JP2010100802A - Epoxy-based resin composition, sheet-like molded product, prepreg, cured product, laminated plate, and multilayer laminated plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy-based resin composition which allows surface roughness of a roughening treated surface of the cured product to be reduced, glass transition temperature of the cured product to be heightened, and coefficient of linear expansion of the cured product to be reduced even when a content of an inorganic material is low, and to provide a cured product thereof. <P>SOLUTION: The epoxy-based resin composition contains an epoxy-based resin, a curing agent, silica, and a maleimide-based compound, wherein the maleimide-based compound is contained in the range of 2-200 pts.wt. based on 100 pts.wt. of the sum total of the epoxy-based resin and the curing agent, and the silica is contained in the range of 5-50 wt.% in the solid content of 100 wt.% in the epoxy-based resin composition. The cured product 1 is formed by heating and preliminarily curing the epoxy-based resin composition, and subsequently conducting roughening treatment thereof. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition containing an epoxy resin, a curing agent, silica, and a maleimide compound, and more specifically, for example, used to obtain a cured body on which a copper plating layer or the like is formed. The present invention relates to an epoxy resin composition, and a sheet-like molded body, prepreg, cured body, laminate and 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 containing a phenolic aminomaleimide prepolymer resin, an alkylene glycol alkyl ether, and an epoxy resin. The phenolic aminomaleimide prepolymer resin is obtained from a phenol resin composition having a triazine ring and a maleimide compound.

  Patent Document 2 below discloses a thermosetting resin composition containing an insulating resin having an aromatic ring and a curing agent. This thermosetting resin composition is used for producing a laminated board. The molecular weight between crosslink points of the insulating resin determined from the shear modulus of elasticity of the insulating resin above the glass transition temperature is 300 to 1000 at the stage after the laminate is manufactured. Moreover, as the insulating resin having the aromatic ring, an epoxy resin is cited.

  Patent Document 3 below discloses a thermosetting resin composition containing an insulating polymer and a curing agent. Further, here, an electric insulating layer is formed by curing the thermosetting resin composition on a substrate, and a multilayer in which a conductor circuit layer including a metal thin film layer is formed on the electric insulating layer. The circuit structure is described.

JP 2006-022179 A JP 2007-314782 A JP 2003-332738 A

  When the cured body is formed by pre-curing the thermosetting resin composition described in Patent Documents 1 to 3 and then roughening, the surface roughness of the surface of the cured body may not be sufficiently reduced. there were. For this reason, when forming a metal layer on the surface of the cured body by plating, it may be difficult to form fine wiring. Furthermore, the adhesive strength between the cured body and the metal layer may be lowered.

  Furthermore, the linear expansion coefficient of the hardened | cured material which hardened the thermosetting resin composition of patent documents 1-3 was high, and the glass transition temperature might become low.

  Further, in Patent Document 3, when the electric insulating layer is roughened, the electric conductor circuit layer on the electric insulating layer is not flat, and thus the electric current of the electric conductor circuit in a high frequency region of 1 GHz or more is disclosed. It is described that there is a problem that the signal transmission characteristics deteriorate due to the influence of the skin effect. In the case of 1 GHz, the electrical signal transmission of the conductor circuit is concentrated in a region having a thickness of about 2 μm from the surface of the conductor circuit layer. For this reason, if the unevenness | corrugation of the surface of the said electric insulation layer is large, effective transmission line length will become long and an electric signal transmission characteristic will deteriorate.

  The object of the present invention is to reduce the surface roughness of the roughened cured body, to increase the glass transition temperature of the cured body, and to cure even if the inorganic content is small. An object of the present invention is to provide an epoxy resin composition capable of lowering the linear expansion coefficient of the body, and a sheet-like molded body, prepreg, cured body, laminate and multilayer laminate using the epoxy resin composition.

  A limited object of the present invention is to provide an epoxy resin composition capable of reducing the unevenness of the surface of the cured body and thus improving the electrical signal transmission characteristics of the circuit in a high frequency region of, for example, 1 GHz or more, and the It is providing the sheet-like molded object, prepreg, hardening body, laminated board, and multilayer laminated board which used the epoxy resin composition.

