by mass) shown in Table 1, premixed with a stirrer, and then kneaded with a three-roll mill to obtain a curable resin composition The thing was prepared. Reference Examples 1 and 2 and Comparative Examples 1 and 2 are thermosetting resin compositions, and Examples 3 to 22 and Comparative Examples 3 to 6 are alkali development type photocurable thermosetting resin compositions.

<Measurement of glass transition temperature (Tg)>
The alkali-developable photocurable thermosetting resin composition was obtained by applying the curable resin composition on the entire surface of a copper foil substrate. This was dried and allowed to cool to room temperature to form a resin layer made of the curable resin composition. On the other hand, exposure was performed through a strip-shaped negative mask of 50 mm×3 mm at the optimum exposure amount. Then, development was performed by spraying a 1 wt% sodium carbonate aqueous solution at 30° C. to obtain a cured coating pattern. Further, it was heated and cured under predetermined conditions to obtain an evaluation substrate.
In the case of the thermosetting resin composition, a strip-shaped pattern of 50 mm×3 mm was printed on the copper foil substrate. This was dried and further heated and cured under predetermined conditions to obtain an evaluation substrate.
The cured film of the evaluation substrate obtained as described above was peeled from the copper foil and evaluated. The measurement was performed using a TMA measuring device (TMA/SS6000 manufactured by Shimadzu Corporation) to evaluate Tg. The criteria for judgment are as follows.
◎...145°C or higher ○...140°C or higher and lower than 145°C Δ...135°C or higher and lower than 140°C ×...less than 135°C

<Evaluation of CTE>
The alkali-developable photocurable thermosetting resin composition was obtained by applying the curable resin composition on the entire surface of a copper foil substrate. This was dried and allowed to cool to room temperature to form a resin layer made of the curable resin composition. On the other hand, exposure was performed through a strip-shaped negative mask of 50 mm×3 mm at the optimum exposure amount. Then, development was performed by spraying a 1 wt% sodium carbonate aqueous solution at 30° C. to obtain a cured coating pattern. Further, it was heated and cured under predetermined conditions to obtain an evaluation substrate.
In the case of the thermosetting resin composition, a strip-shaped pattern of 50 mm×3 mm was printed on the copper foil substrate. This was dried and further heated and cured under predetermined conditions to obtain an evaluation substrate.
The cured film of the evaluation substrate obtained as described above was peeled from the copper foil and evaluated. The measurement was performed using a TMA measuring device (TMA/SS6000 manufactured by Shimadzu Corporation), and CTEα1 (0 to 50° C.) was performed. The criteria for judgment are as follows.
◎...less than 40 ppm ○...40 ppm or more but less than 50 ppm Δ...50 ppm or more but less than 60 ppm x...60 ppm or more

<Evaluation of toughness>
The alkali-developable photocurable thermosetting resin composition was obtained by applying the curable resin composition on the entire surface of a copper foil substrate. This was dried and allowed to cool to room temperature to form a resin layer made of the curable resin composition. On the other hand, exposure was performed through a strip-shaped negative mask of 80 mm×10 mm at the optimum exposure amount. Then, development was performed by spraying a 1 wt% sodium carbonate aqueous solution at 30° C. to obtain a cured coating pattern. Further, it was heated and cured under predetermined conditions to obtain an evaluation substrate.
In the case of the thermosetting resin composition, 80 mm×10 mm strip-shaped pattern printing was performed on the copper foil substrate. This was dried and further heated and cured under predetermined conditions to obtain an evaluation substrate.
The cured film of the evaluation substrate obtained as described above was peeled from the copper foil and evaluated. The measurement was performed using a tensile tester (AGS-G 100N manufactured by Shimadzu Corporation), and the maximum point stress or the elongation at break was evaluated. The criteria for judgment are as follows.
∘: elongation at break 6% or more ○: elongation at break 4% or more and less than 6% Δ: elongation at break 2% or more and less than 4% ×... elongation at break 2% or less

