JP2010053334A - Epoxy-based resin composition, prepreg, cured product, sheet-like molded article, laminate plate, and multilayer laminate plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy-based resin composition excellent in dispersibility of a silica component, and in which surface roughness of a cured product, where the surface of a cured material is roughening treated, is made to be small. <P>SOLUTION: The epoxy-based resin composition includes an epoxy-based resin, a curing agent, and the silica component in which a silica particle is surface treated with a silane coupling agent, and the silica component is contained within a range of 25-400 pts.wt. based on the total of 100 pts.wt. of the epoxy-based resin and the curing agent. An average particle diameter of the silica particle is ≤1 μm, and the silane coupling agent is at least one selected from a group consisting of a silane compound having an amino group, silane compound having a mercapto group, silane compound having an isocyanate group, silane compound having an acid anhydride group, and silane compound having an isocyanuric acid group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition used for obtaining a cured product having, for example, a copper plating layer formed on the surface thereof, and more specifically, an epoxy resin containing an epoxy resin, a curing agent, and a silica component. The present invention relates to a composition, and a prepreg, a cured body, a sheet-like molded body, a laminate, and a multilayer laminate using the epoxy resin composition.

  Conventionally, various thermosetting resin compositions have been used to form multilayer substrates or semiconductor devices.

  For example, Patent Literature 1 below discloses a thermosetting resin composition including a thermosetting resin, a curing agent, and a filler surface-treated with imidazole silane. An imidazole group exists on the surface of the filler. The imidazole group acts as a curing catalyst and a reaction starting point. For this reason, the intensity | strength of the hardened | cured material of a thermosetting resin composition can be raised. Patent Document 1 describes that the thermosetting resin composition is useful for applications that require adhesion, such as an adhesive, a sealing material, a paint, a laminate, and a molding material.

  Patent Document 2 below discloses an epoxy resin composition containing an epoxy resin, a phenol resin, a curing agent, an inorganic filler, and an imidazole silane in which Si atoms and N atoms are not directly bonded. . Here, it is described that the cured product of the epoxy resin composition has high adhesion to the semiconductor chip and that the cured product has high moisture resistance, so that the cured product is difficult to peel off from the semiconductor chip or the like even after IR reflow. Yes.

  Patent Document 3 below discloses an epoxy resin composition containing an epoxy resin, a curing agent, and silica treated with imidazole silane and having an average particle diameter of 5 μm or less. By roughening the surface of the cured product obtained by curing the epoxy resin composition, silica can be easily detached without etching much resin. For this reason, the surface roughness of the surface of hardened | cured material can be made small. Furthermore, the adhesion between the cured product and the copper plating can be increased.

JP-A-9-168771 Japanese Patent Laid-Open No. 2002-128772 International Publication No. 2007/032424 Pamphlet

  A wiring made of a metal such as copper may be formed on the surface of the cured body of the thermosetting resin composition as described above. In recent years, the miniaturization of wiring formed on the surface of such a cured body has progressed. That is, L / S indicating the dimension (L) in the width direction of the wiring and the dimension (S) in the width direction of the portion where the wiring is not formed has been further reduced. For this reason, it has been studied to further reduce the linear expansion coefficient of the cured product of the thermosetting resin composition. Conventionally, in order to reduce the linear expansion coefficient of a cured product, generally, a filler such as silica is often blended in a thermosetting resin composition.

  However, in Patent Documents 1 to 3, an inorganic filler such as a filler or silica is surface-treated with imidazole silane. When a large amount of silica or the like surface-treated with such imidazole silane was blended, the silica or the like was easily aggregated. Therefore, when the surface of the cured body is roughened, the agglomerated silica and the like are collectively separated and the surface roughness may increase.

  The object of the present invention is excellent in dispersibility of the silica component, can reduce the surface roughness of the cured body whose surface of the cured product is roughened, and further, the surface of the roughened cured body When a metal layer is formed on the epoxy resin composition that can increase the adhesive strength between the cured body and the metal layer, as well as a prepreg, a cured body, and a sheet-like molded body using the epoxy resin composition, It is providing a laminated board and a multilayer laminated board.

  According to the present invention, an epoxy resin, a curing agent, and a silica component in which silica particles are surface-treated with a silane coupling agent are contained, and the total amount of the epoxy resin and the curing agent is 100 parts by weight. The silica component is contained within a range of 25 to 400 parts by weight, the silica particles have an average particle size of 1 μm or less, and the silane coupling agent is an amino group-containing silane compound or mercapto group-containing silane. There is provided an epoxy resin composition which is at least one selected from the group consisting of a compound, a silane compound having an isocyanate group, a silane compound having an acid anhydride group, and a silane compound having an isocyanuric acid group.

  In a specific aspect of the epoxy resin composition according to the present invention, 15 wt% to 80 wt% of a total of 100 wt% of the epoxy resin, the curing agent, and the silica component is liquid at 23 ° C. is there.

  In another specific aspect of the epoxy resin composition according to the present invention, an epoxy resin having an anthracene skeleton, an epoxy resin having a naphthalene skeleton, an epoxy resin having an adamantane skeleton, and a triazine skeleton in 100% by weight of the epoxy resin. And at least one epoxy resin selected from the group consisting of epoxy resins having a biphenyl skeleton and a biphenyl skeleton in a total range of 2 to 20% by weight.

  In still another specific aspect of the epoxy resin composition according to the present invention, in 100% by weight of the curing agent, a phenol compound having a biphenyl structure, a phenol compound having a naphthalene structure, a phenol compound having a dicyclopentadiene structure, At least one curing agent selected from the group consisting of a phenol compound having an aminotriazine structure and an active ester compound is included within a total range of 5 to 100% by weight.

  In another specific aspect of the epoxy resin composition according to the present invention, a maleimide compound is further contained, and the content of the maleimide compound is in the range of 2 to 45% by weight.

  In still another specific aspect of the epoxy resin composition according to the present invention, the maximum particle size of the silica particles is 5 μm or less.

  In another specific aspect of the epoxy resin composition according to the present invention, the organic layered silicate is in the range of 0.01 to 2 parts by weight with respect to a total of 100 parts by weight of the epoxy resin and the curing agent. It is further contained.

  In the prepreg according to the present invention, the porous base material is impregnated with the epoxy resin composition constituted according to the present invention.

  Further, according to the present invention, the epoxy resin composition constituted according to the present invention or a prepreg impregnated in a porous substrate with the epoxy resin composition is heated and precured. A cured product in which a product is roughened, and has an arithmetic average roughness Ra of 0.3 μm or less and a ten-point average roughness Rz of 3.0 μm or less. The body is provided.

  On the specific situation with the hardening body which concerns on this invention, the said hardened | cured material is swollen before the said roughening process after the said pre-hardening.

  A sheet-like molded product according to the present invention includes an epoxy resin composition configured according to the present invention, a prepreg in which a porous base material is impregnated with the epoxy resin composition, or the epoxy resin composition or the prepreg. The hardened | cured material in which the hardened | cured material obtained by hardening | curing is roughened is shape | molded in the sheet form.

  The laminated board which concerns on this invention is equipped with the sheet-like molded object comprised according to this invention, and the metal layer laminated | stacked on the at least single side | surface of this sheet-like molded object.

  On the specific situation with the laminated board which concerns on this invention, the said metal layer is formed as a circuit.

  The multilayer laminated board which concerns on this invention is equipped with the several said sheet-like molded object laminated | stacked, and the metal layer arrange | positioned between this sheet-like molded object.

  On the specific situation with the multilayer laminated board which concerns on this invention, the metal layer laminated | stacked on the outer surface of the said sheet-like molded object of the outermost layer is further provided.

  In another specific aspect of the multilayer laminate according to the present invention, the metal layer is formed as a circuit.

  Since the epoxy resin composition according to the present invention includes a silica component in which the surface of silica particles having an average particle diameter of 1 μm or less is surface-treated with the specific silane coupling agent, the dispersibility of the silica component can be improved. it can. Therefore, a relatively large amount of the silica component can be blended while suppressing the aggregation of the silica component.

  Furthermore, in the epoxy resin composition according to the present invention, since the silica component hardly aggregates, the surface roughness of the cured product obtained by roughening the surface of the cured product can be reduced. Furthermore, when a metal layer is formed on the surface of the roughened cured body, the adhesive strength between the cured product and the metal layer can be increased.

FIG. 1 is a partially cutaway front sectional view schematically showing the surface of a cured body obtained by roughening a cured product of an epoxy resin composition according to an embodiment of the present invention. FIG. 2 is a partially cutaway front cross-section showing a state in which a metal layer is formed on the surface of the cured body shown in FIG. FIG. 3 is a partially cutaway front cross-sectional view schematically showing a multilayer laminate using the epoxy resin composition according to one embodiment of the present invention.

  As a result of intensive studies to solve the above problems, the inventors of the present application have surface-treated the surface of the epoxy resin, the curing agent, and the silica particles having an average particle diameter of 1 μm or less with the specific silane coupling agent. By adopting a composition containing the above-mentioned specific proportion of silica component, the dispersibility of the silica component can be increased, and the surface roughness of the cured product obtained by roughening the surface of the cured product can be reduced. As a result, the present invention has been completed.

  The epoxy resin composition according to the present invention contains an epoxy resin, a curing agent, and a silica component in which silica particles are surface-treated with a silane coupling agent. The components contained in the epoxy resin composition will be described below.

(Epoxy resin)
The “epoxy resin” contained in the epoxy resin composition according to the present invention refers to an organic compound having at least one epoxy group (oxirane ring).

  The number of epoxy groups per molecule of the epoxy resin is one or more. The number of epoxy groups is more preferably 2 or more.

  A conventionally known epoxy resin can be used as the epoxy resin. As for an epoxy resin, only 1 type may be used and 2 or more types may be used together. The “epoxy resin” includes a derivative of an epoxy resin or a hydrogenated product of an epoxy resin.

  Examples of the epoxy resin include aromatic epoxy resin (1), alicyclic epoxy resin (2), aliphatic epoxy resin (3), glycidyl ester type epoxy resin (4), and glycidyl amine type. Examples thereof include an epoxy resin (5), a glycidyl acrylic epoxy resin (6), and a polyester epoxy resin (7).

  Examples of the aromatic epoxy resin (1) include a bisphenol type epoxy resin or a novolac type epoxy resin.

  Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and bisphenol S type epoxy resin.

  Examples of the novolac epoxy resin include phenol novolac epoxy resins and cresol novolac epoxy resins.

  Furthermore, as the aromatic epoxy resin (1), an epoxy resin having an aromatic ring such as naphthalene, naphthylene ether, biphenyl, anthracene, pyrene, xanthene, or indole in the main chain can be used. Moreover, an indole-phenol co-condensation epoxy resin or a phenol aralkyl type epoxy resin can be used. Furthermore, an epoxy resin made of an aromatic compound such as trisphenolmethane triglycidyl ether can be used.

  Examples of the alicyclic epoxy resin (2) include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy- 2-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (3 , 4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane, or bis (2,3-epoxycyclopentyl) ether.

  As a commercial item of the said alicyclic epoxy-type resin (2), the brand name "EHPE-3150" (softening temperature 71 degreeC) by Daicel Chemical Industries, etc. are mentioned, for example.

  Examples of the aliphatic epoxy resin (3) include, for example, diglycidyl ether of neopentyl glycol, diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, Examples include triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, or polyglycidyl ether of long-chain polyol.

  The long-chain polyol preferably contains polyoxyalkylene glycol or polytetramethylene ether glycol. Moreover, it is preferable that the carbon number of the alkylene group of the said polyoxyalkylene glycol exists in the range of 2-9, and it is more preferable to exist in the range of 2-4.

  Examples of the glycidyl ester type epoxy resin (4) include diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl-p-oxybenzoic acid, and glycidyl ether-glycidyl of salicylic acid. Examples thereof include esters or dimer acid glycidyl esters.

  Examples of the glycidylamine type epoxy resin (5) include triglycidyl isocyanurate, N, N′-diglycidyl derivative of cyclic alkylene urea, N, N, O-triglycidyl derivative of p-aminophenol, or m- Examples thereof include N, N, O-triglycidyl derivatives of aminophenol.

  Examples of the glycidyl acrylic epoxy resin (6) include a copolymer of glycidyl (meth) acrylate and a radical polymerizable monomer. Examples of the radical polymerizable monomer include ethylene, vinyl acetate, and (meth) acrylic acid ester.

  Examples of the polyester-type epoxy resin (7) include polyester resins having an epoxy group. The polyester resin preferably has two or more epoxy groups per molecule.

  As the epoxy resin, the following epoxy resins (8) to (11) may be used in addition to the epoxy resins (1) to (7).

  Examples of the epoxy resin (8) include a compound obtained by epoxidizing a carbon-carbon double bond of a (co) polymer mainly composed of a conjugated diene compound, or a (co) polymer mainly composed of a conjugated diene compound. And a compound obtained by epoxidizing a carbon-carbon double bond of the partially hydrogenated product. Specific examples of the epoxy resin (8) include epoxidized polybutadiene or epoxidized dicyclopentadiene.

  The epoxy resin (9) has a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound or a partially hydrogenated polymer block in the same molecule. Examples of the block copolymer include a compound in which a carbon-carbon double bond is epoxidized. Examples of such a compound include epoxidized SBS.

  Examples of the epoxy resin (10) include a urethane-modified epoxy resin in which a urethane bond is introduced or a polycaprolactone in which a polycaprolactone bond is introduced in the structure of the epoxy resin of the above (1) to (9). Examples thereof include modified epoxy resins.

  Examples of the epoxy resin (11) include an epoxy resin having a bisarylfluorene skeleton.

  As a commercial item of the said epoxy resin (11), the brand name "Oncoat EX series" by Osaka Gas Chemical Company etc. are mentioned, for example.

  Moreover, a flexible epoxy resin is suitably used as the epoxy resin. The use of a flexible epoxy resin can increase the flexibility of the cured product.

  Examples of the flexible epoxy resin include diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, polyglycidyl ether of long chain polyol, a copolymer of glycidyl (meth) acrylate and a radical polymerizable monomer, and an epoxy group. Polyester resin having a conjugated diene compound as a main component, a compound obtained by epoxidizing a carbon-carbon double bond of a (co) polymer, a carbon-carbon as a partially hydrogenated product of a (co) polymer mainly including a conjugated diene compound Examples include a compound in which a double bond is epoxidized, a urethane-modified epoxy resin, or a polycaprolactone-modified epoxy resin.

  Further, the flexible epoxy resin includes a dimer acid-modified epoxy resin in which an epoxy group is introduced into the molecule of a dimer acid or a dimer acid derivative, or a rubber-modified epoxy in which an epoxy group is introduced into a molecule of a rubber component. Examples thereof include resins.

  Examples of the rubber component include NBR, CTBN, polybutadiene, and acrylic rubber.

  The flexible epoxy resin preferably has a butadiene skeleton. By using a flexible epoxy resin having a butadiene skeleton, the flexibility of the cured product can be further enhanced. In addition, the elongation of the cured product can be increased over a wide temperature range from a low temperature range to a high temperature range.

  A biphenyl type epoxy resin may be used as the epoxy resin. Examples of the biphenyl type epoxy resin include compounds in which part of the hydroxyl group of the phenol compound is substituted with an epoxy group-containing group and the remaining hydroxyl group is substituted with a substituent such as hydrogen other than the hydroxyl group.

  The biphenyl type epoxy resin is preferably a biphenyl type epoxy resin represented by the following formula (8). By using this preferable biphenyl type epoxy resin, the linear expansion coefficient of the cured product can be further reduced.

  In said formula (8), t shows the integer of 1-11.

  In the epoxy resin composition according to the present invention, 15 wt% to 80 wt% of the total of 100 wt% of the epoxy resin, the curing agent and the silica component is preferably liquid at 23 ° C. More preferably, 25% by weight or more of the total of 100% by weight of the epoxy resin, the curing agent and the silica component is liquid at 23 ° C. If the amount of the component that is liquid at 23 ° C. is less than 15% by weight, the epoxy resin composition in the B-stage state becomes brittle and cracks when the epoxy resin composition is bent. Furthermore, when the content of the component that is liquid at 23 ° C. is too small, the epoxy resin composition was cut with a cutter or the like when the curing agent was a phenol compound having a biphenyl structure or a phenol compound having a naphthalene structure. Occasionally chips may be generated. As a liquid component at 23 ° C., a bisphenol A type epoxy resin or a bisphenol F type epoxy resin can be suitably used.

  The epoxy resin is at least one selected from the group consisting of an epoxy resin having an anthracene skeleton, an epoxy resin having a naphthalene skeleton, an epoxy resin having an adamantane skeleton, an epoxy resin having a triazine skeleton, and an epoxy resin having a biphenyl skeleton. It is preferable that epoxy resin (hereinafter abbreviated as epoxy resin A) is included. Moreover, it is preferable that content of the said epoxy resin A exists in the range of 2-20 weight% in the total 100 weight% of all the epoxy resins contained in the epoxy resin composition.

  When the epoxy resin A is included, and when the content of the epoxy resin A is within the preferable range, the glass transition temperature of the cured product can be increased and the linear expansion coefficient can be decreased. The handling property of the resin-based resin composition or the sheet-like molded product can be improved. Furthermore, when the content of the epoxy resin A is within the preferable range, the surface roughness of the roughened cured body can be further reduced. For this reason, an epoxy-type resin composition can be used conveniently for the insulating film for buildups.

(Curing agent)
The curing agent contained in the epoxy resin composition according to the present invention is not particularly limited as long as it can cure the epoxy resin. As the curing agent, a conventionally known curing agent can be used.

  Examples of the curing agent include dicyandiamide, amine compounds, compounds synthesized from amine compounds, imidazole compounds, hydrazide compounds, melamine compounds, acid anhydrides, phenol compounds, active ester compounds, benzoxazine compounds, and thermal latent cationic polymerization. A catalyst, photolatent cationic polymerization initiator, cyanate ester resin, etc. are mentioned. Derivatives of these curing agents may be used. As for a hardening | curing agent, only 1 type may be used and 2 or more types may be used together. A curing catalyst such as acetylacetone iron may be used together with the curing agent.

  Examples of the amine compound include a chain aliphatic amine compound, a cyclic aliphatic amine compound, and an aromatic amine compound.

  Examples of the chain aliphatic amine compound include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, and polyoxypropylenetriamine.

  Examples of the cycloaliphatic amine compound include mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, or 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane and the like can be mentioned.

  Examples of the aromatic amine compound include m-xylenediamine, α- (m / p-aminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and α, α-bis (4-aminophenyl). ) -P-diisopropylbenzene.

  A tertiary amine compound may be used as the amine compound. Examples of the tertiary amine compound include N, N-dimethylpiperazine, pyridine, picoline, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, and 1,8. -Diazabiscyclo (5,4,0) undecene-1 etc. are mentioned.

  Specific examples of the compound synthesized from the amine compound include a polyaminoamide compound, a polyaminoimide compound, or a ketimine compound.

  Examples of the polyaminoamide compound include compounds synthesized from the amine compounds and carboxylic acids. Examples of the carboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecadioic acid, isophthalic acid, terephthalic acid, dihydroisophthalic acid, tetrahydroisophthalic acid, and hexahydroisophthalic acid.

  Examples of the polyaminoimide compound include compounds synthesized from the amine compound and maleimide compound. Examples of the maleimide compound include diaminodiphenylmethane bismaleimide.

  Moreover, as said ketimine compound, the compound etc. which are synthesize | combined from the said amine compound and a ketone compound are mentioned, for example.

  Other specific examples of the compound synthesized from the amine compound include compounds synthesized from the amine compound and an epoxy compound, a urea compound, a thiourea compound, an aldehyde compound, a phenol compound, or an acrylic compound. .

  Examples of the imidazole compound include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2' -Undecylimidazolyl- (1 ')]-Ethi -S-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methyl Imidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Examples include phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazoline, or 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole.

  Examples of the hydrazide compound include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 7,11-octadecadien-1,18-dicarbohydrazide, eicosane diacid dihydrazide, and adipic acid dihydrazide. Is mentioned.

  Examples of the melamine compound include 2,4-diamino-6-vinyl-1,3,5-triazine.

  Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, Methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 5- (2,5-dioxo Tetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, polyazelinic anhydride, polydodecanedioic anhydride Or chlorendic acid Anhydride, and the like.