  According to the present invention, the epoxy resin, the curing agent, silica, and the maleimide compound are contained, and the maleimide compound is added to 100 parts by weight of the epoxy resin and the curing agent in total. There is provided an epoxy resin composition which is contained in the range of ˜200 parts by weight and contains the silica in a range of 5 to 50% by weight in 100% by weight of the solid content in the epoxy resin composition.

  In a specific aspect of the epoxy resin composition according to the present invention, the maleimide compound is contained in the range of 2 to 45% by weight in 100% by weight of the solid content in the epoxy resin composition. .

  In another specific aspect of the epoxy resin composition according to the present invention, the maleimide compound includes N, N′-4,4-diphenylmethane bismaleimide, N, N′-1,3-phenylene dimaleimide, N , N′-1,4-phenylene dimaleimide, 1,2-bis (maleimido) ethane, 1,6-bismaleimide hexane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, polyphenylmethane From maleimide, bisphenol A diphenyl ether bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide- (2,2,4-trimethyl) hexane and oligomers thereof, and maleimide skeleton-containing diamine condensate At least one selected from the group consisting of:

  In another specific aspect of the epoxy resin composition according to the present invention, the maleimide compound is a maleimide compound represented by the following formula (11).

  In said formula (11), R11-R13 shows a hydrogen atom, a halogen atom, or an organic group, and x represents the number within the range of 0-1.

  In still another specific aspect of the epoxy resin composition according to the present invention, the maleimide compound is a mixture of maleimide compounds represented by the formula (11), and the formula (11) of the mixture. The average value of x is in the range of 0.1 to 0.5.

  In still another specific aspect of the epoxy resin composition according to the present invention, the maleimide compound and the silica are 35 to 70% by weight in total in 100% by weight of the solid content in the epoxy resin composition. Included within range.

  In another specific aspect of the epoxy resin composition according to the present invention, the curing agent has a phenol compound having a naphthalene structure, a phenol compound having a dicyclopentadiene structure, a phenol compound having a biphenyl structure, and an aminotriazine structure. It is at least one selected from the group consisting of phenolic compounds.

  In still another specific aspect of the epoxy resin composition according to the present invention, the epoxy resin includes an epoxy resin having an anthracene skeleton, an epoxy resin having a naphthalene skeleton, an epoxy resin having a dicyclopentadiene skeleton, It is at least one selected from the group consisting of an epoxy resin having an adamantane skeleton, an epoxy resin having a triazine skeleton, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin and a bisphenol S type epoxy resin.

  In another specific aspect of the epoxy resin composition according to the present invention, the liquid epoxy resin is contained in the range of 20 to 50% by weight in 100% by weight of the solid content of the epoxy resin composition.

  In still another specific aspect of the epoxy resin composition according to the present invention, the phenoxy resin is further contained in the range of 1 to 10% by weight in 100% by weight of the solid content in the epoxy resin composition. .

  The sheet-like molded body according to the present invention is formed by molding an epoxy resin composition constituted according to the present invention into a sheet shape.

  The prepreg according to the present invention is formed by impregnating a porous base material with an epoxy resin composition constituted according to the present invention.

  The cured body according to the present invention includes an epoxy resin composition constituted according to the present invention, a sheet-shaped molded body formed by molding the epoxy resin composition into a sheet, or the epoxy resin composition. A prepreg formed by impregnating a porous substrate is heated and precured, and then a roughened cured body, and the arithmetic average roughness Ra of the roughened surface is 0.00. 3 μm or less and 10-point average roughness Rz is 3.0 μm or less.

  The laminated board which concerns on this invention is equipped with the hardening body which hardened 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 hardening body.

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

  The multilayer laminate plate according to the present invention includes a cured body laminated and a metal layer disposed between the cured bodies, and the cured body is a cured sheet-shaped body configured according to the present invention. Is the body.

  The epoxy resin composition according to the present invention contains an epoxy resin, a curing agent, silica, and a maleimide compound, and the maleimide compound with respect to 100 parts by weight of the total of the epoxy resin and the curing agent. Since the content of the spherical silica in the epoxy resin composition is in the specific range and the content of the spherical silica in the solid content of 100% by weight in the epoxy resin composition is in the specific range, a roughened cured body is obtained. The surface roughness of the surface can be reduced. Furthermore, the glass transition temperature of the cured body can be increased, and the linear expansion coefficient of the cured body can be decreased even if the inorganic content is small.

