JP2018119110A - Resin composition, resin sheet, printed board and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that can improve heat resistance and plating adhesion while having sufficient coating properties and developability, and a resin sheet, a printed wiring board, and a semiconductor device using the same.SOLUTION: A resin composition contains an epoxy (meth) acrylate compound of formula (1) (A), and, as a photocuring initiator, a phosphine oxide compound (B) (as one example, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide). The resin composition may further contain an ethylenic unsaturated compound other than the epoxy (meth) acrylate compound (A). The resin composition may further contain a maleimide compound (C).SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a resin sheet using the resin composition, a printed wiring board, and a semiconductor device.

  In recent years, higher integration and miniaturization of semiconductor devices widely used in electronic devices, communication devices, personal computers, and the like have been accelerated, and data communication used in information communication has been increased in speed and capacity. . Under such circumstances, in order to respond to the miniaturization and high density of the printed wiring board, the build-up layer used for the multilayer printed wiring board is made into multiple layers, and miniaturization and high density of the wiring itself are required. Therefore, the resin composition used for the build-up layer has sufficient coatability and developability in addition to the photosensitivity capable of forming a pattern including a photovia using a photolithographic method that is easy to process finely and inexpensively. It is requested. As such a photosensitive material, for example, Patent Documents 1 and 2 describe a photosensitive resin composition containing a predetermined component.

JP 2014-74764 A JP 2009-251451 A

  On the other hand, various characteristics (for example, low water absorption, moisture absorption heat resistance, flame retardancy, low dielectric constant, low dielectric loss tangent, low thermal expansion coefficient, heat resistance, chemical resistance, coating required for laminated boards used for printed wiring boards. Film properties, developability, plating adhesion, high plating peel strength, etc.) are becoming increasingly severe. In addition, it is also important to sufficiently suppress the warpage of the semiconductor plastic package caused by the difference in thermal expansion coefficient between the semiconductor element (chip) and the printed wiring board. It is also required to sufficiently reduce the warpage of the laminate itself.

  However, according to the detailed study of the present inventors, the conventional photosensitive resin composition has sufficient coating properties and developability, and suppresses the warp of the laminated board for a printed wiring board itself. However, it is still difficult to realize the heat resistance (high glass transition temperature (high Tg)) and sufficiently increase the plating adhesion, and further improvements in these properties are desired.

  Therefore, the present invention has been made in view of the above problems, and has a resin composition capable of improving heat resistance and plating adhesion while having sufficient coating properties and developability, and uses the same. An object of the present invention is to provide a resin sheet, a printed wiring board, and a semiconductor device.

  The present inventors have found that the above problems can be solved by using a resin composition containing a specific epoxy (meth) acrylic acid ester compound (A) and a specific phosphine oxide compound (B). It came to complete.

That is, the present invention includes the following contents.
[1]
An epoxy (meth) acrylic acid ester compound (A) represented by the following formula (1);
A phosphine oxide compound (B) represented by the following formula (4);
Containing a resin composition.

(In Formula (1), each of R ₁ independently represents a hydrogen atom or a methyl group, each of R ₂ independently represents a hydrogen atom or a methyl group, and each of R ₃ represents Independently, a substituent represented by the following formula (2), a substituent represented by the following formula (3) or a hydroxy group is shown.

(In formula (3), R ₄ represents a hydrogen atom or a methyl group.)

(In Formula (4), R < ₅ > -R < ₁₀ > shows a hydrogen atom or a C1-C4 alkyl group each independently, and R < ₁₁ > is a C1-C20 alkyl group or C6-C20. An aryl group of

[2]
The phosphine oxide compound (B) is a compound represented by the following formula (5).
[1] The resin composition according to [1].

[3]
Further containing a maleimide compound (C),
The resin composition as described in [1] or [2].

[4]
Further containing a filler (D),
The resin composition according to any one of [1] to [3].

[5]
Further containing a compound (E) having an ethylenically unsaturated group other than the epoxy (meth) acrylate compound (A),
The resin composition according to any one of [1] to [4].

[6]
Further containing at least one compound (F) from the group selected from an epoxy resin, a cyanate ester compound, a phenol resin, an oxetane resin, and a benzoxazine compound,
The resin composition according to any one of [1] to [5].

[7]
The acid value of the epoxy (meth) acrylic acid ester compound (A) is 30 to 120 mgKOH / g,
The resin composition according to any one of [1] to [6].

[8]
The compound (E) having an ethylenically unsaturated group is a compound having a (meth) acryloyl group and / or a compound having a vinyl group.
The resin composition according to any one of [5] to [7].

[9]
The filler (D) is made of silica, boehmite, barium sulfate, silicone powder, fluorine resin filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene / butadiene rubber and silicone rubber. Any one or more selected from the group,
[4] The resin composition according to any one of [8].

[10]
Further containing a thermosetting accelerator (G),
The resin composition according to any one of [1] to [9].

[11]
The resin sheet containing the resin composition in any one of [1]-[10].

[12]
[1] A printed wiring board containing the resin composition according to any one of [10].

[13]
[1] A semiconductor device containing the resin composition according to any one of [10].

  According to the present invention, there are provided a resin composition capable of improving heat resistance and plating adhesion while having sufficient coating properties and developability, a resin sheet, a printed wiring board and a semiconductor device using the same. can do.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist. In this specification, “(meth) acryloyl group” means both “acryloyl group” and “methacryloyl group” corresponding thereto, and “(meth) acrylate” means “acrylate” and corresponding to it. “Methacrylate” means both, and “(meth) acrylic acid” means both “acrylic acid” and the corresponding “methacrylic acid”. In the present embodiment, “resin solid content” means a component in the resin composition excluding the solvent and filler (D) unless otherwise specified, and “resin solid content 100 parts by mass” The total of the components excluding the solvent and filler (D) in the resin composition is 100 parts by mass.

  The resin composition of this embodiment contains a specific epoxy (meth) acrylic ester compound (A) and a specific phosphine oxide compound (B).

<Epoxy (meth) acrylic ester compound (A)>
The epoxy (meth) acrylic acid ester compound (A) used in the present embodiment is an active energy ray-curable (photo-curable) resin, and is represented by the following formula (1). It may be used, may include isomers such as structural isomers and stereoisomers, and two or more compounds having different structures may be used in appropriate combination.

Here, in Formula (1), several R < ₁ > shows a hydrogen atom or a methyl group each independently, and it is preferable to contain a hydrogen atom from a viewpoint of improving the reactivity of photocuring reaction among these, Preferably, all of R ₁ are hydrogen atoms.

Several R < ₂ > shows a hydrogen atom or a methyl group each independently, It is preferable that a methyl group is included from a viewpoint of improving the heat resistance of hardened | cured material among these, More preferably, all of R < ₂ > is a methyl group. is there.

A plurality of R ₃ each independently represent a substituent represented by the following formula (2), a substituent represented by the following formula (3) or a hydroxy group, and among them, from the viewpoint of improving heat resistance, It preferably contains a hydroxyl group. Moreover, in this embodiment, it is also from the viewpoint of improving developability to use the epoxy (meth) acrylic acid ester compound (A) containing the substituent represented by Formula (2) among several R < ₃ >. ,preferable. In the present embodiment, it is also preferable to use an epoxy (meth) acrylate compound (A) containing a substituent represented by the formula (3) among a plurality of R ₃ from the viewpoint of improving heat resistance. . Moreover, in Formula (3), R < ₄ > shows a hydrogen atom or a methyl group, and it is preferable that it is a hydrogen atom from a viewpoint of improving the reactivity of photocuring reaction among these.

Further, from the viewpoint of improving developability, a plurality of R ₃ has a ratio of the substituent represented by the formula (2) among all the substituents of R ₃ of 20% or more and 85% or less, and the formula (3) Is preferably 5% to 70%, and the hydroxy group is preferably 10% to 75%.

  As an epoxy (meth) acrylic acid ester compound (A), including at least one of the following compounds (A1) to (A5) can improve the reactivity of the photocuring reaction, the heat resistance and developability of the cured product. It is preferable because it can be improved, it is more preferable that at least the compound (A1) is contained, more preferably any two or more of the compounds (A1) to (A5), and the compound (A1) and the compound (A2). More preferably, any one or more of (A5) is included. As an epoxy (meth) acrylic acid ester compound (A), it is also preferable to contain a compound (A2) and (A3) at least.