  Examples of the thermal latent cationic polymerization catalyst include an ionic thermal latent cationic polymerization catalyst and a nonionic thermal latent cationic polymerization catalyst.

  Examples of the ionic thermal latent cationic polymerization catalyst include benzylsulfonium salt, benzylammonium salt, benzylpyridinium salt or benzylsulfonium salt having antimony hexafluoride, phosphorus hexafluoride or boron tetrafluoride as a counter anion. Can be mentioned.

  Examples of the nonionic thermal latent cationic polymerization catalyst include N-benzylphthalimide or aromatic sulfonic acid ester.

  Examples of the photolatent cationic polymerization catalyst include ionic photolatent cationic polymerization initiators and nonionic photolatent cationic polymerization initiators.

  Specific examples of the ionic photolatent cationic polymerization initiator include onium salts and organometallic complexes. Examples of the onium salts include aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts using antimony hexafluoride, phosphorus hexafluoride, boron tetrafluoride, or the like as a counter anion. Examples of the organometallic complexes include iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes.

  Specific examples of the nonionic photolatent cationic polymerization initiator include nitrobenzyl ester, sulfonic acid derivative, phosphoric ester, phenol sulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate, and the like.

  Examples of the phenol compound include phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, phenol aralkyl resin, α-naphthol aralkyl resin, β-naphthol aralkyl resin or aminotriazine novolak. Examples thereof include resins. These derivatives may be used as the phenol compound. As for a phenol compound, only 1 type may be used and 2 or more types may be used together.

  The phenol compound is preferably used as the curing agent. By using the phenol compound, the heat resistance and dimensional stability of the cured product can be increased, and the water absorption of the cured product can be lowered. Furthermore, the surface roughness of the roughened cured body can be further reduced. Specifically, the arithmetic average roughness Ra and the ten-point average roughness Rz of the surface of the roughened cured body can be further reduced.

  As the curing agent, a phenol compound represented by any one of the following formula (1), the following formula (2), and the following formula (3) is more preferably used. In this case, the surface roughness of the cured body can be further reduced.

  In said formula (1), R1 shows a methyl group or an ethyl group, R2 shows hydrogen or a hydrocarbon group, n shows the integer of 2-4.

  In said formula (2), m shows the integer of 0-5.

  In the above formula (3), R3 represents a group represented by the following formula (4a) or the following formula (4b), and R4 is represented by the following formula (5a), the following formula (5b) or the following formula (5c). R5 represents a group represented by the following formula (6a) or the following formula (6b), R6 represents hydrogen or an organic group having 1 to 20 carbon atoms, and p represents an integer of 1 to 6. , Q represents an integer of 1 to 6, and r represents an integer of 1 to 11.

  Among them, a phenol compound represented by the above formula (3), and a phenol compound having a biphenyl structure in which R4 in the above formula (3) is a group represented by the above formula (5c) is preferable. By using this preferable curing agent, the electrical properties and heat resistance of the cured product can be further increased, and the linear expansion coefficient and water absorption can be further decreased. Furthermore, the dimensional stability of the cured product when a thermal history is given can be further enhanced.

  The curing agent is particularly preferably a phenol compound having a structure represented by the following formula (7). In this case, the electrical properties and heat resistance of the cured product can be further increased, and the linear expansion coefficient and water absorption can be further decreased. Furthermore, the dimensional stability of the cured product when a thermal history is given can be further enhanced.

  In said formula (7), s shows the integer of 1-11.

  As said active ester compound, an aromatic polyvalent ester compound etc. are mentioned, for example. When an active ester compound is used, no OH group is generated during the reaction between the active ester group and the epoxy resin, so that a cured product having excellent dielectric constant and dielectric loss tangent can be obtained. Specific examples of the active ester compound are disclosed in, for example, JP-A No. 2002-12650.

  As a commercial item of the said active ester compound, the brand name "EPICLON EXB9451-65T" by Dainippon Ink & Chemicals, Inc. etc. are mentioned, for example.

  Examples of the benzoxazine compound include aliphatic benzoxazine resins and aromatic benzoxazine resins.

  As a commercial item of the said benzoxazine compound, the brand name "Pd type benzoxazine", "Fa type benzoxazine", etc. by Shikoku Chemical Industry Co., Ltd. etc. are mentioned, for example.

  As the cyanate ester resin, for example, a novolak-type cyanate ester resin, a bisphenol-type cyanate ester resin, a prepolymer obtained by partially triazinating, or the like can be used. By using a cyanate ester resin, the linear expansion coefficient of the cured product can be further reduced.

  When using the said imidazole compound, you may use a hardening accelerator with this imidazole compound.

  Examples of the curing accelerator include phosphine compounds such as triphenorphosphine, DBU, DBN, DBU phenol salt, DBN phenol salt, octylate, p-toluenesulfonate, formate, orthophthalate or phenol novolac resin. Examples include salts.

  The curing agent is at least one selected from the group consisting of a phenol compound having a biphenyl structure, a phenol compound having a naphthalene structure, a phenol compound having a dicyclopentadiene structure, a phenol compound having an aminotriazine structure, and an active ester compound. It preferably contains a curing agent (hereinafter abbreviated as curing agent B). It is preferable that content of the said hardening | curing agent B exists in the range of 1 to 100 weight% in 100 weight% of all the hardening | curing agents contained in the epoxy resin composition. When the curing agent B is included, and when the content of the curing agent B is within the preferable range, the resin component is hardly adversely affected by the roughening treatment when the cured product is roughened.

  The curing agent is preferably at least one selected from the group consisting of a phenol compound, an active ester compound, and a benzoxazine compound. When these preferable curing agents are used, when the cured product is roughened, the resin component is hardly affected by the roughening treatment.

  By using an active ester compound or a benzoxazine compound, it is possible to obtain a cured product having a better dielectric constant and dielectric loss tangent. The active ester compound is preferably an aromatic polyvalent ester compound. By using the aromatic polyvalent ester compound, it is possible to obtain a cured product that is further excellent in dielectric constant and dielectric loss tangent.

  The curing agent may be at least one selected from the group consisting of a phenol compound having a biphenyl structure, a phenol compound having a naphthalene structure, a phenol compound having a dicyclopentadiene structure, and a phenol compound having an aminotriazine structure. It is particularly preferred. When these preferable hardening | curing agents are used, when roughening a hardened | cured material, a resin component is harder to receive a bad influence by a roughening process. Specifically, when roughening the cured product, the silica component can be selectively desorbed and fine pores can be formed without the surface of the cured product becoming too rough. For this reason, the fine unevenness | corrugation whose surface roughness is very small can be formed in the surface of hardened | cured material. Of these, a phenol compound having a biphenyl structure is preferable.

  By using a phenolic compound having a biphenyl structure or a phenolic compound having a naphthalene structure, a cured product having excellent electrical characteristics, particularly dielectric loss tangent, excellent strength and linear expansion coefficient, and low water absorption is obtained. Can do.

  When the molecular weights of the epoxy resin and the curing agent are large, it is easy to form a fine rough surface on the surface of the cured product. The weight average molecular weight of the epoxy resin affects the formation of a fine rough surface. However, the weight average molecular weight of the curing agent has a greater influence on the formation of a fine rough surface than the weight average molecular weight of the epoxy resin. The weight average molecular weight of the curing agent is preferably 500 or more, and more preferably 1800 or more. A preferable upper limit of the weight average molecular weight of the curing agent is 15000. If the weight average molecular weight of the curing agent is too large, the resin may not be easily etched in the swelling and roughening process, or the resin may not be removed during laser drilling.

  Moreover, when the epoxy equivalent of an epoxy resin and the equivalent of a hardening | curing agent are large, it is easy to form a fine rough surface on the surface of hardened | cured material. Furthermore, when the curing agent is solid and the softening temperature of the curing agent is 60 ° C. or higher, it is easy to form a fine rough surface on the surface of the cured product.

  The curing agent is preferably contained within a range of 1 to 200 parts by weight with respect to 100 parts by weight of the epoxy resin. When there is too little content of a hardening | curing agent, an epoxy resin may not fully harden | cure. If the content of the curing agent is too large, the effect of curing the epoxy resin may be saturated. The minimum with more preferable content of the said hardening | curing agent is 30 weight part, and a more preferable upper limit is 140 weight part.

(Silica component)
The epoxy resin composition of the present invention contains a silica component in which silica particles are formed from the surface by a silane coupling agent. Only 1 type may be used for a silica component and 2 or more types may be used together.

  The average particle diameter of the silica particles is 1 μm or less. When the average particle diameter is 1 μm or less, a fine rough surface can be formed on the cured body obtained by roughening the cured product. In addition, fine holes having an average diameter of about 1 μm or less can be formed on the surface of the cured product. The average particle diameter of the silica particles is preferably 50 nm or more.

  When the average particle diameter of the silica particles is larger than 1 μm, the silica component is hardly detached when the cured product is roughened. In addition, when a plating process is performed to form a metal layer on the surface of the hardened body that has been subjected to the roughening treatment, the plating may sink into the gap between the silica component and the resin component that have not been detached. For this reason, when the metal layer is formed in the surface of hardened | cured material as a circuit, there exists a possibility that a malfunction may arise in a circuit.

  In particular, when a phenol compound having a biphenyl structure, a phenol compound having a naphthalene structure, a phenol compound having a dicyclopentadiene structure, a phenol compound having an aminotriazine structure, an aromatic polyvalent ester compound, or a benzoxazine compound is used as a curing agent In the case of the roughening treatment, the resin component around the silica component is hardly scraped off. In this case, when the average particle diameter of the silica particles is larger than 1 μm, the silica component is more difficult to desorb.

  When silica particles having an average particle diameter of 1 μm or less and not surface-treated with a silane coupling agent are used, the silica particles tend to aggregate. Moreover, also when using the imidazole silane processing silica in which the silica particle whose average particle diameter is 1 micrometer or less is surface-treated with imidazole silane, the imidazole silane processing silica tends to aggregate. For this reason, silica particles or imidazole silane-treated silica may not be sufficiently dispersed in the epoxy resin composition.

  In contrast, in the present invention, not an imidazole silane, but a silane compound having an amino group, a silane compound having a mercapto group, a silane compound having an isocyanate group, a silane compound having an acid anhydride group, and a silane compound having an isocyanuric acid group Since the silica component in which the silica particles are surface-treated is used by at least one silane coupling agent selected from the group consisting of: the silica component hardly aggregates. For this reason, the dispersibility of the silica component in an epoxy resin composition can be improved. For this reason, the addition amount of a silica component can be made comparatively large. Even if the addition amount of the silica component is large, a fine rough surface can be formed on the cured product obtained by roughening the cured product.