  When the maleimide compound is contained in the range of 2 to 45% by weight in the solid content of 100% by weight in the epoxy resin composition, the unevenness of the surface of the cured product can be further reduced. . Therefore, the electric signal transmission characteristics of the circuit in a high frequency region of 1 GHz or higher can be improved.

FIG. 1 is a partially cutaway front sectional view schematically showing the surface of a cured body obtained by pre-curing an epoxy resin composition according to an embodiment of the present invention and then roughening the surface. 2 is a partially cutaway front sectional view 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.

  The inventors of the present application include an epoxy resin, a curing agent, silica, and a maleimide compound, and the content of the maleimide compound with respect to 100 parts by weight in total of the epoxy resin and the curing agent is the above. By adopting a composition that is in a specific range and the content of the silica in a solid content of 100% by weight in the epoxy resin composition is in the specific range, the roughened cured product It has been found that the surface roughness of the surface can be reduced, and the present invention has been completed. Furthermore, it has also been found that by adopting this composition, the glass transition temperature of the cured product can be increased, and the linear expansion coefficient of the cured product can be decreased even if the inorganic content is small.

  Further, as described above, in Japanese Patent Laid-Open No. 2003-332738, the conductor circuit layer on the roughened insulating layer is not flat, and thus the electrical signal of the conductor circuit in a high frequency region of 1 GHz or higher is disclosed. It is described that there is a problem that transmission characteristics deteriorate due to the effect of the skin effect. In the case of 1 GHz, the electrical signal transmission of the conductor circuit is concentrated in a region having a thickness of about 2 μm from the surface of the conductor circuit layer. For this reason, if the unevenness | corrugation of the surface of the said electric insulation layer is large, effective transmission line length will become long and an electric signal transmission characteristic will deteriorate.

  From such a viewpoint, in order to improve the electric signal transmission characteristics of the circuit in a high frequency region of 1 GHz or more, it is preferable that the surface of the cured body on which the conductor circuit layer is formed has a small unevenness, for example, the surface of the cured body It was considered that the height average distance between the deep part and the top part of the unevenness was preferably 3 μm or less.

  Furthermore, in recent years, miniaturization of wiring patterns on built-up substrates and the like has been progressing. When forming a fine wiring pattern, the smoothness of the surface of the insulating layer on which the wiring pattern is formed greatly affects the yield. If the unevenness of the surface of the insulating layer is large, a wiring pattern is formed on the inclined surface of the insulating layer, so that the peel strength between the insulating layer and the wiring pattern is reduced, and the wiring may be peeled off or poorly connected. . From such a viewpoint, in order to form a fine wiring pattern with high yield on the insulating layer, it was considered that the smaller the surface roughness of the insulating layer, the better.

  Accordingly, the inventors of the present application have found that when the maleimide compound is contained in the range of 2 to 45% by weight in the solid content of 100% by weight in the epoxy resin composition, the cured product is obtained. It has also been found that the average height distance between the deep part and the top part of the unevenness of the surface can be further reduced, and the electric signal transmission characteristics of the circuit in a high frequency region of 1 GHz or more can be improved.

  The epoxy resin composition according to the present invention contains an epoxy resin, a curing agent, silica, and a maleimide compound. The maleimide compound is contained in the range of 2 to 200 parts by weight with respect to 100 parts by weight of the total of the epoxy resin and the curing agent. Silica is contained in the range of 5 to 50% by weight in 100% by weight of the solid content in the epoxy resin composition. The maleimide compound is preferably contained in the range of 2 to 45% by weight in 100% by weight of the solid content in the epoxy resin composition.

  First, each component contained in the epoxy resin composition according to the present invention 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 resins, alicyclic epoxy resins, aliphatic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, glycidyl acrylic type epoxy resins, and polyesters. Type epoxy resin and the like.

  Examples of the aromatic epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin or bisphenol S type epoxy resin, or phenol novolac type epoxy resin or cresol. Examples include novolac type epoxy resins such as novolac type epoxy resins.

  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 epoxy resin includes an epoxy resin having an anthracene skeleton, an epoxy resin having a naphthalene skeleton, an epoxy resin having a dicyclopentadiene skeleton, an epoxy resin having an adamantane skeleton, an epoxy resin having a triazine skeleton, and bisphenol A. It is preferably at least one selected from the group consisting of a type epoxy resin, a bisphenol F type epoxy resin and a bisphenol S type epoxy resin. In this case, the surface roughness of the roughened cured body can be further reduced.