<Evaluation of TCT resistance>
The alkali-developable photocurable thermosetting resin composition was obtained by applying the curable resin composition on the entire surface of a package substrate. This was dried and allowed to cool to room temperature to form a resin layer made of the curable resin composition. On the other hand, direct imaging exposure was performed on the copper pad with an opening size of 80 μm SRO (Solder Resist Opening) at the optimum exposure amount. Then, development was performed by spraying a 1 wt% sodium carbonate aqueous solution at 30° C. to obtain a cured coating pattern. Further, it was heated and cured under predetermined conditions. Then, Au plating treatment, solder bump formation, and Si chip mounting were carried out to obtain an evaluation board.
In the case of the thermosetting resin composition, the curable resin composition was applied over the entire surface of the package substrate, dried, and further heated and cured under predetermined conditions. After that, an opening size of SRO of 80 μm was opened with a UV laser or the like to obtain a pattern of the cured film. Then, Au plating treatment, solder bump formation, and Si chip mounting were carried out to obtain an evaluation board.
The evaluation substrate obtained as described above was put in a thermal cycler in which a temperature cycle was performed between −65° C. and 150° C., and TCT (Thermal Cycle Test) was performed. Then, the surface of the cured film was observed at 600 cycles, 800 cycles and 1000 cycles. The criteria for judgment are as follows.
◎: No abnormality at 1000 cycles ○: No abnormality at 800 cycles, cracks occurred at 1000 cycles △: No abnormality at 600 cycles, cracks occurred at 800 cycles ×: Cracks occurred at 600 cycles

<Evaluation of PCT resistance>
The alkali-developable photocurable thermosetting resin composition was obtained by applying the curable resin composition on the entire surface of a package substrate. This was dried and allowed to cool to room temperature to form a resin layer made of the curable resin composition. On the other hand, direct imaging exposure was performed on the copper pad with the opening size of SRO of 80 μm at the optimum exposure amount. Then, development was performed by spraying a 1 wt% sodium carbonate aqueous solution at 30° C. to obtain a cured coating pattern. Further, it was heated and cured under predetermined conditions to obtain an evaluation substrate.
In the case of the thermosetting resin composition, the curable resin composition was applied over the entire surface of the package substrate, dried, and further heated and cured under predetermined conditions. After that, an opening size of SRO of 80 μm was opened with a UV laser or the like to obtain a pattern of the cured film.
The obtained evaluation substrate was subjected to PCT (Pressure Maker Test) for 168 hours under the conditions of 121° C., saturation, and 0.2 MPa using a PCT device (HAST SYSTEM TPC-412MD manufactured by ESPEC Corp.). Then, the state of the coating film after PCT was evaluated. The criteria for judgment are as follows.
○: No swelling, peeling, discoloration, or elution ×: Many swelling, peeling, discoloration, or elution