  Silica particles tend to aggregate as the particle size decreases. At least one silane cup selected from the group consisting of a silane compound having an amino group, a silane compound having a mercapto group, a silane compound having an isocyanate group, a silane compound having an acid anhydride group, and a silane compound having an isocyanuric acid group Since the silica component in which the silica particles are surface-treated with the ring agent is less likely to aggregate than imidazole silane, the particle diameter of the silica used can be reduced. In particular, when a silica component whose silica particles are surface-treated with a silane compound having an amino group is used, the surface roughness of the roughened cured body can be extremely reduced.

  In the epoxy resin composition according to the present invention, for example, an aggregate in which about 10 or more silica components are aggregated is extremely unlikely to occur.

  As the average particle diameter of the silica particles, a median diameter (d50) value of 50% can be adopted. The average particle size can be measured using a laser diffraction / scattering particle size distribution measuring apparatus.

  A plurality of types of silica particles having different average particle diameters may be used. In consideration of fine packing, it is preferable to use a plurality of types of silica particles having different particle size distributions. In this case, for example, the epoxy resin composition can be suitably used for applications requiring fluidity such as a component-embedded substrate. In addition to the silica component, by using silica particles having an average particle size of several tens of nanometers, the viscosity of the epoxy resin composition can be increased, or the thixotropy of the epoxy resin composition can be controlled. it can.

  The maximum particle size of the silica particles is preferably 5 μm or less. When the maximum particle size is 5 μm or less, the silica component is more easily detached when the cured product is roughened. Furthermore, it is difficult to form relatively large holes on the surface of the cured product, and uniform and fine irregularities can be formed.

  In particular, when a phenol compound having a biphenyl structure, an aromatic polyvalent ester compound, or a benzoxazine compound is used as a curing agent, the roughening liquid does not easily penetrate into the cured product from the surface of the cured product, and the silica component is compared. It is difficult to detach. However, by using a silica component having a maximum particle size of 5 μm or less, the silica component can be easily removed. When forming fine wiring with L / S of 15 μm / 15 μm or less on the surface of the cured product, the insulation reliability can be improved, so the maximum particle diameter of silica is preferably 2 μm or less. Note that “L / S” indicates the dimension (L) in the width direction of the wiring / the dimension (S) in the width direction of the portion where the wiring is not formed.

  The shape of the silica particles is not particularly limited. Examples of the shape of the silica particles include a spherical shape or an indefinite shape. Since the silica component is more easily detached when the cured product is roughened, the silica particles are preferably spherical and more preferably true spherical.

The specific surface area of the silica particles is preferably 3 m ² / g or more. There exists a possibility that the mechanical characteristic of hardened | cured material may fall that a specific surface area is less than 3 m < ² > / g. Furthermore, for example, when a metal layer is formed on the surface of the roughened cured body, the adhesion between the cured product and the metal layer may be reduced. The specific surface area can be determined by the BET method.

  As the silica particles, crystalline silica obtained by pulverizing natural silica raw material, crushed fused silica obtained by flame melting and pulverizing natural silica raw material, and natural silica raw material obtained by flame melting, pulverizing and flame melting And synthetic silica such as spherical fused silica, fumed silica (Aerosil), or sol-gel silica.

  The synthetic silica often contains ionic impurities. Since the purity is high, fused silica is preferably used. The silica particles may be used as a silica slurry in a state dispersed in a solvent. By using the silica slurry, workability and productivity can be improved during the production of the epoxy resin composition.

  The silane coupling agent is selected from the group consisting of silane compounds having amino groups, silane compounds having mercapto groups, silane compounds having isocyanate groups, silane compounds having acid anhydride groups, and silane compounds having isocyanuric acid groups. At least one kind is used. As for a silane coupling agent, only 1 type may be used and 2 or more types may be used together.

  Specific examples of the silane compound having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyltrimethoxysilane, N- 2- (aminoethyl) -3-aminopropylmethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propyl Examples include amine, N-phenyl-3-aminopropyltrimethoxysilane, and 3- (4-methylpiperazino) propyltrimethoxysilane.

  Specific examples of the silane compound having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

  Specific examples of the isocyanate silane include 3-isocyanatopropyltriethoxysilane.

  As the silane compound having an acid anhydride group, a conventionally known silane compound having an acid anhydride group can be used.

  As the silane compound having an isocyanuric acid group, a conventionally known silane compound having an isocyanuric acid group can be used.

  After the silica particles are surface-treated with the silane coupling agent to obtain a silica component, the silica component is preferably added to the resin composition. In this case, the dispersibility of the silica component can be further enhanced.

  Examples of the method for surface-treating the silica particles with a silane coupling agent include the following first to third methods.

  The first method includes a dry method. Examples of the dry method include a method of directly attaching a silane coupling agent to silica particles. In the dry method, silica particles are charged into a mixer, and an alcohol solution or an aqueous solution of a silane coupling agent is dropped or sprayed with stirring, and then further stirred and classified by sieving. Thereafter, the silica component can be obtained by dehydrating and condensing the silane coupling agent and the silica particles by heating. The obtained silica component may be used as a silica slurry in a state dispersed in a solvent.

  The second method includes a wet method. In the wet method, a silane coupling agent is added while stirring a silica slurry containing silica particles, and after stirring, classification is performed by filtration, drying, and sieving. Next, the silica component can be obtained by dehydrating and condensing the silane compound and silica by heating.

  As a third method, there is a method in which dehydration condensation proceeds by heating and refluxing after adding a silane coupling agent while stirring a silica slurry containing silica particles. The obtained silica component may be used as a silica slurry in a state dispersed in a solvent.

  When untreated silica particles are used, the silica particles are not combined with the epoxy resin even if the epoxy resin composition is cured. When the silica component in which the silica particles are surface-treated with the specific silane coupling agent is used, when the epoxy resin composition is cured, the silica component is combined with the epoxy resin. For this reason, the glass transition temperature Tg of hardened | cured material becomes high. That is, the silica component in which the silica particles are surface-treated with the silane coupling agent, not the untreated silica particles, is contained in the epoxy resin composition, so that the glass transition temperature Tg of the cured product is increased. can do.

  In particular, the use of a silica component in which silica particles are surface-treated with a silane compound having an isocyanuric acid group can further increase the glass transition temperature Tg of the cured product.

  Moreover, the reflow resistance of hardened | cured material can be improved by use of the silica component by which the said silica particle is surface-treated with the said specific silane coupling agent.

  When a silica component whose silica particles are surface-treated with imidazole silane is used, the water absorption of the cured product is increased because the hydrophilicity of the silica component is relatively high.

  On the other hand, at least one selected from the group consisting of a silane compound having an amino group, a silane compound having a mercapto group, a silane compound having an isocyanate group, a silane compound having an acid anhydride group, and a silane compound having an isocyanuric acid group When silica whose surface is treated with seeds is used, the water absorption of the cured product can be lowered, and the insulation reliability of the cured product can be increased. Specifically, for example, the volume resistivity of the cured product can be maintained high even under high temperature and high humidity conditions such as in a HAST (highly accelerated stress test) environment or a PCT (pressure cooker test) environment.

  The silica component is contained within a range of 25 to 400 parts by weight with respect to a total of 100 parts by weight of the epoxy resin and the curing agent. The minimum with preferable content of the said silica component with respect to a total of 100 weight part of the said epoxy resin and the said hardening | curing agent is 43 weight part, A preferable upper limit is 250 weight part, A more preferable upper limit is 150 weight part. When there is too little content of a silica component, when roughening a hardened | cured material, the total surface area of the hole formed by detachment | desorption of a silica component will become small. For this reason, when a metal layer is formed on the surface of the roughened cured body, the adhesive strength between the cured product and the metal layer may not be sufficiently increased. When there is too much content of the said silica component, the hardened | cured material roughened is easy to become weak, and the adhesive strength of a hardened | cured material and a metal layer may fall.

  In the present invention, even if the content of the silica component is large, for example, even if the content of the silica component with respect to a total of 100 parts by weight of the epoxy resin and the curing agent is 100 parts by weight or more, the silica component is epoxy-based. It can be sufficiently dispersed in the resin composition. Therefore, the surface roughness of the cured product obtained by roughening the surface of the cured product can be reduced, and the linear expansion coefficient of the cured product can be reduced. Further, in the present invention, since the dispersibility of the silica component is excellent, the linear expansion coefficient is low even when the amount of the silica component is the same as compared with the conventional case where the silica component that is difficult to disperse is used. can do.

  The silica component is preferably a silica component in which 100 parts by weight of silica particles are surface-treated with 0.6 to 5 parts by weight of a silane coupling agent. A preferable lower limit of the amount of the silane coupling agent is 2 parts by weight, and a preferable upper limit is 4 parts by weight. If the amount of the silane coupling agent is too small, the surface roughness of the roughened cured body tends to increase. When there is too much quantity of a silane coupling agent, the storage stability of an epoxy resin composition will fall, and an epoxy resin composition will become easy to gelatinize.

(Organized layered silicate)
The epoxy resin composition according to the present invention preferably contains an organically modified layered silicate.

  In the epoxy resin composition containing the organic layered silicate, the organic layered silicate exists around the silica component. For this reason, when the cured product is subjected to a swelling treatment and a roughening treatment, the silica component present on the surface of the cured product is more easily detached. This is because the swelling liquid or the roughening liquid permeates through an infinite number of nano-order interfaces between the organic layered silicate layers or between the organic layered silicate and the resin component, and between the epoxy resin and the silica component. It is presumed that the swelling liquid or the roughening liquid also permeates the interface. However, the mechanism that facilitates the separation of the silica component is not clear.

  Examples of the organically modified layered silicate include an organically modified layered silicate obtained by organically treating a layered silicate such as smectite clay mineral, swelling mica, vermiculite, or halloysite. As for the organic layered silicate, only 1 type may be used and 2 or more types may be used together.

  Examples of the smectite clay mineral include montmorillonite, hectorite, saponite, beidellite, stevensite, and nontronite.

  As the organic layered silicate, an organic layered silicate obtained by organically treating at least one layered silicate selected from the group consisting of montmorillonite, hectorite and swellable mica is preferably used.