  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.

  The epoxy resin is preferably an epoxy resin having an anthracene skeleton. By using an epoxy resin having an anthracene skeleton, the linear expansion coefficient of the cured product can be further reduced. In addition, the glass transition temperature of the cured product can be further increased. Furthermore, when making an epoxy resin composition into a B-stage sheet, it is more preferable to use an epoxy resin having an anthracene skeleton and a bisphenol A type epoxy resin in combination. In this case, it is possible to improve the handling of the sheet in the B stage state, and it is possible to reduce the unevenness of the surface when the sheet is cured on the substrate.

  The epoxy resin is preferably at least one of an epoxy resin having a triazine skeleton and an epoxy resin having an adamantane skeleton. By using an epoxy resin having a triazine skeleton or an epoxy resin having an adamantane skeleton, the linear expansion coefficient of the cured product can be further reduced. Moreover, the surface roughness of the surface of the hardening body after a roughening process can be made small. When the epoxy resin composition is made into a B-stage sheet, it is more preferable to use an epoxy resin having a triazine skeleton or an epoxy resin having an adamantane skeleton and a bisphenol A type epoxy resin in combination. In this case, it is possible to improve the handling of the sheet in the B stage state, and it is possible to reduce the unevenness of the surface when the sheet is cured on the substrate.

  The liquid epoxy resin is preferably contained in the range of 20 to 50% by weight in 100% by weight of the solid content in the epoxy resin composition. When the content of the liquid epoxy resin is within the above range, the handling property of the epoxy resin composition and the sheet-like molded body using the epoxy resin composition can be further enhanced. Furthermore, the unevenness of the surface of the cured body can be further reduced.

(Curing agent)
A conventionally well-known hardening | curing agent can be used as a hardening | curing agent contained in the epoxy resin composition which concerns on this invention.

  Examples of the curing agent include dicyandiamide, amine compounds, compounds synthesized from amine compounds, hydrazide compounds, melamine compounds, acid anhydrides, phenolic compounds, active ester compounds, thermal latent cationic polymerization catalysts, and photolatent cationic polymerization. Examples thereof include an initiator or a cyanate ester resin. 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. In addition to a curing agent, a curing catalyst such as acetylacetone iron may be used.

  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 body can be increased, and the water absorption of the cured body 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 on the surface of the 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. By using this preferable curing agent, the surface roughness of the surface of the roughened 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 body 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 characteristics and heat resistance of the cured body can be further enhanced. Furthermore, the dimensional stability of the cured body when a thermal history is given can be further enhanced. The curing agent is preferably a phenol compound represented by the above formula (3) and a phenol compound having an aminotriazine structure. By using this preferable curing agent, the linear expansion coefficient of the cured product can be further reduced.

  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. By using the active ester compound, a cured product excellent in 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 EXB-9460S" by Dainippon Ink & Chemicals, Inc. etc. are mentioned, for example.

  As the cyanate ester resin, for example, a novolak-type cyanate ester resin, a bisphenol-type cyanate ester resin, and a prepolymer partially triazine-modified can be used. By using the cyanate ester resin, the linear expansion coefficient of the cured product can be further reduced.

  The curing agent is preferably a phenol compound or an active ester compound. By using the active ester compound, it is possible to obtain a cured product that is more excellent in 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.

  In particular, the curing agent is at least one selected from the group consisting of a phenol compound having a naphthalene structure, a phenol compound having a dicyclopentadiene structure, a phenol compound having a biphenyl structure, and a phenol compound having an aminotriazine structure. preferable. When these preferable curing agents are used, when the roughening treatment is carried out after reacting the epoxy resin composition, the resin component is more unlikely to be adversely affected by the roughening treatment. Specifically, fine pores can be formed by selectively detaching the spherical silica without excessively roughening the surface of the resulting cured body during the roughening treatment. For this reason, the fine unevenness | corrugation whose surface roughness is very small can be formed in the surface of a hardening body. Of these, a phenol compound having a biphenyl structure is preferable.