  Such epoxy (meth) acrylic acid ester compound (A) may be a commercially available product, such as KAYARAD (registered trademark) ZCR-6001H, KAYARAD (registered trademark) ZCR-6002H, KAYARAD (registered trademark) ZCR. -6006H, KAYARAD (registered trademark) ZCR-6007H (manufactured by Nippon Kayaku Co., Ltd.) and the like.

  Content of an epoxy (meth) acrylic acid ester compound (A) is not specifically limited, From a viewpoint of hardening a resin composition with an active energy ray, Preferably it is 1 mass part with respect to 100 mass parts of resin solid content. It is above, More preferably, it is 2 mass parts or more, More preferably, it is 3 mass parts or more. Further, from the viewpoint of sufficiently curing with active energy rays and improving heat resistance, the amount is preferably 99 parts by mass or less, more preferably 98 parts by mass or less, and still more preferably 100 parts by mass of the resin solid content. Is 97 parts by mass or less.

  Moreover, the acid value of an epoxy (meth) acrylic acid ester compound (A) is not specifically limited, From a viewpoint of improving developability, Preferably it is 30 mgKOH / g or more, More preferably, it is 50 mgKOH / g or more. In addition, from the viewpoint of preventing dissolution by a developer after curing with active energy rays, it is preferably 120 mgKOH / g or less, more preferably 110 mgKOH / g or less. The “acid value” in the present embodiment indicates a value measured by a method according to JISK 0070: 1992.

<Phosphine oxide compound (B)>
The phosphine oxide compound (B) used in the present embodiment is an active energy ray polymerization initiator (photocuring initiator) for improving the photocurability of the epoxy (meth) acrylate compound (A). It is represented by Formula (4).

Here, in formula (4), R _{5 to} R ₁₀ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁₁ represents an alkyl group having 1 to 20 carbon atoms or 6 carbon atoms. Represents an aryl group of ˜20.

  A commercial item may be used for such a phosphine oxide compound (B), and you may synthesize | combine by a conventional method. Examples of such commercially available products include compounds represented by the following formula (5) (phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide: Irgacure (registered trademark) 819 manufactured by BASF Japan Ltd.) and the like. . These phosphine oxide compounds (B) can be used alone or in combination of two or more.

  The content of the phosphine oxide compound (B) is not particularly limited, and is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 25 parts by mass with respect to 100 parts by mass of the resin solid content. It is a mass part, More preferably, it is 0.3 mass part-20 mass parts. When the content of the phosphine oxide compound (B) is within the above range, the coating property and developability as a photosensitive resin composition are excellent, and the glass transition temperature (Tg) and plating adhesion of the resulting cured product are excellent. There is a tendency for the properties to further improve.

<Maleimide compound (C)>
The resin composition of this embodiment may further contain a maleimide compound (C). The maleimide compound (C) is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule. Specific examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, 4,4. -Diphenylmethane bismaleimide, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) Methane, phenylmethanemaleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, 2,2-bis (4- (4-Maleimidov Noxy) -phenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide- (2,2 , 4-trimethyl) hexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 4,4-diphenylmethane biscitraconimide, 2,2-bis [4- (4-citraconimidophenoxy) phenyl] propane, bis (3,5-dimethyl-4-citraconimidophenyl) methane, bis (3-ethyl- 5-methyl-4-citraconimidophenyl) methane, bis (3,5-die Ru-4-citraconimidophenyl) methane, polyphenylmethanemaleimide, novolac-type maleimide compound, biphenylaralkyl-type maleimide compound, maleimide compound represented by the following formula (10), maleimide compound represented by the following formula (11), And prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds.

In formula (10), several R < ₅ > represents a hydrogen atom or a methyl group each independently. n ₁ represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5.

In formula (10), several R < ₆ > represents a hydrogen atom or a methyl group each independently. n ₂ represents an integer of 1 or more, preferably an integer of 1 to 5.

  These maleimide compounds can be used singly or in appropriate combination of two or more. Among these, from the viewpoint of excellent heat resistance, the maleimide compound represented by the formula (10) and the compound represented by the formula (11) are preferable, and the maleimide compound represented by the formula (10) is more preferable. preferable. A commercially available product may be used as the maleimide compound represented by the formula (10), and examples thereof include BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd.). A commercially available product may be used as the maleimide compound represented by the formula (11), and examples thereof include MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.).

  Content of a maleimide compound (C) is not restrict | limited in particular, Preferably it is 0.01 mass part-50 mass parts with respect to 100 mass parts of resin solid content in a resin composition, More preferably, it is 0.02. Mass parts to 45 parts by mass, more preferably 0.03 parts by mass to 20 parts by mass, still more preferably 0.1 parts by mass to 10 parts by mass, and even more preferably 1 part by mass to 7 parts by mass. Part by mass. When the content of the maleimide compound (C) is within the above range, the heat resistance of the cured product tends to be further improved.

<Filler (D)>
The resin composition of the present embodiment may further contain a filler (D). The filler (D) is not particularly limited as long as it has insulating properties. For example, natural silica, fused silica, synthetic silica, amorphous silica, aerosil, hollow silica and other silicas, white carbon, titanium white , Oxides such as zinc oxide, magnesium oxide, zirconium oxide, boron nitride, agglomerated boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide heat treated products (heat treated aluminum hydroxide, crystal Water with reduced water), boehmite, magnesium hydroxide and other metal hydrates, molybdenum compounds such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined Clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, E-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fibers (glass fine powders such as E glass, T glass, D glass, S glass, Q glass, etc. In addition to inorganic fillers such as hollow glass and spherical glass, silicone powder, fluororesin filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene / butadiene rubber, Organic fillers such as silicone rubber can be used. Among these, from the group consisting of silica, boehmite, barium sulfate, silicone powder, fluorine resin filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene-butadiene rubber, and silicone rubber It is preferable that it is 1 or more types selected.

  Among inorganic fillers, silica is particularly preferable and fused silica is particularly preferable from the viewpoint of further improving the heat resistance of the cured product. Specific examples of silica include SFP-130MC manufactured by Denka Corporation, SC2050-MB, SC2050-MNU, SC1050-MLE, YA010C-MFN, YA050C-MJA manufactured by Admatechs Corporation.

  Further, among organic fillers, fluororesin fillers are preferable, and in particular, fluorine with silica attached to the surface from the viewpoint of improving wiring embedding property and moisture absorption heat resistance after wiring embedding. Resin-based fillers are particularly preferred. The fluororesin particles used in the fluororesin-based filler are not particularly limited, and are polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoroalkoxyethylene copolymer (PFA), tetrafluoroethylene / hexafluoroethylene. And propylene fluoride copolymer (FEP), ethylene / chlorotrifluoroethylene copolymer (PCTFE), ethylene / tetrafluoroethylene copolymer (ETFE), and polyvinylidene fluoride (PVDF). Among these, PTFE is particularly preferable from the viewpoint of excellent electrical characteristics.

  Content of a filler (D) is not restrict | limited in particular, Preferably it is 5 mass parts-400 mass parts with respect to 100 mass parts of resin solid content, More preferably, they are 10 mass parts-350 mass parts, More preferably, it is 15 mass parts-300 mass parts. When content of a filler (D) exists in the said range, it exists in the tendency for the thermal expansion coefficient of hardened | cured material to fall more and for heat resistance to improve more.

<Compound (E) having an ethylenically unsaturated group>
The resin composition of this embodiment has an ethylenically unsaturated group other than the epoxy (meth) acrylic acid ester compound (A) in order to enhance curability by active energy rays (for example, photocurability by ultraviolet rays). The compound (E) may further be contained. The compound (E) having an ethylenically unsaturated group is a compound having one or more ethylenically unsaturated groups in the molecule (provided that the epoxy (meth) acrylic acid ester compound (A) is excluded). Although not particularly limited, preferred specific examples include a compound having a (meth) acryloyl group and / or a compound having a vinyl group.