  The organically modified layered silicate is preferably contained within a range of 0.01 to 2 parts by weight with respect to a total of 100 parts by weight of the epoxy resin and the curing agent. If the content of the organically modified layered silicate is too small, the effect of easily detaching the silica component may be insufficient. When there is too much content of the said organic-ized layered silicate, the interface which a swelling liquid or a roughening liquid osmose | permeates will increase too much, and the surface roughness of the roughened hardening body will become comparatively large. In particular, when the epoxy resin composition is used for sealant applications, if the content of the organically modified layered silicate is too large, the permeation rate of the swelling liquid or the roughening liquid becomes faster. The speed at which the surface roughness of the cured body changes is too fast, and it may not be possible to secure sufficient treatment time for the swelling treatment or roughening treatment.

  When the content of the organically modified layered silicate with respect to 100 parts by weight of the total of the epoxy resin and the curing agent exceeds 2 parts by weight, the surface roughness of the roughened cured body tends to be relatively large.

  Note that when the organic layered silicate is not used, the surface roughness of the roughened cured body is further reduced. By adjusting the blending ratio of the silica component and the organically modified layered silicate, the surface roughness of the roughened cured product can be controlled.

  The silica component is contained in the range of 25 to 400 parts by weight and the organically modified layered silicate is contained in the range of 0.1 to 2 parts by weight with respect to a total of 100 parts by weight of the epoxy resin and the curing agent. Preferably it is. In this case, when the substrate formed of the cured product of the epoxy resin composition is perforated by a laser such as a carbon dioxide laser, the epoxy resin, the curing agent and the organically modified layered silicate are simultaneously decomposed, Evaporates easily. For this reason, the amount of the resin-derived component partially remaining and the residue of the organically modified layered silicate can be extremely reduced. Therefore, for example, when desmear treatment is performed, the remaining organic layered silicate residue can be easily removed without performing desmear treatment a plurality of times or in combination of a plurality of types. Therefore, a residue is not easily generated by the drilling process, and hence plating defects and the like can be suppressed.

  In addition, the said desmear process can use a well-known method. For the desmear treatment, for example, a plasma treatment method or a chemical solution treatment method can be used.

(Maleimide compound)
The epoxy resin composition of the present invention preferably contains a maleimide compound.

  The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule. Examples of the maleimide compound include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis [4- (4-maleimidophenoxy) -phenyl] propane, and bis (3 , 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane, polyphenylmethanemaleimide, these Examples include a prepolymer of a maleimide compound or a prepolymer of a maleimide compound and an amine compound. As for the said maleimide compound, only 1 type may be used and 2 or more types may be used together.

  As the maleimide compound, bis (4-maleimidophenyl) methane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane or poly Phenylmethane maleimide is preferably used.

  Commercially available products of the maleimide compound include bis (4-maleimidophenyl) methane (4,4′-diphenylmethane bismaleimide) with a trade name “BMI-1000”, polyphenylmethanemaleimide (phenyl) with a trade name “BMI-2000”. Oligomer of methane maleimide), bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (trade name “BMI” manufactured by Daiwa Kasei Kogyo Co., Ltd.) and trade name “BMI-5100” (4-maleimidophenyl) methane (4,4′-diphenylmethane bismaleimide), bis (3-ethyl-5-methyl-4-maleimidophenyl) methane under the trade name “BMI-70”, and trade name “BMI-80” 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane (above) Re also include KI Chemical Industry Co., Ltd.), and the like.

  By using the maleimide compound, it is possible to further increase the thermal expansion characteristics of the cured product, the heat resistance and flame retardance during moisture absorption, and the peel strength of the metal foil against the cured product.

  In 100 wt% of the epoxy resin composition, the content of the maleimide compound is preferably in the range of 2 to 45 wt%. The more preferable lower limit of the content of the maleimide compound in 100% by weight of the epoxy resin composition is 5% by weight, and the more preferable upper limit is 25% by weight. If the content of the maleimide compound is too small, the effect of adding the maleimide compound may not be sufficiently obtained. If the content of the maleimide compound is too large, the surface roughness of the roughened cured product will increase, the tensile strength or elongation of the cured product will decrease, or the epoxy resin composition or sheet-shaped molded product will be handled. May deteriorate.

(Other ingredients that can be added)
The epoxy resin composition according to the present invention may contain a resin copolymerizable with the epoxy resin, if necessary, in addition to the epoxy resin.

  The copolymerizable resin is not particularly limited. Examples of the copolymerizable resin include phenoxy resin, thermosetting modified polyphenylene ether resin, or benzoxazine resin. As the copolymerizable resin, only one type may be used, or two or more types may be used in combination.

  Specific examples of the thermosetting modified polyphenylene ether resin include resins obtained by modifying a polyphenylene ether resin with a functional group such as an epoxy group, an isocyanate group, or an amino group. As for the said thermosetting modified polyphenylene ether resin, only 1 type may be used and 2 or more types may be used together.

  Examples of commercially available curable modified polyphenylene ether resins obtained by modifying a polyphenylene ether resin with an epoxy group include trade name “OPE-2Gly” manufactured by Mitsubishi Gas Chemical Company.

  The benzoxazine resin is not particularly limited. Specific examples of the benzoxazine resin include a resin in which a substituent having an aryl group skeleton such as a methyl group, an ethyl group, a phenyl group, a biphenyl group, or a cyclohexyl group is bonded to nitrogen of the oxazine ring, or a methylene group, an ethylene group And a resin in which a substituent having an arylene skeleton such as a phenylene group, a biphenylene group, a naphthalene group, or a cyclohexylene group is bonded between nitrogen atoms of two oxazine rings. As for the said benzoxazine resin, only 1 type may be used and 2 or more types may be used together. By the reaction between the benzoxazine resin and the epoxy resin, the heat resistance of the cured product can be increased, and the water absorption and the linear expansion coefficient can be decreased.

  A benzoxazine monomer or oligomer, or a resin in which a benzoxazine monomer or oligomer is polymerized by ring-opening polymerization of an oxazine ring is included in the benzoxazine resin.

  The epoxy resin composition according to the present invention includes, as necessary, thermoplastic resins, thermosetting resins other than epoxy resins, thermoplastic elastomers, crosslinked rubber, oligomers, inorganic compounds, and nucleating agents. , Antioxidant, anti-aging agent, heat stabilizer, light stabilizer, ultraviolet absorber, lubricant, flame retardant aid, silane coupling agent, antistatic agent, antifogging agent, filler, softener, plasticizer or Additives such as colorants may be added. As for these additives, only 1 type may be used and 2 or more types may be used together.

  Specific examples of the thermoplastic resins include polysulfone resins, polyether sulfone resins, polyimide resins, polyetherimide resins, and phenoxy resins. As for the said thermoplastic resins, only 1 type may be used and 2 or more types may be used together.

  Examples of the thermosetting resins include a polyvinyl benzyl ether resin or a reaction product obtained by a reaction between a bifunctional polyphenylene ether oligomer and chloromethylstyrene. As a commercial product of the reaction product obtained by the reaction of the bifunctional polyphenylene ether oligomer and chloromethylstyrene, there is a trade name “OPE-2St” manufactured by Mitsubishi Gas Chemical Company. As for the said thermosetting resins, only 1 type may be used and 2 or more types may be used together.

  When the thermoplastic resin or the thermosetting resin is used, the thermoplastic resin or the thermosetting resin is 0.5 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin composition. It is preferably contained within the range, and more preferably contained within the range of 1 to 20 parts by weight. When there is too little content of a thermoplastic resin or a thermosetting resin, the elongation and toughness of hardened | cured material may not fully be improved, and when too large, the intensity | strength of hardened | cured material may fall.

  The silane coupling agent may be added to the epoxy resin composition for the purpose of enhancing the adhesion with other members such as copper foil.

(Epoxy resin composition)
The manufacturing method of the epoxy resin composition according to the present invention is not particularly limited. As a method for producing an epoxy resin composition, for example, after adding the epoxy resin, the curing agent, the silica component, and an organized layered silicate blended as necessary, to a solvent And a method of drying and removing the solvent.

  The epoxy resin composition according to the present invention may be used after being dissolved in, for example, a suitable solvent.

  The use of the epoxy resin composition according to the present invention is not particularly limited. Epoxy resin compositions include, for example, substrate materials for forming core layers and buildup layers of multilayer substrates, adhesive sheets, laminates, copper foils with resin, copper-clad laminates, TAB tapes, printed boards, prepregs, etc. Or it is used suitably for a varnish etc.

  Moreover, a fine hole can be formed in the surface of the hardening body roughened by using the epoxy resin composition which concerns on this invention. For this reason, fine wiring can be formed on the surface of the cured body, and the signal transmission speed in the wiring can be increased. Therefore, the epoxy resin composition is suitably used for applications that require insulation, such as a resin-coated copper foil, a copper-clad laminate, a printed board, a prepreg, an adhesive sheet, or a TAB tape.

  The epoxy resin of the present invention is applied to an additive method in which a circuit is formed after a conductive plating layer is formed on the surface of a cured product, a build-up substrate in which a plurality of cured products and conductive plating layers are laminated by a semi-additive method, etc. The composition is more preferably used. In this case, the bonding reliability between the conductive plating layer and the cured product can be increased. Moreover, since the hole which the silica component formed in the surface of the hardening body roughened is small, the insulation reliability between patterns can be improved. Furthermore, since the depth of the hole through which the silica component is removed is shallow, the insulation reliability between the layers can be improved. Therefore, highly reliable fine wiring can be formed.

  The epoxy resin composition according to the present invention can also be used for a sealing material or a solder resist. Further, since the high-speed signal transmission performance of the wiring formed on the surface of the cured body can be enhanced, the present invention can be applied to a component-embedded substrate or the like in which a passive component or an active component is built that requires high-frequency characteristics. An epoxy resin composition can be used.

(Prepreg)
The prepreg according to the present invention is a prepreg in which a porous base material is impregnated with the epoxy resin composition.

  The porous substrate is not particularly limited as long as it can be impregnated with the epoxy resin composition. Examples of the porous substrate include organic fibers or glass fibers. Examples of the organic fiber include carbon fiber, polyamide fiber, polyaramid fiber, and polyester fiber. Moreover, as a form of a porous base material, the form of textiles, such as a plain weave or a twill, or the form of a nonwoven fabric, etc. are mentioned. The porous substrate is preferably a glass fiber nonwoven fabric.