＊１：上記で得たワニスＣ−２−１（カルボキシル基含有感光性樹脂のワニス）（固形分６５.８％、カルボン酸当量７９０ｇ／ｅｑ．）
＊２：上記で得たワニスＣ−２−２（カルボキシル基含有感光性樹脂のワニス）（固形分７０％、カルボン酸当量６５４ｇ／ｅｑ．）
＊３：上記で得たワニスＣ−２−３（カルボキシル基含有感光性樹脂のワニス）（固形分６５．８％、カルボン酸当量６６８ｇ／ｅｑ．）
＊４：オキシムエステル類（ＢＡＳＦジャパン社製ＩｒｇＯＸＥ０２：エタノン，１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−１−（ｏ−アセチルオキシム））
＊５：アセトフェノン類（ＢＡＳＦジャパン社製Ｉｒｇ１８４：１−ヒドロキシ−シクロヘキシル−フェニル−ケトン）
＊６：モノアシルフォスフィンオキサイド類（ＢＡＳＦジャパン社製ＴＰＯ：２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド）
＊７：Ｂｉｓ−Ａ型液状エポキシ樹脂（三菱化学社製ｊＥＲ８２８）
＊８：フェノールノボラックエポキシ樹脂（ザ・ダウ・ケミカル・カンパニー社製ＤＥＮ４３１：フェノールノボラックエポキシ樹脂）
＊９：ナフタレン型フェノールノボラックエポキシ樹脂（日本化薬社製ＮＣ−７０００Ｌをプロピレングリコールモノメチルエーテルアセテート（ＰＭＡ）で溶解、固形分６０％）
＊１０：上記で作製した硬化性反応基を有するコアシェルゴム粒子（エポキシ分散品Ａ−１：コアシェルゴム粒子をＢｉｓ−Ａ型エポキシ樹脂に均一分散。エポキシ反応基有。コアシェルゴム粒子４０％。コアシェルゴム粒子径０．５μｍ）
＊１１：上記で作製した硬化性反応基を有するコアシェルゴム粒子（エポキシ分散品Ａ−２：コアシェルゴム粒子をＢｉｓ−Ｆ型エポキシ樹脂に均一分散。エポキシ反応基有。コアシェルゴム粒子２５％。コアシェルゴム粒子径０．５μｍ）
＊１２：上記で作製した硬化性反応基を有しないコアシェルゴム粒子（エポキシ分散品Ｒ−１：コアシェルゴム粒子をＢｉｓ−Ａ型エポキシ樹脂に均一分散。エポキシ反応基無。コアシェルゴム粒子２５％。コアシェルゴム粒子径０．５μｍ）
＊１３：エポキシ化ポリブタジエン（ダイセル社製ＰＢ３６００）
＊１４：上記で調整した表面処理されたシリカ溶剤分散品Ｂ−１（球状シリカをＰＭＡに均一分散。メタクリル表面処理。シリカ含有量７０ｗｔ％（固形分）。シリカ平均粒径０．８μｍ）
＊１５：上記で調整した表面処理されたシリカ溶剤分散品Ｂ−２（球状シリカをＰＭＡに均一分散。ビニル表面処理。シリカ含有量７０ｗｔ％（固形分）。シリカ平均粒径０．８μｍ）
＊１６：上記で調整した表面処理されたシリカ溶剤分散品Ｂ−３（球状シリカをＰＭＡに均一分散。エポキシ表面処理。シリカ含有量７０ｗｔ％（固形分）。シリカ平均粒径０．８μｍ）
＊１７：上記で調整した表面処理された硫酸バリウム溶剤分散品Ｂ−４（硫酸バリウムをＰＭＡに均一分散。メタクリル表面処理。硫酸バリウム含有量７０ｗｔ％（固形分）。硫酸バリウム平均粒径０．５μｍ。
＊１８：上記で調整した表面処理された硫酸バリウム溶剤分散品Ｂ−５（硫酸バリウムをＰＭＡに均一分散。アルミナ表面処理。硫酸バリウム含有量７０ｗｔ％（固形分）。硫酸バリウム平均粒径（０．５μｍ））
＊１９：上記で調整した表面処理されていないシリカ溶剤分散品（球状シリカをＰＭＡに均一分散。表面処理無。シリカ含有量７０ｗｔ％（固形分）。シリカ平均粒径０．８μｍ）