  As a compound having a (meth) acryloyl group, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether , Phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) acrylate, diethylene di (meth) acrylate Rate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogenated bisphenol ethylene oxide (Meth) acrylate, bisphenol di (meth) acrylate, ε-caprolactone modified hydroxypivalic acid neopent glycol di (meth) acrylate, ε-caprolactone modified dipentaerythritol hexa (meth) acrylate, ε-caprolactone modified dipentaerythritol poly ( (Meth) acrylate, dipentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) acrylate Relate, triethylolpropane tri (meth) acrylate, and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate, and its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, And ethylene oxide adducts thereof.

  In addition, urethane (meth) acrylates that have (meth) acryloyl groups and urethane bonds in the same molecule, polyester (meth) acrylates that have (meth) acryloyl groups and ester bonds in the same molecule, and epoxy resins Epoxy (meth) acrylates derived from the above and having a (meth) acryloyl group, and reactive oligomers in which these bonds are used in combination.

  The urethane (meth) acrylates are a reaction product of a hydroxyl group-containing (meth) acrylate, a polyisocyanate, and other alcohols used as necessary. For example, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerin (meta) such as glycerin mono (meth) acrylate, glycerin di (meth) acrylate, etc. ) Sugar alcohol (meth) acrylates such as acrylates, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate , Isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate Dicyclohexane diisocyanate, and their isocyanurate, by reacting polyisocyanates such as buret reactants, the urethane (meth) acrylates.

  The epoxy (meth) acrylates are carboxylate compounds of a compound having an epoxy group and (meth) acrylic acid. For example, phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, trishydroxyphenylmethane type epoxy (meth) acrylate, dicyclopentadienephenol type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate Bisphenol F type epoxy (meth) acrylate, biphenol type epoxy (meth) acrylate, bisphenol A novolak type epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, glyoxal type epoxy (meth) acrylate, heterocyclic epoxy ( And meth) acrylates and their anhydride-modified epoxy (meth) acrylates.

  Examples of the compound having a vinyl group include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methyl styrene, ethyl styrene, divinyl benzene, α-methyl styrene, and oligomers thereof. Other vinyl compounds include triallyl isocyanurate, trimethallyl isocyanurate, bisallyl nadiimide and the like.

  These compounds (E) having an ethylenically unsaturated group can be used singly or in combination of two or more. Among these, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, cresol novolac type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate And at least one selected from the group consisting of bisallylnadiimide. By including the compound (E) having such kind of ethylenically unsaturated group, the heat resistance of the obtained cured product tends to be further improved.

<Compound (F) as other component>
The resin composition of the present embodiment may contain a compound (F) as another component, if necessary, in addition to the above components. Such a compound (F) is not particularly limited, and examples thereof include one or more selected from the group selected from an epoxy resin, a cyanate ester compound, a phenol resin, an oxetane resin, and a benzoxazine compound.

〔Epoxy resin〕
The epoxy resin is not particularly limited as long as it is a compound having two or more epoxy groups in the molecule. Specific examples thereof include bisphenol A type epoxy resin, bisphenol E type epoxy resin, and bisphenol F type epoxy resin. Bisphenol S type epoxy resin, bisphenol A novolak type epoxy resin, biphenyl type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, xylene novolak type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene Skeletal modified novolac type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type Poxy resin, triglycidyl isocyanurate, glycidyl ester type epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, phenol aralkyl novolak type epoxy resin, naphthol aralkyl novolak type epoxy resin, aralkyl novolak Type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, glycidyl amine, butadiene epoxidized compound, hydroxyl group-containing Examples thereof include compounds obtained by a reaction between silicone resins and epichlorohydrin, and halides thereof. These epoxy resins can be used alone or in combination of two or more. Among these, from the viewpoint of further improving the flame retardancy and heat resistance of the cured product, dicyclopentadiene novolac type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, polyfunctional phenol type epoxy resin And naphthalene type epoxy resins are more preferred.

  The content of the epoxy resin is not particularly limited, and is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 45 parts by mass with respect to 100 parts by mass of the resin solid content. More preferably, it is 0.3 to 40 parts by mass. When the content of the epoxy resin is within the above range, the heat resistance and chemical resistance of the cured product tend to be further improved.

[Cyanate ester compound]
The cyanate ester compound is not particularly limited as long as it is a resin having in its molecule an aromatic moiety substituted with at least one cyanate group (cyanate ester group).

  Examples of the cyanate ester compound include those represented by the formula (6).

Here, in Formula (6), Ar ₁ represents a single bond of a benzene ring, a naphthalene ring or two benzene rings. When there are a plurality, they may be the same or different. Each Ra is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 6 carbon atoms and an alkyl group having 6 to 12 carbon atoms. A group to which an aryl group is bonded is shown. The aromatic ring in Ra may have a substituent, and the substituent in Ar ₁ and Ra can be selected at any position. p is a number of cyanate groups bonded to Ar _1, is an integer of 1 to 3 independently. q indicates the number of Ra bonded to Ar _1, and 4-p when Ar ₁ is a benzene ring, 6-p when Ar ₁ is a naphthalene ring, and 8-p when two benzene rings are a single bond. . t represents an average number of repetitions and is an integer of 0 to 50, and the other cyanate compound (C) may be a mixture of compounds having different t. When there are a plurality of Xs, each independently represents a single bond, a divalent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a hetero atom), or a divalent group having 1 to 10 nitrogen atoms. An organic group (for example, —N—R—N— (wherein R represents an organic group)), a carbonyl group (—CO—), a carboxy group (—C (═O) O—), a carbonyl dioxide group ( —OC (═O) O—), a sulfonyl group (—SO ₂ —), a divalent sulfur atom, or a divalent oxygen atom.

  The alkyl group in Ra of Formula (6) may have any of a linear or branched chain structure and a cyclic structure (for example, a cycloalkyl group).

  In addition, the hydrogen atom in the alkyl group in Formula (6) and the aryl group in Ra may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, or a cyano group. Good.

  Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group, 2,2-dimethylpropyl group. Group, cyclopentyl group, hexyl group, cyclohexyl group, trifluoromethyl group and the like.

  Specific examples of the aryl group include phenyl group, xylyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyanophenyl group, trifluorophenyl. A group, a methoxyphenyl group, and an o-, m- or p-tolyl group. Furthermore, examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.

  Specific examples of the divalent organic group having 1 to 50 carbon atoms in X in the formula (6) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, and a biphenylylmethylene group. Group, dimethylmethylene-phenylene-dimethylmethylene group, fluorenediyl group, phthalidodiyl group and the like. The hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, a cyano group, or the like.

  Examples of the divalent organic group having 1 to 10 nitrogen atoms in X of formula (6) include an imino group and a polyimide group.

  Moreover, as an organic group of X in Formula (6), what is a structure represented by following formula (7) or following formula (8) is mentioned, for example.

Here, in formula (7), Ar ₂ represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and when u is 2 or more, they may be the same or different. Rb, Rc, Rf and Rg are each independently an aryl having at least one hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or a phenolic hydroxy group. Indicates a group. Rd and Re are each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, and a hydroxy group. The u represents an integer of 0 to 5.

Here, in the formula (8), Ar ₃ represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and when v is 2 or more, they may be the same or different. Ri and Rj are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydroxy group, a trifluoromethyl group, Or an aryl group substituted with at least one cyanato group. v represents an integer of 0 to 5, but may be a mixture of compounds having different v.

  Furthermore, as X in Formula (6), the bivalent group represented by a following formula is mentioned.

  Here, in the formula, z represents an integer of 4 to 7. Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Specific examples of Ar _{2 in} formula (7) and Ar _{3 in} formula (8) include two carbon atoms represented by formula (7) or two oxygen atoms represented by formula (8) having 1, 4 Benzenetetrayl group bonded to position or 1,3 position, the above two carbon atoms or two oxygen atoms are 4,4 ′ position, 2,4 ′ position, 2,2 ′ position, 2,3 ′ position , 3, 3′-position, or 3,4′-position, and the above two carbon atoms or two oxygen atoms are 2, 6-position, 1, 5-position, 1, 6 Naphthalenetetrayl group bonded to the 1-position, 1,8-position, 1,3-position, 1,4-position, or 2,7-position.