(Hardened body)
A cured product can be obtained by pre-curing (semi-curing) the epoxy resin composition of the present invention or a prepreg in which the porous substrate is impregnated with the epoxy resin composition. A hardened body can be obtained by roughening the obtained cured product.

  The obtained cured product is generally in a semi-cured state called a B stage. In the present specification, the “cured product” means a range from a semi-cured product to a cured product in a completely cured state.

  Specifically, the cured product of the present invention is obtained as follows.

  In order to form fine irregularities on the surface of the cured product on which the metal layer is formed, the epoxy resin composition or the prepreg is precured to obtain a cured product. In order to pre-cure appropriately, it is preferable to cure the epoxy resin composition or the prepreg by heating at 130 to 190 ° C. for 30 minutes or more.

  When the pre-curing temperature is lower than 130 ° C., the epoxy resin composition is not sufficiently cured, so that the unevenness of the surface of the cured body after the roughening treatment becomes large. When the preliminary curing temperature is higher than 190 ° C., the curing reaction of the epoxy resin composition tends to proceed rapidly. For this reason, the degree of curing tends to be partially different, and a rough portion and a dense portion are likely to be formed. As a result, the unevenness of the surface of the cured body after the roughening treatment is increased. When the pre-curing time is shorter than 30 minutes, the epoxy resin composition is not sufficiently cured, so that the unevenness of the surface of the cured body after the roughening treatment becomes large. Since productivity can be improved, it is preferable that pre-curing time is 1 hour or less.

  In order to form fine irregularities on the surface of the obtained cured product, the cured product is roughened. It is preferable that the cured product is subjected to a swelling treatment before the roughening treatment. However, the cured product is not necessarily subjected to the swelling treatment.

  As the swelling treatment method, for example, a method of treating a cured product with an aqueous solution or an organic solvent dispersion solution of a compound mainly composed of ethylene glycol or the like is used. Specifically, the swelling treatment is carried out by treating the cured product with a 40 wt% ethylene glycol aqueous solution or the like at a treatment temperature of 30 to 85 ° C. for 1 to 20 minutes.

  For the roughening treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound, or a persulfuric acid compound is used. These chemical oxidizers are used as an aqueous solution or an organic solvent dispersion after water or an organic solvent is added.

  Examples of the manganese compound include potassium permanganate and sodium permanganate. Examples of the chromium compound include potassium dichromate and anhydrous potassium chromate. Examples of the persulfate compound include sodium persulfate, potassium persulfate, and ammonium persulfate.

  The roughening treatment method is not particularly limited. As the roughening treatment method, for example, using a 30 to 90 g / L permanganate or permanganate solution and a 30 to 90 g / L sodium hydroxide solution, a treatment temperature of 30 to 85 ° C. and a condition of 1 to 10 minutes A method of treating the cured product once or twice is preferable. When the number of roughening treatments is large, the roughening effect is large. However, when the number of roughening treatments exceeds 3, the roughening effect may be saturated, or the resin component on the surface of the cured body is scraped more than necessary, and the silica component is detached from the surface of the cured body. It becomes difficult to form holes having the shape.

  In FIG. 1, the surface of the hardening body by which the hardened | cured material of the epoxy-type resin composition which concerns on one Embodiment of this invention was roughened is shown with a partial notch front sectional drawing typically.

  As shown in FIG. 1, holes 1 b formed by desorption of the silica component are formed on the surface 1 a of the cured body 1.

  The epoxy resin composition according to the present invention is excellent in dispersibility of the silica component because the silica particles contain a silica component whose surface is treated with the specific silane coupling agent. Therefore, it is difficult for the roughened cured body 1 to form large pores due to the desorption of the silica component aggregates. Therefore, the strength of the cured body 1 is unlikely to decrease locally, and the adhesive strength between the cured body and the metal layer can be increased. Further, in order to lower the linear expansion coefficient of the cured body 1, a large amount of silica component can be blended in the epoxy resin composition. Hole 1b can be formed. However, the hole 1b may be a hole in which about several silica components, for example, 2 to 10 are removed.

  Further, in the vicinity of the hole 1b formed by the desorption of the silica component, the resin component in the portion indicated by the arrow A in FIG. In particular, when a phenol compound having a biphenyl structure, an aromatic polyvalent ester compound, or a compound having a benzoxazine structure is used as a curing agent, the resin component is compared on the surface of the hole 1b formed by the elimination of the silica component. It is easy to be sharpened. However, when the silica particle is a silica component treated with the specific silane coupling agent, a phenol compound having a biphenyl structure, an aromatic polyvalent ester compound, or a compound having a benzoxazine structure is used as a curing agent. Even if used, the resin component is not removed more than necessary. For this reason, the intensity | strength of the hardening body 1 can be raised.

  The arithmetic average roughness Ra of the roughened surface of the cured product obtained as described above is preferably 0.3 μm or less, and the ten-point average roughness Rz is preferably 3.0 μm or less. The arithmetic average roughness Ra of the roughened surface is more preferably 0.2 μm or less. The ten-point average roughness Rz of the roughened surface is more preferably 2.0 μm or less. If the arithmetic average roughness Ra is too large, when the wiring is formed on the surface of the cured body, the transmission speed of the electrical signal in the wiring may not be increased. If the ten-point average roughness Rz is too large, when a wiring is formed on the surface of the cured body, the transmission speed of the electrical signal in the wiring may not be increased. The arithmetic average roughness Ra and the ten-point average roughness Rz can be obtained by a measuring method based on JIS B0601-1994.

The average diameter of the plurality of holes formed on the surface of the cured body is preferably 5 μm or less.
When the average diameter of the plurality of holes is larger than 5 μm, it may be difficult to form a wiring having a small L / S on the surface of the cured body, and the formed wirings are easily short-circuited.

  The roughened cured body can be subjected to electrolytic plating after being subjected to a known plating catalyst or electroless plating, if necessary. Thereby, the plating layer as a metal layer can be formed on the surface of the cured body.

  FIG. 2 shows a state in which the metal layer 2 is formed on the surface of the cured body 1 subjected to the roughening treatment by plating. As shown in FIG. 2, the metal layer 2 reaches into the fine holes 1 b formed on the surface 1 a of the cured body 1. Therefore, the adhesive strength between the cured body 1 and the metal layer 2 can be increased by a physical anchor effect. Further, in the vicinity of the hole 1b formed by the desorption of the silica component, the resin component is not shaved more than necessary, so that the adhesive strength between the cured body 1 and the metal layer 2 can be increased.

  As the average particle diameter of the silica component is smaller, fine irregularities can be formed on the surface of the cured body 1. Since the silica component in which silica particles having an average particle diameter of 1 μm are surface-treated with a silane coupling agent is used, the pores 1b can be made small, and thus fine irregularities are formed on the surface of the cured body 1. it can. For this reason, L / S which shows the fineness of the wiring of a circuit can be made small.

  When wiring such as copper having a small L / S is formed on the surface of the cured body 1, the signal processing speed of the wiring can be increased. For example, even if the signal has a high frequency of 5 GHz or higher, the surface roughness of the cured body 1 is small, so that the loss of an electrical signal at the interface between the cured body 1 and the metal layer 2 can be reduced.

  When L / S is smaller than 65 μm / 65 μm, particularly when L / S is smaller than 45 μm / 45 μm, the average particle diameter of the silica particles is preferably 5 μm or less, and preferably 2 μm or less. When L / S is smaller than 13 μm / 13 μm, the average particle diameter of the silica particles is preferably 2 μm or less, and more preferably 1 μm or less.

  In the epoxy resin composition according to the present invention, silica particles having an average particle diameter of 1 μm or less are subjected to surface treatment with the silane coupling agent, so that variation in surface roughness is small. , Fine wiring with L / S of about 13 μm / 13 μm can be formed on the surface of the cured body. Moreover, fine wiring with L / S of 10 μm / 10 μm or less can be formed on the surface of the cured body without causing a short circuit between the wirings. In the cured body in which such wiring is formed, an electric signal can be transmitted stably and with a small loss.

  As a material for forming the metal layer, a metal foil or metal plating used for shielding or circuit formation, or a plating material used for circuit protection can be used.

  Examples of the plating material include gold, silver, copper, rhodium, palladium, nickel, and tin. Two or more kinds of these alloys may be used, and a plurality of metal layers may be formed of two or more kinds of plating materials. Furthermore, depending on the purpose, the plating material may contain other metals or substances other than the above metals.

(Sheet compacts, laminates and multilayer laminates)
The sheet-shaped molded product according to the present invention is a sheet-shaped molded product in which the epoxy resin composition, the prepreg, or the cured product obtained by curing the epoxy resin composition or the prepreg is molded into a sheet shape. is there.

  In the present specification, the “sheet” is not limited to a thickness or a width, but means a plate shape, and the sheet includes a film. The “sheet-like molded product” includes an adhesive sheet.

  As a method for forming the epoxy resin composition into a sheet, for example, using an extruder, the epoxy resin composition is melt-kneaded, extruded, and then formed into a film with a T die or a circular die. And an extrusion molding method, a casting molding method in which an epoxy resin composition is dissolved or dispersed in a solvent such as an organic solvent and then cast into a film, or other conventionally known sheet molding methods. Of these, the extrusion molding method or the casting molding method is preferable because the thickness can be reduced.

  The laminated board which concerns on this invention is equipped with the said sheet-like molded object and the metal layer laminated | stacked on the at least single side | surface of this sheet-like molded object.

  The multilayer laminated board which concerns on this invention is equipped with the several said sheet-like molded object laminated | stacked, and the at least 1 metal layer arrange | positioned between this sheet-like molded object. The multilayer substrate may further include a metal layer laminated on the outer surface of the outermost sheet-like molded body.

  An adhesive layer may be disposed in at least a part of the sheet-like molded body of the laminate. Moreover, the adhesive layer may be arrange | positioned in the at least one part area | region in the sheet-like molded object on which the multilayer laminated board was laminated | stacked.

  The metal layer of the laminate or multilayer laminate is preferably formed as a circuit. In this case, since the adhesive strength between the sheet-like molded body and the metal layer is high, the reliability of the circuit can be improved.