  A cured product using a phenolic compound having a biphenyl structure or a phenolic compound having a naphthalene structure is excellent in electrical characteristics, particularly dielectric loss tangent. Moreover, it is excellent also in the intensity | strength and linear expansion coefficient of a hardening body.

  When the molecular weight of the epoxy resin and the curing agent is large, it is easy to form a fine rough surface on the surface of the cured body. The weight average molecular weight of the epoxy resin may affect the formation of a fine rough surface. However, the weight average molecular weight of the curing agent may have 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.

  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 a hardening body. Furthermore, when the curing agent is solid and the softening temperature of the curing agent is 60 ° C. or higher, a fine rough surface is easily formed on the surface of the cured body.

  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. If the amount of the curing agent is too small, the epoxy resin composition may not be sufficiently cured. If the amount of the curing agent is too large, the effect of curing the epoxy resin may be saturated. The minimum with preferable content of the said hardening | curing agent is 30 weight part, and a preferable upper limit is 140 weight part.

(Curing accelerator)
The epoxy resin composition according to the present invention preferably contains a curing accelerator. In the present invention, the curing accelerator is an optional component. The curing accelerator is not particularly limited.

  The curing accelerator is preferably an imidazole curing accelerator. The imidazole curing accelerator is 2-undecylimidazole, 2-heptadecylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl. Imidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2′- Methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6 -[2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-tria 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct It is preferably at least one selected from the group consisting of 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole.

  Moreover, as said hardening accelerator, phosphine compounds, such as a triphenyl phosphine, DBU, DBN, the phenol salt of DBU, the phenol salt of DBN, octylate, p-toluenesulfonate, formate, orthophthalate, or phenol A novolak resin salt is exemplified.

  It is preferable that the said hardening accelerator is a peroxide type hardening accelerator. The peroxide-based curing accelerator is dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and 1, It is preferably at least one selected from the group consisting of 3-bis (t-butylperoxyisopropyl) benzene.

  The curing accelerator is preferably contained within a range of 0.01 to 3 parts by weight with respect to 100 parts by weight of the epoxy resin. If the amount of the curing accelerator is too small, the epoxy resin composition may not be cured sufficiently.

  In the present invention, the surface roughness of the surface of the roughened cured body can be reduced without adding a curing accelerator. However, when the curing accelerator is not added, the curing of the epoxy resin composition does not proceed sufficiently, and the Tg of the cured body may be lowered, or the strength of the cured body may not be sufficiently increased. . Therefore, it is more preferable that the epoxy resin composition contains a curing accelerator. The minimum with preferable content of the said hardening accelerator is 0.3 weight part, and a preferable upper limit is 2.0 weight part.

(silica)
As for the silica contained in the epoxy resin composition concerning this invention, only 1 type may be used and 2 or more types may be used together.

  The silica is preferably spherical silica. In the case of spherical silica, since the spherical silica is easily detached by the roughening treatment, a finer rough surface can be formed on the surface of the roughened cured body.

  The average particle diameter of the spherical silica is preferably 1 μm or less. When the average particle diameter is 1 μm or less, an even finer rough surface can be formed on the surface of the roughened cured body. In addition, fine holes having an average diameter of about 1 μm or less can be formed on the surface of the roughened cured body. The average particle diameter of the spherical silica is more preferably 0.6 μm or less. The average particle diameter of the spherical silica is preferably 100 nm or more.

  When the average particle diameter of the spherical silica is larger than 1 μm, the spherical silica is difficult to be detached during the roughening treatment after pre-curing the epoxy resin composition. In addition, when a plating process is performed to form a metal layer on the surface of the cured body, the plating may sink into the gap between the spherical silica that has not been detached and the resin component. For this reason, when the metal layer is formed in the surface of the hardening body as a circuit, there exists a possibility that a malfunction may arise in a circuit.

  When a phenol compound having one of the naphthalene structure, dicyclopentadiene structure, biphenyl structure and aminotriazine structure, or an aromatic polyvalent ester compound is used as a curing agent, a roughening treatment can be performed around the spherical silica. Resin component is difficult to scrape. In this case, when the average particle diameter of the spherical silica is larger than 1 μm, the spherical silica is more difficult to be detached, and the adhesive strength between the cured body and the metal layer is likely to be lowered.