  Rb, Rc, Rd, Re, Rf and Rg in formula (7), and the alkyl group and aryl group in Ri and Rj in formula (8) have the same meanings as in formula (6) above.

  Specific examples of the cyanato-substituted aromatic compound represented by the above formula (6) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1- Cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-, 1-cyanato-2,4-, 1-cyanato-2,5-, 1 -Cyanato-2,6-, 1-cyanato-3,4- or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanatononylbenzene, 2- ( 4-cyanphenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, -Cyanato-2- or 1-cyanato-3-chlorobenzene, 1-cyanato-2,6-dichlorobenzene, 1-cyanato-2-methyl-3-chlorobenzene, cyanatonitrobenzene, 1-cyanato-4-nitro-2 -Ethylbenzene, 1-cyanato-2-methoxy-4-allylbenzene (eugenol cyanate), methyl (4-cyanatophenyl) sulfide, 1-cyanato-3-trifluoromethylbenzene, 4-cyanatobiphenyl, 1- Cyanato-2- or 1-cyanato-4-acetylbenzene, 4-cyanatobenzaldehyde, 4-cyanatobenzoic acid methyl ester, 4-cyanatobenzoic acid phenyl ester, 1-cyanato-4-acetaminobenzene, 4-cyanato Benzophenone, 1-cyanato-2,6-di-tert-butyl Tylbenzene, 1,2-dicyanatobenzene, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,4-dicyanato-2,4-dimethyl Benzene, 1,4-dicyanato-2,3,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 1-cyanato or 2-si Anatonaphthalene, 1-cyanato-4-methoxynaphthalene, 2-cyanato-6-methylnaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2′-dicyanato-1,1′-binaphthyl, 1,3-, 1, 4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-dicyanatosinaphthalene, 2,2'- or 4,4'-dicyanana Biphenyl, 4,4′-dicyanatooctafluorobiphenyl, 2,4′- or 4,4′-dicyanatodiphenylmethane, bis (4-cyanato-3,5-dimethylphenyl) methane, 1,1-bis (4 -Cyanatophenyl) ethane, 1,1-bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanato-3-methylphenyl) Propane, 2,2-bis (2-cyanato-5-biphenylyl) propane, 2,2-bis (4-cyanatophenyl) hexafluoropropane, 2,2-bis (4-cyanato-3,5-dimethyl) Phenyl) propane, 1,1-bis (4-cyanatophenyl) butane, 1,1-bis (4-cyanatophenyl) isobutane, 1,1-bis (4-cyanatopheny) ) Pentane, 1,1-bis (4-cyanatophenyl) -3-methylbutane, 1,1-bis (4-cyanatophenyl) -2-methylbutane, 1,1-bis (4-cyanatophenyl)- 2,2-dimethylpropane, 2,2-bis (4-cyanatophenyl) butane, 2,2-bis (4-cyanatophenyl) pentane, 2,2-bis (4-cyanatophenyl) hexane, 2 , 2-bis (4-cyanatophenyl) -3-methylbutane, 2,2-bis (4-cyanatophenyl) -4-methylpentane, 2,2-bis (4-cyanatophenyl) -3,3 -Dimethylbutane, 3,3-bis (4-cyanatophenyl) hexane, 3,3-bis (4-cyanatophenyl) heptane, 3,3-bis (4-cyanatophenyl) octane, 3,3- Bis (4-Cyanatov Enyl) -2-methylpentane, 3,3-bis (4-cyanatophenyl) -2-methylhexane, 3,3-bis (4-cyanatophenyl) -2,2-dimethylpentane, 4,4- Bis (4-cyanatophenyl) -3-methylheptane, 3,3-bis (4-cyanatophenyl) -2-methylheptane, 3,3-bis (4-cyanatophenyl) -2,2-dimethyl Hexane, 3,3-bis (4-cyanatophenyl) -2,4-dimethylhexane, 3,3-bis (4-cyanatophenyl) -2,2,4-trimethylpentane, 2,2-bis ( 4-Cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, bis (4-cyanatophenyl) phenylmethane, 1,1-bis (4-cyanatophenyl) -1-phenyl Ethane, bis (4-si Natophenyl) biphenylmethane, 1,1-bis (4-cyanatophenyl) cyclopentane, 1,1-bis (4-cyanatophenyl) cyclohexane, 2,2-bis (4-cyanato-3-isopropylphenyl) propane 1,1-bis (3-cyclohexyl-4-cyanatophenyl) cyclohexane, bis (4-cyanatophenyl) diphenylmethane, bis (4-cyanatophenyl) -2,2-dichloroethylene, 1,3-bis [ 2- (4-Cyanatophenyl) -2-propyl] benzene, 1,4-bis [2- (4-cyanatophenyl) -2-propyl] benzene, 1,1-bis (4-cyanatophenyl) -3,3,5-trimethylcyclohexane, 4- [bis (4-cyanatophenyl) methyl] biphenyl, 4,4-dicyanatobenzo Enone, 1,3-bis (4-cyanatophenyl) -2-propen-1-one, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) sulfide, bis (4-cyanatophenyl) ) Sulfone, 4-cyanatobenzoic acid-4-cyanatophenyl ester (4-cyanatophenyl-4-cyanatobenzoate), bis- (4-cyanatophenyl) carbonate, 1,3-bis (4-cyanato) Phenyl) adamantane, 1,3-bis (4-cyanatophenyl) -5,7-dimethyladamantane, 3,3-bis (4-cyanatophenyl) isobenzofuran-1 (3H) -one (for phenolphthalein) Cyanate), 3,3-bis (4-cyanato-3-methylphenyl) isobenzofuran-1 (3H) -one (o-cresolphthalein) Cyanate), 9,9′-bis (4-cyanatophenyl) fluorene, 9,9-bis (4-cyanato-3-methylphenyl) fluorene, 9,9-bis (2-cyanato-5-biphenylyl) ) Fluorene, tris (4-cyanatophenyl) methane, 1,1,1-tris (4-cyanatophenyl) ethane, 1,1,3-tris (4-cyanatophenyl) propane, α, α, α '-Tris (4-cyanatophenyl) -1-ethyl-4-isopropylbenzene, 1,1,2,2-tetrakis (4-cyanatophenyl) ethane, tetrakis (4-cyanatophenyl) methane, 2, 4,6-tris (N-methyl-4-cyanatoanilino) -1,3,5-triazine, 2,4-bis (N-methyl-4-cyanatoanilino) -6- (N-methylanilino)- , 3,5-triazine, bis (N-4-cyanato-2-methylphenyl) -4,4′-oxydiphthalimide, bis (N-3-cyanato-4-methylphenyl) -4,4′-oxy Diphthalimide, bis (N-4-cyanatophenyl) -4,4′-oxydiphthalimide, bis (N-4-cyanato-2-methylphenyl) -4,4 ′-(hexafluoroisopropylidene) diphthalimide , Tris (3,5-dimethyl-4-cyanatobenzyl) isocyanurate, 2-phenyl-3,3-bis (4-cyanatophenyl) phthalimidine, 2- (4-methylphenyl) -3,3-bis (4-Cyanatophenyl) phthalimidine, 2-phenyl-3,3-bis (4-cyanato-3-methylphenyl) phthalimidine, 1-methyl-3,3-bis 4-cyanatophenyl) indolin-2-one, and 2-phenyl-3,3-bis (4-cyanatophenyl) include indolin-2-one.