*1: Varnish C-2-1 (varnish of carboxyl group-containing photosensitive resin) obtained above (solid content 65.8%, carboxylic acid equivalent 790 g/eq.)
*2: Varnish C-2-2 (varnish of carboxyl group-containing photosensitive resin) obtained above (solid content 70%, carboxylic acid equivalent 654 g/eq.)
*3: Varnish C-2-3 (varnish of carboxyl group-containing photosensitive resin) obtained above (solid content 65.8%, carboxylic acid equivalent 668 g/eq.)
*4: Oxime ester (IrgOXE02 manufactured by BASF Japan Ltd.: ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime))
*5: Acetophenones (Irg184: 1-hydroxy-cyclohexyl-phenyl-ketone manufactured by BASF Japan Ltd.)
*6: Monoacylphosphine oxides (BASF Japan Ltd. TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide)
*7: Bis-A type liquid epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation)
*8: Phenol novolac epoxy resin (DEN 431: Phenol novolac epoxy resin manufactured by The Dow Chemical Company)
*9: Naphthalene type phenol novolac epoxy resin (NC-7000L manufactured by Nippon Kayaku Co., Ltd. is dissolved in propylene glycol monomethyl ether acetate (PMA), solid content 60%)
*10: Core-shell rubber particles having a curable reactive group prepared above (epoxy dispersion A-1: core-shell rubber particles are uniformly dispersed in a Bis-A type epoxy resin. Epoxy reactive group is present. Core-shell rubber particles 40%. Rubber particle diameter 0.5 μm)
*11: Core-shell rubber particles having a curable reactive group prepared above (epoxy dispersion A-2: core-shell rubber particles are uniformly dispersed in Bis-F type epoxy resin. Epoxy reactive group is present. Core-shell rubber particles 25%. Rubber particle diameter 0.5 μm)
*12: Core-shell rubber particles having no curable reactive group prepared above (epoxy dispersion R-1: core-shell rubber particles are uniformly dispersed in Bis-A type epoxy resin. No epoxy reactive group, core-shell rubber particles 25%. Core shell rubber particle diameter 0.5 μm)
*13: Epoxidized polybutadiene (PB3600 manufactured by Daicel)
*14: Surface-treated silica solvent dispersion B-1 prepared above (uniform dispersion of spherical silica in PMA. Methacrylic surface treatment. Silica content 70 wt% (solid content). Silica average particle diameter 0.8 μm)
*15: Surface-treated silica solvent dispersion B-2 prepared as above (homogeneous dispersion of spherical silica in PMA. Vinyl surface treatment. Silica content 70 wt% (solid content). Silica average particle size 0.8 μm)
*16: Surface-treated silica solvent dispersion B-3 prepared above (uniform dispersion of spherical silica in PMA. Epoxy surface treatment. Silica content 70 wt% (solid content). Silica average particle size 0.8 μm)
*17: Surface-treated barium sulfate solvent dispersion B-4 prepared as described above (barium sulfate is uniformly dispersed in PMA. Methacrylic surface treatment. Barium sulfate content 70 wt% (solid content). Barium sulfate average particle size of 0. 5 μm.
*18: Surface-treated barium sulfate solvent dispersion B-5 prepared as described above (barium sulfate is uniformly dispersed in PMA. Alumina surface treatment. Barium sulfate content 70 wt% (solid content). Barium sulfate average particle size (0 .5 μm))
*19: Non-surface-treated silica solvent dispersion prepared as above (uniform dispersion of spherical silica in PMA. No surface treatment. Silica content 70 wt% (solid content). Silica average particle size 0.8 μm)

  From the results shown in the above table, it is understood that the cured product of the curable resin composition of the present invention has excellent TCT resistance. It is also found that Tg, CTE, toughness and PCT resistance are not deteriorated. On the other hand, (B) the curable resin composition of Comparative Examples 1 and 3 containing an inorganic filler which is not surface-treated in place of the inorganic filler, and (A) a core-shell rubber which does not have a curable reactive group in place of the core-shell rubber particles. Curable resin compositions of Comparative Examples 2 and 4 containing particles, (A) Curable resin composition of Comparative Example 5 containing no core-shell rubber particles, and (A) core-shell rubber particles in place of a thermoplastic resin. It can be seen that the cured product of the curable resin composition of Comparative Example 6 contained therein is inferior in TCT resistance.

Claims (11)

(A) core-shell rubber particles having a curable reactive group on the surface,
(B) a surface-treated inorganic filler,
(C) including a curable resin,
As the (C) curable resin, (C-2) contains a photocurable resin,
The curable resin composition, wherein the curable reactive group of the core-shell rubber particles having the curable reactive group (A) on the surface is a group that reacts with the curable resin (C). Furthermore, (C-1) thermosetting resin is included as said (C) curable resin , The curable resin composition of Claim 1 characterized by the above-mentioned. The curable resin composition according to claim 1 or 2, wherein the surface-treated inorganic filler (B) has a curable reactive group that reacts with the photocurable resin (C-2) on the surface. (B) the surface-treated inorganic filler, the curable resin composition according to any one of claims 1 to 3, characterized in that a surface-treated inorganic filler with a silane coupling agent. Further, (D) a photopolymerization initiator, and (E) a curable resin composition according to any one of claims 1 to 4, characterized in that it comprises at least one selected from among the photobase generator object. (B) the surface-treated size of the inorganic filler, the curable resin composition according to any one of claims 1 to 5, characterized in that the average particle size is 2μm or less. (B) the curing according to any one of claims 1 to 6, the content of the surface treated inorganic filler, characterized in that 20 to 80 wt% per total amount of solids in the composition Resin composition. Dry film to the curable resin composition according to any one of claims 1 to 7 applied to the film, characterized by having a resin layer obtained by drying. The curable resin composition according to any one of claims 1 to 7 cured product characterized by being obtained by curing. A cured product obtained by curing the resin layer of the dry film according to claim 8 . Printed wiring board characterized by having a claim 9 or 10 cured product according.