  FIG. 3 schematically shows a multilayer laminate using the epoxy resin composition according to one embodiment of the present invention in a partially cutaway front sectional view.

  In the multilayer laminated plate 11 shown in FIG. 3, a plurality of cured bodies 13 to 16 are laminated on the upper surface 12 a of the substrate 12. In the cured bodies 13 to 15 other than the uppermost cured body 16, a metal layer 17 is formed in a partial region of the upper surface. That is, the metal layer 17 is arrange | positioned between each layer of the laminated | stacked hardening bodies 13-16, respectively. The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of via hole connection and through hole connection (not shown).

  In the multilayer laminate 11, the cured bodies 13 to 16 are formed by curing a sheet-like molded body obtained by molding the epoxy resin composition according to one embodiment of the present invention into a sheet shape. Yes. For this reason, fine holes (not shown) are formed on the surfaces of the cured bodies 13 to 16. Further, the metal layer 17 reaches the inside of the fine hole. Therefore, the adhesive strength between the cured bodies 13 to 16 and the metal layer 17 can be increased. Moreover, in the multilayer laminated board 11, the width direction dimension (L) of the metal layer 17 and the width direction dimension (S) of the part in which the metal layer 17 is not formed can be made small.

  In addition, a film may be laminated | stacked on the surface of the sheet-like molded object or laminated board mentioned above for the purpose of conveyance assistance, prevention of adhesion of a refuse, or a damage | wound.

  Examples of the film include resin-coated paper, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, and polypropylene (PP) film. These films may be subjected to a release treatment in order to improve the release properties as necessary.

  As a method for the release treatment, a method for containing a silicon compound, a fluorine compound or a surfactant in the film, a method for imparting irregularities to the surface of the film, a silicon compound, a fluorine compound or Examples thereof include a method of applying a releasable substance such as a surfactant to the surface of the film. Examples of a method for providing irregularities on the surface of the film include a method of embossing the surface of the film.

  In order to protect the film, a protective film such as a resin-coated paper, a polyester film, a PET film, or a PP film may be laminated on the film.

  Hereinafter, the present invention will be specifically described by giving examples and comparative examples. The present invention is not limited to the following examples.

  In the examples and comparative examples, the following materials were used.

(Epoxy resin)
(1) Biphenyl-based epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name “NC-3000H”, weight average molecular weight 2070, epoxy equivalent 288, corresponding to the epoxy-based resin represented by the above formula (8))
(2) Bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd., trade name “RE-410S”, weight average molecular weight about 350)
(3) Anthracene skeleton-containing epoxy resin (manufactured by Japan Epoxy Resin, trade name “YX8800”, epoxy equivalent 181)
(4) Naphthalene skeleton-containing epoxy resin (manufactured by DIC, trade name “HP-4032”, epoxy equivalent 152)
(5) Adamantane skeleton-containing epoxy resin (manufactured by Idemitsu Kosan Co., Ltd., trade name “adamantate X-E-202”, epoxy equivalent 193)
(6) Triazine skeleton-containing epoxy resin (manufactured by Nissan Chemical Industries, trade name “TEPIC-PAS B22”, epoxy equivalent 180-200)

(Curing agent)
(1) Phenol-based curing agent (Maywa Kasei Co., Ltd., trade name “MEH7851-4H”, weight average molecular weight of about 10200, softening point of 120 ° C. or higher, corresponding to the phenol compound represented by the above formula (7))
(2) α-naphthol type phenol curing agent (manufactured by Tohto Kasei Co., Ltd., trade name “SN-475”, softening point 75 ° C.)
(3) Dicyclopentadiene type phenol curing agent (DCPD curing agent, manufactured by Nippon Oil Corporation, trade name “DPP-6125”, softening point 120 ° C.)
(4) Aminotriazine novolak phenol type curing agent (manufactured by DIC, trade name “LA-1356”, solid content 60 wt% MEK (methyl ketyl ketone) solution)
(5) Active ester compound type curing agent:
An active ester compound type curing agent (manufactured by DIC, trade name “EXB-9451-65T”, polystyrene equivalent weight average molecular weight 2840, solid content 65 wt% toluene solution) is dried by heating at 100 ° C. or more to obtain a solid content of 100 Weight%

(Curing accelerator)
(1) Imidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name “2PN-CN”)

(Organized layered silicate)
Synthetic hectorite chemically treated with trioctylmethylammonium salt (trade name “Lucentite STN”, manufactured by Corp Chemical)

(Maleimide)
Polyphenylmethane maleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name “BMI-2300”)

(solvent)
N, N-dimethylformamide (DMF, special grade, manufactured by Wako Pure Chemical Industries, Ltd.)

(Silica particles)
Silica particles (average particle size 0.3 μm, maximum particle size 5 μm, specific surface area 18 m ² / g)

(Silane coupling agent)
Silane coupling agent (1) Aminosilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBE-903”)
Silane coupling agent (2) Mercaptosilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-803”)
Silane coupling agent (3) Isocyanate silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBP-44”)
Silane coupling agent (4) Silane compound having an acid anhydride group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X-12-967")
Silane coupling agent (5) Silane compound having an isocyanuric acid group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “X-12-965”)
Silane Coupling Agent (6) Imidazolesilane (manufactured by Nikko Metals, trade name “IM-1000”)
Silane coupling agent (7) Vinylsilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-1003”)

(Method of treating silica particles with a silane coupling agent)
100 parts by weight of the above silica particles (average particle size 0.3 μm, maximum particle size 5 μm), 4 parts by weight of silane coupling agent (1) aminosilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBE-903”), ethanol After mixing with 100 parts by weight and stirring at 60 ° C. for 1 hour, volatile components were distilled off. Subsequently, silica component (1) treated with aminosilane was obtained by drying at 100 ° C. for 6 hours with a vacuum dryer. The obtained silica component (1) is added to DMF so that the concentration of the silica component is 50% by weight, dispersed in a bead mill, and silica slurry (1) (1) containing silica component (1) surface-treated with aminosilane ( Silica component (1) 50% by weight and DMF 50% by weight were obtained).

  Further, the surface of the silane coupling agent (1) is treated with mercaptosilane by the same treatment method as that for the silica component (1) except that the silane coupling agent (2) to (7) is changed. Surface treated with treated silica component (2), silica component (3) surface treated with isocyanate silane, silica component (4) surface treated with silane compound having acid anhydride group, silane compound having isocyanuric acid group Silica slurries (2) to (7) (silica component (2)) containing treated silica component (5), silica component (6) surface-treated with imidazole silane, and silica component (7) surface-treated with vinylsilane To (7) including 50 wt% and DMF 50 wt%).

Example 1
46.40 g of silica slurry (1) and 10.02 g of DMF were mixed and stirred at room temperature for 6 hours until a uniform solution was obtained. Thereafter, 0.21 g of imidazole “2PZ-CN” was added and stirred at room temperature for 1 hour.

  Next, 19.52 g of bisphenol A type epoxy resin “RE-410S” as an epoxy resin was added and stirred at room temperature for 1 hour. Next, 23.35 g of an α-naphthol type phenol curing agent “SN-475” as a curing agent was added to the above solution and stirred at room temperature for 2 hours to prepare an epoxy resin composition.

(Examples 2 to 21 and Comparative Examples 1 to 4)
An epoxy resin composition was prepared in the same manner as in Example 1 except that the type and blending amount of the materials used were changed as shown in Tables 1 to 5 below. In addition, when the maleimide compound was contained, the maleimide compound was added in the case of the addition of the said hardening | curing agent.

(Preparation of uncured resin sheet)
A release-treated transparent polyethylene terephthalate (PET) film (trade name “PET5011 550”, thickness 50 μm, manufactured by Lintec Corporation) was prepared. Using the applicator on this PET film, the epoxy resin compositions of the obtained Examples and Comparative Examples were applied so that the thickness after drying was 50 μm. Next, it was dried in a gear oven at 100 ° C. for 12 minutes to prepare an uncured product of a resin sheet having an area of 200 mm × 200 mm and a thickness of 50 μm. The following cured body A, semi-cured product of resin sheet, and cured body B were prepared using the uncured product of the produced resin sheet.

(Preparation of cured product A)
A circuit board was prepared on a glass epoxy substrate having a copper thickness of 25 μm, a pattern length of 3 cm, and 10 patterns of L / S = 75 μm / 75 μm. An uncured product of the obtained resin sheet was vacuum laminated on the circuit board. At the time of vacuum lamination, lamination was performed using a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.) under lamination conditions of 90 ° C., 0.6 MPa, vacuum 40 seconds, and pressure 40 seconds. It should be noted that lamination was performed under the same conditions when vacuum laminating described later. Thereafter, the uncured product of the resin sheet was precured at 150 ° C. for 1 hour to obtain a laminate A composed of a semi-cured product A1 and a circuit board obtained by semi-curing the uncured product of the resin sheet.

  Thereafter, the surface of the semi-cured body A1 of the obtained laminate A is subjected to the following (a) swelling treatment, then the following (b) permanganate treatment, that is, roughening treatment, and the following (c) ) Copper plating treatment.

(A) Swelling treatment:
Laminate A was placed in an 80 ° C. swelling liquid (Swelling Dip Securigant P, manufactured by Atotech Japan) and rocked for 10 minutes. Thereafter, it was washed with pure water.

(B) Permanganate treatment (roughening treatment):
The swelled laminate A was placed in a 80 ° C. potassium permanganate (concentrate compact CP, manufactured by Atotech Japan) roughening aqueous solution and rocked for 20 minutes. Then, it wash | cleaned for 2 minutes with the washing | cleaning liquid (Reduction securigant P, the Atotech Japan company make) of 25 degreeC, and also wash | cleaned further with the pure water. A semi-cured product A2 having a roughened surface was obtained.

(C) Copper plating treatment:
Next, the roughened semi-cured product A2 was subjected to electroless copper plating and electrolytic copper plating in the following procedure.

  The roughened semi-cured product A2 was treated with an alkali cleaner (cleaner securigant 902) at 60 ° C. for 5 minutes and degreased and washed. Next, it was treated with a predip solution (predip Neogant B) at 25 ° C. for 2 minutes. Thereafter, it was treated with an activator solution (activator Neogant 834) at 40 ° C. for 5 minutes to attach a palladium catalyst. Further, it was treated with a reducing solution (reducer Neogant WA) at 30 ° C. for 5 minutes.