Moreover, as another specific example of the compound represented by the above formula (6), phenol novolak resin and cresol novolak resin (phenol, alkyl-substituted phenol or halogen-substituted phenol, formalin, paraformaldehyde, etc. Formaldehyde compound reacted in an acidic solution), trisphenol novolak resin (reacted hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), fluorene novolak resin (fluorenone compound and 9,9-bis) (hydroxyaryl) fluorenes those reacted in the presence of an acid catalyst), phenol aralkyl resins, cresol aralkyl resin, a naphthol aralkyl resin and a biphenyl aralkyl resin (a known method, Ar ₄ - (CH ₂ ) ₂ (Ar ₄ represents a phenyl group, Y represents a halogen atom. Hereinafter, the same.) A bishalogenomethyl compound and a phenol compound such as represented by is reacted with an acid catalyst or no catalyst in this paragraph A compound obtained by reacting a bis (alkoxymethyl) compound and a phenol compound represented by Ar ₄ — (CH ₂ OR) ₂ in the presence of an acidic catalyst, or Ar ₄ — (CH ₂ OH) ₂ A bis (hydroxymethyl) compound and a phenol compound represented by the above formula in the presence of an acidic catalyst, or a polycondensation of an aromatic aldehyde compound, an aralkyl compound and a phenol compound), phenol modification Xylene formaldehyde resin (by a known method, xylene formaldehyde resin and phenolic compound in the presence of acidic catalyst Modified naphthalene formaldehyde resin (reacted naphthalene formaldehyde resin and hydroxy-substituted aromatic compound in the presence of an acidic catalyst by a known method), phenol-modified dicyclopentadiene resin, polynaphthylene ether structure Phenol resins such as phenol resins (which are obtained by dehydrating and condensing polyhydric hydroxynaphthalene compounds having two or more phenolic hydroxy groups in one molecule in the presence of a basic catalyst by a known method) And the like, as well as those prepolymers thereof. These are not particularly limited. These other cyanate ester compounds can be used singly or in combination of two or more.

  Among these, phenol novolak cyanate ester compounds, naphthol aralkyl cyanate ester compounds, biphenyl aralkyl cyanate ester compounds, naphthylene ether type cyanate ester compounds, xylene resin type cyanate ester compounds, adamantane skeleton type cyanide Acid ester compounds are preferred, and naphthol aralkyl cyanate ester compounds are particularly preferred.

  The cured resin using these cyanate ester compounds has excellent properties such as glass transition temperature (Tg), low thermal expansion, plating adhesion and the like.

  The method for producing these cyanate ester compounds is not particularly limited, and a known method can be used. Examples of such production methods include a method of obtaining or synthesizing a hydroxy group-containing compound having a desired skeleton, and modifying the hydroxy group by a known method to form cyanate. Examples of the method for cyanating a hydroxy group include the method described in Ian Hamerton, “Chemistry and Technology of Cyanate Esters Resins,” “Blackie Academic & Professional”.

  The content of the cyanate ester compound is not particularly limited, and is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 45 parts by mass with respect to 100 parts by mass of the resin solid content. More preferably, it is 0.3 to 40 parts by mass. When the content of the cyanate ester compound is within the above range, the heat resistance and chemical resistance of the cured product tend to be further improved.

[Phenolic resin]
The phenol resin is not particularly limited as long as it is a phenol resin having two or more hydroxyl groups in the molecule. Specific examples thereof include, for example, bisphenol A type phenol resin, bisphenol E type phenol resin, and bisphenol F type phenol. Resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin , Naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolak type phenol resin, phenol aralkyl Phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus-containing phenol resin, polymerizable unsaturated hydrocarbon group-containing phenol resin and hydroxyl group-containing Examples thereof include silicone resins. These phenol resins can be used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of further improving the flame retardancy of the cured product, biphenyl aralkyl type phenol resins, naphthol aralkyl type phenol resins, phosphorus-containing phenol resins, and hydroxyl group-containing silicone resins are more preferable.

  The content of the phenol resin is not particularly limited, and is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 45 parts by mass with respect to 100 parts by mass of the resin solid content. More preferably, it is 0.3 to 40 parts by mass. When the content of the phenol resin is within the above range, the heat resistance and chemical resistance of the cured product tend to be further improved.

[Oxetane resin]
As the oxetane resin, generally known ones can be used. Specific examples thereof include alkyl oxetane such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di (trifluoromethyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (Toho Synthetic product name), OXT-121 (Toagosei product name), and the like. These oxetane resins can be used singly or in combination of two or more.

  The content of the oxetane resin is not particularly limited, and is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 45 parts by mass with respect to 100 parts by mass of the resin solid content. More preferably, it is 0.3 to 40 parts by mass. When the content of the oxetane resin is within the above range, the heat resistance and chemical resistance of the cured product tend to be further improved.

[Benzoxazine compound]
The benzoxazine compound is not particularly limited as long as it has two or more dihydrobenzoxazine rings in the molecule. Specific examples thereof include, for example, bisphenol A type benzoxazine BA-BXZ (trade name, manufactured by Konishi Chemical). ), Bisphenol F-type benzoxazine BF-BXZ (trade name, manufactured by Konishi Chemical), bisphenol S-type benzoxazine BS-BXZ (trade name, manufactured by Konishi Chemical), and phenolphthalein-type benzoxazine. These benzoxazine compounds can be used alone or in combination of two or more.

  Content in particular of a benzoxazine compound is not restrict | limited, Preferably it is 0.1 mass part-50 mass parts with respect to 100 mass parts of resin solid content, More preferably, it is 0.2 mass part-45 mass parts. Yes, and more preferably 0.3 to 40 parts by mass. When the content of the benzoxazine compound is within the above range, the heat resistance and chemical resistance of the cured product tend to be further improved.

<Thermosetting accelerator (G)>
The resin composition of this embodiment may further contain a thermosetting accelerator (G). The thermosetting accelerator (G) is not particularly limited, and examples thereof include benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, and di-tert-butyl-di-perphthalate. Organic peroxides; azo compounds such as azobisnitrile; dicyandiamide, benzyldimethylamine, N, N-dimethylbenzylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N- Dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, N, N-dimethylpyridine, 2-N-ethylanilinoethanol, tri-n- Butylamine, pyridine, quinoline, N-methylmorpholine, triethano Amine compounds such as ruamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcin, catechol; lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, olein Organic metal salts such as tin oxide, dibutyltin malate, manganese naphthenate, cobalt naphthenate, and acetylacetone iron; those obtained by dissolving these organic metal salts in hydroxyl-containing compounds such as phenol and bisphenol; tin chloride, zinc chloride, chloride Inorganic metal salts such as aluminum; dioctyl tin oxide, other organic tin compounds such as alkyl tin and alkyl tin oxide; 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole , 2,4,5-imidazole compounds such as triphenyl imidazole. These thermosetting accelerators (G) can be used alone or in combination of two or more.

<Silane coupling agent and wetting and dispersing agent>
The resin composition of this embodiment may further contain a silane coupling agent or a wetting dispersant from the viewpoint of improving the dispersibility of the filler (D), the adhesive strength between the resin and the filler (D), and the like. Good.

  The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of fillers. Specific examples include, for example, γ-aminopropyltriethoxysilane, N-β- (Aminoethyl) -amino silanes such as γ-aminopropyltrimethoxysilane; epoxy silanes such as γ-glycidoxypropyl trimethoxysilane; acrylic silanes such as γ-acryloxypropyltrimethoxysilane; N-β- Cationic silanes such as (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride; phenylsilane-based silane coupling agents and the like. These silane coupling agents can be used alone or in combination of two or more.

  The wetting dispersant is not particularly limited as long as it is a dispersion stabilizer used for paints. Specific examples include, for example, DISPERBYK-110, 111, 118, 180 manufactured by Big Chemie Japan Co., Ltd. 161, BYK-W996, W9010, W903, and the like. These wet dispersing agents can be used individually by 1 type or in combination of 2 or more types.

<Flame Retardant>
The resin composition of the present embodiment may further contain a flame retardant from the viewpoint of further improving the flame retardancy, heat resistance, thermal expansion characteristics, and the like of the cured product. The flame retardant is not particularly limited as long as it has insulating properties. Specific examples thereof include brominated organic compounds such as decabromodiphenylethane, 4,4-dibromobiphenyl, and ethylenebistetrabromophthalimide. Can be mentioned. These flame retardants can be used singly or in combination of two or more.

<Solvent>
The resin composition of the present embodiment may further contain a solvent from the viewpoint that the viscosity at the time of preparation of the resin composition can be easily adjusted as desired. The solvent is not particularly limited as long as it can dissolve part or all of the resin in the resin composition. Specific examples include, for example, ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; toluene, Aromatic hydrocarbons such as xylene; Amides such as dimethylformamide; Propylene glycol monomethyl ether and its acetate. These solvents can be used alone or in combination of two or more.

<Other ingredients>
The resin composition of the present embodiment includes various polymer compounds such as a thermosetting resin, a thermoplastic resin and oligomers thereof, and elastomers that have not been mentioned so far as long as desired characteristics are not impaired; Flame retardant compounds not mentioned above; additives and the like may be further contained. Such other components are not particularly limited as long as they are generally used. Examples of the flame retardant compound include nitrogen-containing compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, and phosphorus compounds. Phosphate compounds, aromatic condensed phosphate esters, halogen-containing condensed phosphate esters, and the like. Additives include UV absorbers, antioxidants, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, surface conditioners, brighteners, polymerization inhibitors, etc. Is mentioned. These other components can be used individually by 1 type or in combination of 2 or more types.

<Method for producing resin composition>
The manufacturing method of the resin composition of this embodiment is not specifically limited, For example, the method of mix | blending each component mentioned above in a solvent sequentially and fully stirring is mentioned. At this time, in order to uniformly dissolve or disperse each component, known processes such as stirring, mixing, and kneading can be performed. Specifically, the dispersibility of the filler (D) with respect to the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank provided with a stirrer having an appropriate stirring ability. The stirring, mixing, and kneading processes described above are, for example, a stirring device for dispersion such as an ultrasonic homogenizer, a device for mixing such as a three-roll, ball mill, bead mill, and sand mill, or a revolving or rotating type. It can carry out suitably using well-known apparatuses, such as a mixing apparatus. Moreover, when preparing the resin composition of this embodiment, an organic solvent can be used as needed. The type of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition, and specific examples thereof are as described above.

<Application>
The resin composition of the present embodiment can be used for applications where an insulating resin composition is required, and the application is not particularly limited. Specific examples include, for example, a resin sheet, a printed wiring board, It can be suitably used for a semiconductor device or the like.

<Resin sheet>
The resin sheet of this embodiment contains the resin composition of this embodiment. Here, the resin sheet is used as one means for thinning, and includes, for example, a resin composition formed into a sheet shape. As a resin sheet, a resin sheet (laminated resin sheet) having a support and the resin composition disposed on the support, or a resin sheet molded into a sheet without using the support or the like (Single layer resin sheet). The manufacturing method of a resin sheet can be performed according to a conventional method, and is not specifically limited.

  For example, the laminated resin sheet can be obtained by directly applying and drying the resin composition of the present embodiment on a support such as a metal foil or a film. Examples of the coating method include a method in which a solution obtained by dissolving the resin composition of the present embodiment in a solvent is coated on a support with a bar coater, a die coater, a doctor blade, a baker applicator, or the like.

  The support used here is not particularly limited, and known materials used for various printed wiring board materials can be used. For example, polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film , Polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polycarbonate film, ethylene tetrafluoroethylene copolymer film, release film having a release agent applied to the surface of these films, etc. Organic film base materials, conductor foils such as aluminum foil, copper foil, and gold foil, and plate-like inorganic films such as glass plates, SUS plates, and FPRs. Among these, copper foil such as rolled copper foil and electrolytic copper foil, and PET film are preferable.

  The laminated resin sheet is preferably one obtained by applying the resin composition to a support and then semi-curing (B-stage). Specifically, for example, after the resin composition is applied to a support such as copper foil, it is semi-cured by a method of heating for 1 minute to 90 minutes in a dryer at 20 ° C. to 200 ° C. Examples include a method for producing a sheet. The adhesion amount of the resin composition to the support is preferably the range of 0.1 μm to 500 μm, for example, the resin thickness of the laminated resin sheet.

  The single-layer resin sheet is formed into a sheet by feeding a solution obtained by dissolving the resin composition of the present embodiment in a solvent into a mold having a sheet-like cavity and drying it. Can be obtained without using. Moreover, a single layer resin sheet can also be obtained by peeling or etching a support body from the said laminated resin sheet.

  Furthermore, in the resin sheet in the present embodiment, the resin composition layer may be protected with a protective film. By protecting the resin composition layer side with a protective film, it is possible to prevent adhesion or scratches of dust or the like to the surface of the resin composition layer. As the protective film, a film made of the same material as the above resin film can be used.

<Printed wiring board>
The printed wiring board of this embodiment contains the resin composition of this embodiment. Specifically, for example, the printed wiring board includes an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the resin composition of the present embodiment. Such a printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited. Hereinafter, an example of the procedure in the manufacturing method of the printed wiring board using the resin sheet of this embodiment is demonstrated. The resin sheet of this embodiment can be suitably used as an interlayer insulating layer of a printed wiring board, and can be obtained by stacking and curing one or more resin sheets of this embodiment.

(Molding process)
Specifically, first, the resin composition layer side of the resin sheet of the present embodiment is formed on one side or both sides of a circuit board. As the molding conditions, a general laminate for printed wiring boards and multilayer boards can be applied, and molding can also be performed by vacuum lamination. Examples of the circuit board include a glass epoxy board, a metal board, a ceramic board, a silicon board, a semiconductor sealing resin board, a polyester board, a polyimide board, a BT resin board, and a thermosetting polyphenylene ether board. Here, the circuit board refers to a board on which a conductor layer (circuit) patterned on one or both sides of the board is formed. Further, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, a substrate that is a conductor layer (circuit) in which one or both surfaces of the outermost layer of the multilayer printed wiring board are patterned, It is included in the circuit board here. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

(Lamination process)
Next, in the molding step, when the resin sheet has a protective film, the protective film is peeled and removed, and then the resin sheet and the circuit board are preheated as necessary, and the resin composition layer is pressurized and Crimp to circuit board while heating. In the resin sheet of the present embodiment, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used.

Lamination conditions are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 50 ° C. to 140 ° C., the pressure bonding pressure is preferably 1 kgf / cm ^{2 to} 15 kgf / cm ² , and the pressure bonding time is preferably 5 seconds. Lamination is preferably performed under a reduced pressure of ˜300 seconds and an air pressure of 20 mmHg or less. The laminating step may be a batch type or a continuous type using a roll. The vacuum laminating method can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a 2-stage build-up laminator manufactured by Nikko Materials Co., Ltd. can be exemplified.

(Exposure process)
After the resin sheet is provided on the circuit board by the laminating process, an exposure process is performed in which a predetermined portion of the resin composition layer is irradiated with active energy rays to cure the resin composition layer of the irradiated portion. The active energy rays may be irradiated through a mask pattern or a direct drawing method in which the active energy rays are directly irradiated. Examples of active energy rays include ultraviolet rays, visible rays, electron beams, X-rays and the like, and ultraviolet rays are particularly preferable. The dose of ultraviolet rays is approximately ^{10mJ / cm 2 ~1000mJ / cm 2} . There are two methods for exposing the mask pattern: a contact exposure method in which the mask pattern is brought into close contact with the printed wiring board, and a non-contact exposure method in which exposure is carried out using parallel light rays without being brought into close contact. You can use it. Moreover, when the support body exists on the resin composition layer, you may expose from a support body and you may expose after a support body peels.

(Development process)
After the exposure step, if a support is present on the resin composition layer, the support is removed, and then the portion that has not been photocured (unexposed portion) is removed and developed by wet development. Thus, the pattern of the insulating layer can be formed.

  In the case of the wet development, the developer is not particularly limited as long as it selectively elutes an unexposed portion, and for example, a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent is used. In the present embodiment, it is particularly preferable to use an alkaline aqueous solution. These developers can be used alone or in combination of two or more. Further, the developing method is not particularly limited, and for example, it can be performed by a known method such as spraying, rocking dipping, brushing, scraping or the like.

  The alkaline aqueous solution used as the developer is not particularly limited, and examples thereof include potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, sodium 4-borate, ammonia, and amines. Etc.

  The concentration of the alkaline aqueous solution is preferably 0.1% by mass to 60% by mass with respect to the total amount of the developer. Moreover, the temperature of aqueous alkali solution can be adjusted according to developability. Furthermore, these alkaline aqueous solutions can be used individually by 1 type or in combination of 2 or more types.

  In the pattern formation of this embodiment, two or more kinds of development methods described above may be used in combination as necessary. Development methods include a dip method, a paddle method, a spray method, a high-pressure spray method, brushing, and slapping, and the high-pressure spray method is suitable for improving the resolution. As a spray pressure in the case of adopting the spray method, 0.02 MPa to 0.5 MPa is preferable.