  Next, the semi-cured product A2 was placed in a chemical copper solution (basic print Gantt MSK-DK, copper print Gantt MSK, stabilizer print Gantt MSK), and electroless plating was performed until the plating thickness reached about 0.5 μm. After the electroless plating, annealing was performed at a temperature of 120 ° C. for 30 minutes in order to remove the remaining hydrogen gas. All the steps up to the electroless plating step were performed while the semi-cured body A2 was swung with a processing solution of 1 L on a beaker scale.

Subsequently, electroplating was performed on the semi-cured body A2 that had been subjected to electroless plating so that the plating thickness was 25 μm. An electric current of 0.6 A / cm ² was passed using copper sulfate (reducer Cu) as the electrolytic copper plating. After the copper plating treatment, it was heated at 170 ° C. for 1 hour and cured to obtain a cured product A on which a copper plating layer was formed.

(Preparation of semi-cured resin sheet)
The obtained uncured product of the resin sheet was heated in a gear oven at 170 ° C. for 1 hour to prepare a semi-cured product of the resin sheet.

(Preparation of cured product B)
The resulting uncured resin sheet was heated in a gear oven at 170 ° C. for 1 hour to obtain a semi-cured resin sheet. The obtained semi-cured product of the resin sheet was heated at 170 ° C. for 1 hour and cured to obtain a cured product B.

(Evaluation)
(1) Dielectric constant and dielectric loss tangent Eight semi-cured products of the resin sheet obtained above were superposed and vacuum laminated, and then a laminate having a thickness of 400 μm was obtained. Then, it hardened | cured at 170 degreeC for 1 hour, and it cut | judged to the planar shape of 15 mm x 15 mm, and obtained the laminated body B which is a hardening body of a laminated body. The dielectric constant and dielectric loss tangent of laminate B at room temperature (23 ° C.) at a frequency of 1 GHz were measured using a dielectric constant measuring device (product number “HP4291B”, manufactured by HEWLETT PACKARD).

(2) Average linear expansion coefficient The obtained cured product B was cut into a 3 mm × 25 mm planar shape. Using a linear expansion meter (product number “TMA / SS120C”, manufactured by Seiko Instruments Inc.), the cured body B was cut under the conditions of a tensile load of 2.94 × 10 ⁻² N and a heating rate of 5 ° C./min. The average linear expansion coefficient (α1) at 23 to 100 ° C. and the average linear expansion coefficient (α2) at 150 to 260 ° C. were measured.

(3) Glass transition temperature (Tg)
The obtained cured body B was cut into a planar shape of 5 mm × 3 mm. Cured body cut from 30 to 250 ° C. at a temperature rising rate of 5 ° C./min using a viscoelastic spectro rheometer (Part No. “RSA-II”, manufactured by Rheometric Scientific F.E.) The loss rate tan δ of B was measured, and the temperature at which the loss rate tan δ reached the maximum value (glass transition temperature Tg) was determined.

(4) Tensile strength and elongation at break Two semi-cured products of the obtained resin sheet were laminated, heated at 170 ° C. for 1 hour, cured, cut into a 10 × 80 mm planar shape, and a test with a thickness of 100 μm. A sample was obtained. Using a tensile tester (trade name “Tensilon”, manufactured by Orientec Co., Ltd.), a tensile test was performed under the conditions of a distance between chucks of 60 mm and a crosshead speed of 5 mm / min. The breaking strength (MPa) and breaking elongation of the test sample (%) Was measured.

(5) Roughening adhesive strength A notch was cut into a 10 mm width on the surface of the copper plating layer of the cured body A on which the obtained copper plating layer was formed. Then, using a tensile tester (trade name “Autograph”, manufactured by Shimadzu Corporation), the adhesive strength between the copper plating layer and the cured body was measured under the condition of a crosshead speed of 5 mm / min, and the obtained measurement. The value was defined as roughened adhesive strength.

(6) Arithmetic average roughness Ra and ten-point average roughness Rz
Arithmetic average roughness Ra and ten-point average of the roughened surface of the semi-cured product A2 roughened using a non-contact type surface roughness meter (trade name “WYKO”, manufactured by Beiko) Roughness Rz was measured. The arithmetic average roughness Ra and the ten-point average roughness Rz were both in accordance with JIS B 0601-1994.

(7) Copper adhesive strength CZ-treated copper foil (CZ-8301, manufactured by MEC) is vacuum-laminated with a semi-cured product of a resin sheet, heated at 170 ° C. for 1 hour to be cured, and cured product C with copper foil. Got. Thereafter, a notch was cut into a 10 mm width on the surface of the copper foil. Using a tensile tester (trade name “Autograph”, manufactured by Shimadzu Corporation), the adhesive strength between the copper foil and the cured body was measured under the condition of a crosshead speed of 5 mm / min. Was defined as the copper adhesive strength.

(8) Volume resistivity The cured body B cut into a planar shape of 100 mm × 100 mm is subjected to a pressure cooker test (PCT) under conditions of 134 ° C., relative humidity 100% RH, 3 atm and 2 hours, and then 23 ° C. and It was left for 1 hour in an environment with a relative humidity of 65% RH. Thereafter, a J-box U type was connected to a high resistivity meter (trade name “High Lester UP”, manufactured by Mitsubishi Chemical Corporation), and the volume resistivity (Ω · cm) of the cured product B was measured.

(9) Melt viscosity The melt viscosity of a semi-cured resin sheet punched into a diameter of 25 mm × 1 mm is measured with a rheometer (trade name “AR-2000ex”, manufactured by T.A. Instruments Japan). Measurement was carried out from 23 ° C. to 180 ° C. under the measurement conditions of a heating rate of 5 ° C./min, 1 Hz, and a strain amount of 22%, and the melt viscosity at 90 ° C. was determined.

(10) Pattern embedding property After the laminate A was cut and polished, cross-sectional observation was performed, and it was evaluated whether or not the resin was embedded in the pattern portion without any gap. The case where the resin was embedded in the pattern part without any gap was indicated as “◯”, and the case where the pattern part had a void was indicated as “x”.

(11) Handling property The semi-cured product of the obtained resin sheet was cut into a size of 25 mm wide by 50 mm long to prepare five test pieces. Under the environment of 23 ° C. and relative humidity 65% RH, five test pieces were bent at 180 ° C., and the handling property was evaluated according to the following evaluation criteria.

[Handling property evaluation criteria]
◎: All five test pieces were not broken. ○: One or more test pieces were cracked, but none of the cracked test pieces were broken into powder. ×: One or more test pieces were Tables 1 to 5 below show the results of cracking and there were test pieces that were broken into powder in the cracked test pieces.

DESCRIPTION OF SYMBOLS 1 ... Hardened body 1a ... Upper surface 1b ... Hole 2 ... Metal layer 11 ... Multilayer laminated board 12 ... Substrate 12a ... Upper surface 13-16 ... Hardened body 17 ... Metal layer

Claims (16)

Containing an epoxy resin, a curing agent, and a silica component in which silica particles are surface-treated with a silane coupling agent,
The silica component is contained within a range of 25 to 400 parts by weight with respect to a total of 100 parts by weight of the epoxy resin and the curing agent,
The silica particles have an average particle size of 1 μm or less,
The silane coupling agent is selected from the group consisting of a silane compound having an amino group, a silane compound having a mercapto group, a silane compound having an isocyanate group, a silane compound having an acid anhydride group, and a silane compound having an isocyanuric acid group. An epoxy resin composition which is at least one kind.   2. The epoxy resin composition according to claim 1, wherein 15 wt% to 80 wt% of a total of 100 wt% of the epoxy resin, the curing agent, and the silica component is liquid at 23 ° C. 3.   100% by weight of the epoxy resin is selected from the group consisting of an epoxy resin having an anthracene skeleton, an epoxy resin having a naphthalene skeleton, an epoxy resin having an adamantane skeleton, an epoxy resin having a triazine skeleton, and an epoxy resin having a biphenyl skeleton. The epoxy resin composition according to claim 1 or 2, further comprising at least one epoxy resin in the range of 2 to 20% by weight in total.   100% by weight of the curing agent was selected from the group consisting of a phenol compound having a biphenyl structure, a phenol compound having a naphthalene structure, a phenol compound having a dicyclopentadiene structure, a phenol compound having an aminotriazine structure, and an active ester compound. The epoxy resin composition according to any one of claims 1 to 3, comprising at least one curing agent in a total range of 5 to 100% by weight. Further containing a maleimide compound,
The epoxy resin composition according to any one of claims 1 to 4, wherein the content of the maleimide compound is in the range of 2 to 45% by weight.   The epoxy resin composition according to any one of claims 1 to 5, wherein a maximum particle diameter of the silica particles is 5 µm or less.   The organically modified layered silicate is further contained within a range of 0.01 to 2 parts by weight with respect to a total of 100 parts by weight of the epoxy resin and the curing agent. Epoxy resin composition.   A prepreg in which the porous base material is impregnated with the epoxy resin composition according to any one of claims 1 to 7. A cured product obtained by heating and pre-curing the epoxy resin composition according to any one of claims 1 to 7 or a prepreg in which the porous resin substrate is impregnated with the epoxy resin composition. Is a hardened body that has been roughened,
A cured product having an arithmetic average roughness Ra of 0.3 μm or less and a ten-point average roughness Rz of 3.0 μm or less on the roughened surface.   The cured body according to claim 9, wherein the cured product is subjected to a swelling treatment after the preliminary curing and before the roughening treatment.   The epoxy resin composition according to any one of claims 1 to 7, a prepreg in which the porous resin substrate is impregnated with the epoxy resin composition, or the epoxy resin composition or the prepreg is cured. The sheet-like molded object by which the hardening body by which the hardened | cured material obtained by this was roughened is shape | molded by the sheet form.   A laminate comprising: the sheet-like molded body according to claim 11; and a metal layer laminated on at least one surface of the sheet-shaped molded body.   The laminate according to claim 12, wherein the metal layer is formed as a circuit.   A multilayer laminate comprising a plurality of laminated sheet-like molded bodies according to claim 11 and a metal layer disposed between the sheet-like molded bodies.   The multilayer laminated board of Claim 14 further provided with the metal layer laminated | stacked on the outer surface of the said sheet-like molded object of the outermost layer.   The multilayer laminate according to claim 14 or 15, wherein the metal layer is formed as a circuit.

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