(Post bake process)
After the development step, a post-bake step is performed to form an insulating layer (cured product). Examples of the post-bake process include an ultraviolet irradiation process using a high-pressure mercury lamp and a heating process using a clean oven, and these can be used in combination. In the case of irradiating ultraviolet rays, the irradiation amount can be adjusted as necessary. For example, irradiation can be performed at an irradiation amount of about 0.05 J / cm ^{2 to} 10 J / cm ² . The heating conditions can be appropriately selected according to the type, content, etc. of the resin component in the resin composition, preferably at 150 to 220 ° C. for 20 to 180 minutes, more preferably 160. It is selected in the range of 30 ° C. to 150 ° C. at 30 ° C. to 200 ° C.

  When there is a conductor layer on the surface of the insulating layer, a plated metal film is formed on the wall surface of the hole to connect the inner layer circuit and the metal foil for the outer layer circuit, and the outer layer circuit is etched by applying an etching treatment to the metal foil for the outer layer circuit. By forming the printed wiring board, a printed wiring board is manufactured.

  If there is no conductor layer on the surface of the insulating layer, a conductor layer is then formed on the surface of the insulating layer by dry plating or wet plating. As the dry plating, known methods such as vapor deposition, sputtering, and ion plating can be used. In the vapor deposition method (vacuum vapor deposition method), for example, a metal film can be formed on the insulating layer by placing the support in a vacuum vessel and evaporating the metal by heating. In the sputtering method, for example, the support is placed in a vacuum vessel, an inert gas such as argon is introduced, a direct current voltage is applied, the ionized inert gas is made to collide with the target metal, and the struck metal is used. A metal film can be formed on the insulating layer.

  In the case of wet plating, the surface of the insulating layer is roughened by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order. . The swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 ° C. to 80 ° C. for 1 minute to 20 minutes. Examples of the swelling liquid include an alkaline solution, and examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include Updes MDS-37 manufactured by Uemura Kogyo Co., Ltd.

  The roughening treatment with the oxidizing agent is performed by immersing the insulating layer in the oxidizing agent solution at 60 ° C. to 80 ° C. for 5 to 30 minutes. Examples of the oxidizing agent include alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can. Moreover, it is preferable that the density | concentration of the permanganate in an alkaline permanganic acid solution shall be 5 mass%-10 mass%. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as Updes MDE-40 and Updes ELC-SH manufactured by Uemura Kogyo Co., Ltd. The neutralization treatment with the neutralizing solution is performed by immersing in the neutralizing solution at 30 ° C. to 50 ° C. for 1 minute to 10 minutes. As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercial product, Updes MDN-62 manufactured by Uemura Kogyo Co., Ltd. may be mentioned.

  Next, a conductor layer is formed by combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a pattern formation method thereafter, for example, a subtractive method, a semi-additive method, or the like can be used.

<Semiconductor device>
The semiconductor device of the present embodiment includes an interlayer insulating layer containing the resin composition of the present embodiment, and specifically can be manufactured by the following method, for example. That is, a semiconductor device can be manufactured by mounting a semiconductor chip at a conduction point of the multilayer printed wiring board of the present embodiment. Here, the conduction location is a location for transmitting an electrical signal in the multilayer printed wiring board, and the location may be the surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present embodiment is not particularly limited as long as the semiconductor chip functions effectively. Specifically, a wire bonding mounting method, a flip chip mounting method, a bump Examples include a mounting method using a none buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

  Moreover, a semiconductor device can also be manufactured by laminating the resin sheet of this embodiment on a semiconductor chip. After lamination, it can be produced by using the same method as the above multilayer printed wiring board.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

[Synthesis Example 1] Synthesis of naphthol aralkyl-type cyanate ester compound (SNCN) 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 300 g (OH group equivalent 1.28 mol) and triethylamine 194.6 g (1.92 mol) ( 1.5 mol) with respect to 1 mol of a hydroxy group was dissolved in 1800 g of dichloromethane.

  On the other hand, 125.9 g (2.05 mol) of cyanogen chloride (1.6 mol with respect to 1 mol of hydroxy group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol with respect to 1 mol of hydroxy group) ) And 1205.9 g of water were mixed to prepare Solution 2. While maintaining the solution 2 at a liquid temperature of −2 to −0.5 ° C. with stirring, the solution 1 was poured into the solution 2 over 30 minutes. After the completion of pouring the solution 1, the solution was stirred at the same temperature for 30 minutes, and then a solution (solution 3) in which 65 g (0.64 mol) of triethylamine (0.5 mol with respect to 1 mol of hydroxy group) was dissolved in 65 g of dichloromethane was added for 10 minutes. Over time, it was poured into solution 2. After the completion of 3 solutions, the reaction was completed by stirring at the same temperature for 30 minutes.

  Thereafter, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The organic phase obtained was washed 5 times with 1300 g of water. The electric conductivity of the waste water in the fifth washing with water was 5 μS / cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.

The organic phase after washing with water was concentrated under reduced pressure and finally dried at 90 ° C. for 1 hour to obtain 331 g of the desired naphthol aralkyl-type cyanate ester compound (SNCN) (orange viscous product). The obtained SNCN had a mass average molecular weight Mw of 600. Further, the IR spectrum of SNCN showed an absorption of 2250 cm ⁻¹ (cyanate ester group) and no absorption of a hydroxy group.

Example 1
As an epoxy (meth) acrylate compound (A), a TrisP-PA type epoxy acrylate compound represented by the above formula (1) in a propylene glycol monomethyl ether acetate (PGMEA) solution (KAYARAD (registered trademark) ZCR-6007H, non-volatile As a phosphine oxide compound (B) as a photocuring initiator, 50.4 parts by mass of 65% by mass, acid value: 70 mg KOH / g, manufactured by Nippon Kayaku Co., Ltd., and represented by the above formula (5) 6.5 parts by mass of phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan Ltd.), maleimide compound (BMI-2300, Yamato) as maleimide compound (C) 2. Kasei Kogyo Co., Ltd., maleimide equivalent: 186 g / eq.) As a mass part and a filler (D), it has MEK slurry of epoxysilane-treated silica (SC2050MB, median diameter 0.5 μm, nonvolatile content 70% by mass, manufactured by Admatex Co., Ltd.) 50 parts by mass, and an ethylenically unsaturated group As compound (E), 17.4 parts by mass of dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) and as epoxy resin as compound (F), dicyclopentadiene novolac type epoxy resin (XD- 1000, Nippon Kayaku Co., Ltd., epoxy equivalent: 240 g / eq. To 260 g / eq.) 22.4 parts by mass were mixed and stirred with an ultrasonic homogenizer to obtain a varnish (resin composition solution). . KAYARAD (registered trademark) ZCR-6007H is a mixture containing at least one of the above compound (A1) and the above compounds (A2) to (A5).

(Example 2)
As an epoxy resin which is a compound (F), it replaces with a dicyclopentadiene novolak-type epoxy resin (XD-1000, Nippon Kayaku Co., Ltd., epoxy equivalent: 240g / eq.-260g / eq.), And is a biphenyl aralkyl type. Varnish was obtained in the same manner as in Example 1 except that 22.4 parts by mass of epoxy resin (NC3000L, Nippon Kayaku Co., Ltd., epoxy equivalent: 260 g / eq. To 290 g / eq.) Was used.

(Example 3)
The dicyclopentadiene novolac type epoxy resin (XD-1000, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 240 g / eq. To 260 g / eq.) As the epoxy resin which is the compound (F) is 21.9 parts by mass. Examples, except that 0.5 part by mass of the naphthol aralkyl cyanate ester compound (SNCN, cyanate equivalent: 261 g / eq.) Of Synthesis Example 1 was further blended as the cyanate ester compound which is compound (F). A varnish was obtained in the same manner as in 1.

(Comparative Example 1)
Phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide represented by the above formula (5) as a phosphine oxide compound (B) which is a photocuring initiator (Irgacure (registered trademark) 819, BASF Japan Ltd.) Instead of 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -butanone-1 (Irgacure (registered trademark) represented by the following formula (9): 369, manufactured by BASF Japan Ltd.) A varnish was obtained in the same manner as in Example 1 except that 6.5 parts by mass was blended.

(Comparative Example 2)
Phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide represented by the above formula (5) as a phosphine oxide compound (B) which is a photocuring initiator (Irgacure (registered trademark) 819, BASF Japan Ltd.) Instead of 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (Irgacure (registered trademark)) represented by the above formula (9) as a photocuring initiator. 369, manufactured by BASF Japan Ltd.) A varnish was obtained in the same manner as in Example 2 except that 6.5 parts by mass was blended.

(Comparative Example 3)
PGMEA solution of the TrisP-PA type epoxy acrylate compound represented by the above formula (1) as the epoxy (meth) acrylic ester compound (A) (KAYARAD (registered trademark) ZCR-6007H, non-volatile content 65% by mass, acid value : 70 mg KOH / g, manufactured by Nippon Kayaku Co., Ltd.) As a compound (E) having an ethylenically unsaturated group, a PGMEA solution of an acid-modified bisphenol F type epoxy acrylate compound (KAYARAD (registered trademark) ZFR-1553H) A varnish was obtained in the same manner as in Example 1 except that 50.4 parts by mass of non-volatile content 68% by mass, acid value: 70 mg KOH / g, manufactured by Nippon Kayaku Co., Ltd.).

(Production of resin sheet)
The varnishes obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were each applied onto a PET film (Unipeel TR1-38, manufactured by Unitika Ltd., product name) having a thickness of 38 μm for 7 minutes at 80 ° C. It heat-dried and obtained the resin sheet which uses PET film as a support body and the thickness of the resin composition layer is 40 micrometers.

(Production of inner layer circuit board)
Glass cloth base material BT resin double-sided copper-clad laminate (copper foil thickness 18 μm, thickness 0.2 mm, Mitsubishi Gas Chemical Co., Ltd. CCL-HL832NS) on which inner layer circuit is formed is CZ8100 manufactured by MEC Co., Ltd. A copper surface was roughened to obtain an inner layer circuit board.

(Preparation of evaluation laminate)
The resin surface of the resin sheet was placed on the inner layer circuit board, and after evacuating for 30 seconds (5.0 MPa or less) using a vacuum laminator (Nikko Materials Co., Ltd.), a pressure of 10 kgf / Lamination was performed at cm ² and a temperature of 70 ° C. for 30 seconds. Furthermore, a laminate in which the inner circuit board, the resin composition layer, and the support were laminated was obtained by performing lamination molding at a pressure of 10 kgf / cm ² and a temperature of 70 ° C. for 60 seconds. The obtained laminate is subjected to an exposure step of irradiating with 200 mJ / cm ² of ultraviolet rays, the support is peeled off, developed with a 1% by mass aqueous sodium carbonate solution, and further exposed to 1000 mJ / cm ² of ultraviolet rays. The laminated body for evaluation was subjected to the post-baking process in which the step was performed and the heat treatment was performed at 180 ° C. for 120 minutes.

(Production of cured product for evaluation)
The resin sheet is irradiated with 200 mJ / cm ² of ultraviolet light, further subjected to an exposure process of irradiating 1000 mJ / cm ² of ultraviolet light, and subjected to a post-baking process of heat treatment at 180 ° C. for 120 minutes, and then the support is peeled off. Thus, a cured product for evaluation was obtained.

[Characteristic measurement evaluation]
Various characteristics of each resin sheet, each evaluation laminate and each evaluation cured product prepared using the varnishes obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were measured and evaluated by the following methods. The results are summarized in Table 1.

<Coating properties>
The measurer's finger was lightly pressed against the resin surface of each resin sheet, and the degree of sticking to the finger was evaluated according to the following criteria.
○: Sticking to the finger is hardly recognized.
X: Sticking to the finger is recognized.

<Developability>
After visually observing the development surface of each evaluation laminate, it was observed with a SEM (magnification 1000 times), and the presence or absence of a residue was evaluated according to the following criteria.
○: There is no development residue in the range of 30 mm square, and the developability is excellent.
X: There is a development residue in the range of 30 mm square, and the developability is inferior.

<Heat resistance (glass transition temperature (Tg))>
Each cured product for evaluation was heated at 10 ° C./min using a DMA device (Dynamic Viscoelasticity Measuring Device DMAQ800 manufactured by TA Instruments), and the peak position of Loss Modulus was defined as the glass transition temperature (Tg).

<Plating adhesion>
The cured product for evaluation was subjected to the following wet roughening treatment and conductor layer plating treatment to produce a plating adhesion evaluation sample. That is, first, an electroless copper plating process manufactured by Uemura Kogyo (names of chemical solutions used: MCD-PL, MDP-2, MAT-SP, MAB-4-C, MEL-3-APEA ver. 2), electroless copper plating of about 0.8 μm was applied and dried at 130 ° C. for 1 hour. Subsequently, electrolytic copper plating was performed so that the thickness of the plated copper was 18 μm, and drying was performed at 180 ° C. for 1 hour. Thus, a plating adhesion evaluation sample in which a conductor layer (plated copper) having a thickness of 18 μm was formed on the insulating layer was obtained. Next, for each of the plating adhesion evaluation samples, the adhesive strength (copper foil peeling strength) of the plated copper was measured three times according to JIS C6481, and the average value thereof was determined. In addition, about the sample for plating adhesion evaluation swollen in the drying after electrolytic copper plating, it measured using the part which is not swollen.

  As is clear from Table 1, Examples 1 to 3 have sufficient coating properties and developability, and are excellent in heat resistance and plating adhesion. On the other hand, Comparative Examples 1 to 3 were all inferior in heat resistance as compared to Examples 1 to 3, and Comparative Example 3 was found to have insufficient plating adhesion. Therefore, according to the present invention, a resin composition capable of improving heat resistance and plating adhesion while having sufficient coating properties and developability, a resin sheet using the same, a printed wiring board, and a semiconductor device Can be obtained.

  The resin composition of this embodiment has industrial applicability as a material for resin sheets, printed wiring boards, and semiconductor devices.

Claims (13)

An epoxy (meth) acrylic acid ester compound (A) represented by the following formula (1);
A phosphine oxide compound (B) represented by the following formula (4);
Containing a resin composition.
(In Formula (1), each of R ₁ independently represents a hydrogen atom or a methyl group, each of R ₂ independently represents a hydrogen atom or a methyl group, and each of R ₃ represents Independently, a substituent represented by the following formula (2), a substituent represented by the following formula (3) or a hydroxy group is shown.
(In formula (3), R ₄ represents a hydrogen atom or a methyl group.)
(In Formula (4), R < ₅ > -R < ₁₀ > shows a hydrogen atom or a C1-C4 alkyl group each independently, and R < ₁₁ > is a C1-C20 alkyl group or C6-C20. An aryl group of The phosphine oxide compound (B) is a compound represented by the following formula (5).
The resin composition according to claim 1.
Further containing a maleimide compound (C),
The resin composition according to claim 1 or 2. Further containing a filler (D),
The resin composition as described in any one of Claims 1-3. Further containing a compound (E) having an ethylenically unsaturated group other than the epoxy (meth) acrylate compound (A),
The resin composition as described in any one of Claims 1-4. Further containing at least one compound (F) from the group selected from an epoxy resin, a cyanate ester compound, a phenol resin, an oxetane resin, and a benzoxazine compound,
The resin composition as described in any one of Claims 1-5. The acid value of the epoxy (meth) acrylic acid ester compound (A) is 30 to 120 mgKOH / g,
The resin composition as described in any one of Claims 1-6. The compound (E) having an ethylenically unsaturated group is a compound having a (meth) acryloyl group and / or a compound having a vinyl group.
The resin composition as described in any one of Claims 5-7. The filler (D) is made of silica, boehmite, barium sulfate, silicone powder, fluorine resin filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene / butadiene rubber and silicone rubber. Any one or more selected from the group,
The resin composition as described in any one of Claims 4-8. Further containing a thermosetting accelerator (G),
The resin composition as described in any one of Claims 1-9.   The resin sheet containing the resin composition as described in any one of Claims 1-10.   The printed wiring board containing the resin composition as described in any one of Claims 1-10.   The semiconductor device containing the resin composition as described in any one of Claims 1-10.