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

  A plurality of types of spherical silica having different average particle diameters may be used. In consideration of fine packing, it is preferable to use a plurality of types of spherical silica 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. Further, by using spherical silica having an average particle diameter of several tens of nm, the viscosity of the epoxy resin composition can be increased, and thixotropy can be controlled.

  The maximum particle diameter of the spherical silica is preferably 5 μm or less. When the maximum particle size is 5 μm or less, the spherical silica is more easily detached during the roughening treatment after pre-curing the epoxy resin composition. Furthermore, relatively large holes are hardly formed on the surface of the cured body, and uniform and fine irregularities can be formed.

  When a phenolic compound having any one of naphthalene structure, dicyclopentadiene structure, biphenyl structure and aminotriazine structure, or an aromatic polyvalent ester compound is used as a curing agent, the epoxy resin composition described above is used. The roughening liquid hardly penetrates into the precured product from the surface of the precured precured product, and the spherical silica is relatively difficult to desorb. However, the use of spherical silica having a maximum particle diameter of 5 μm or less makes it possible to remove spherical silica without difficulty. When forming fine wiring with L / S of 15 μm / 15 μm or less on the surface of the cured body, it is possible to improve the insulation reliability. Therefore, the maximum particle diameter of the spherical 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.

  When the roughening treatment is performed after pre-curing the epoxy resin composition, the spherical silica is more preferably spherical because the spherical silica is more easily detached. “Spherical” means, for example, that the aspect ratio is in the range of 1 to 2.

The specific surface area of the silica is preferably 3 m ² / g or more. There exists a possibility that the mechanical characteristic of a hardening body 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 cured body, the adhesion between the cured body and the metal layer may be reduced. The specific surface area can be determined by the BET method.

  As the silica, 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 Examples include spherical fused silica, fumed silica (Aerosil), and synthetic silica such as sol-gel silica.

  Because of its high purity, fused silica is preferably used as the silica. Silica 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 silica may be used as a silica slurry in a state dispersed in a solvent. Silica may be surface-treated with a silane coupling agent.

  As the silane coupling agent, a general silane compound can be used. The silane coupling agent may be at least one selected from the group consisting of epoxy silane, amino silane, isocyanate silane, acryloxy silane, methacryloxy silane, vinyl silane, styryl silane, ureido silane, sulfide silane and imidazole silane. preferable. Further, the silica may be surface-treated with an alkoxysilane such as silazane. As for a silane coupling agent, only 1 type may be used and 2 or more types may be used together.

  Examples of the method for surface-treating the silica 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. In the dry method, silica is charged into a mixer, and an alcohol solution or an aqueous solution of a silane coupling agent is added dropwise or sprayed with stirring, followed by further stirring and classification with a sieve. Thereafter, the silane coupling agent and silica are dehydrated and condensed by heating.

  The second method includes a wet method. In the wet method, a silane coupling agent is added while stirring a silica slurry containing silica, and after stirring, classification is performed by filtration, drying, and sieving. Next, the silane coupling agent and silica are dehydrated and condensed by heating.

  As a third method, there is a method in which dehydration condensation is performed by heating and refluxing after adding a silane coupling agent while stirring a silica slurry containing silica.

  By using silica that has been surface-treated with a silane coupling agent, the reflow resistance of the cured product can be increased. Further, the water absorption of the cured body can be lowered and the insulation reliability can be increased.

  The silica is contained in the range of 5 to 50% by weight in 100% by weight of the solid content in the epoxy resin composition. The minimum with preferable content of the said silica in 100 weight% of solid content in the said epoxy resin composition is 10 weight%, and a more preferable minimum is 25 weight%. The upper limit with preferable content of the said silica in 100 weight% of solid content in the said epoxy resin composition is 45 weight%, and a more preferable upper limit is 40 weight%. If the amount of silica is too small, the total surface area of the pores formed by the desorption of silica is reduced when the epoxy resin composition is precured and then roughened. For this reason, when a metal layer is formed on the surface of the cured body, the adhesive strength between the cured body and the metal layer may not be sufficiently increased. The greater the amount of silica, the lower the linear expansion coefficient of the cured body. However, if the amount of silica is too large, the cured product tends to become brittle and the surface roughness of the roughened cured product tends to increase. Moreover, when a laminated board and a multilayer laminated board are produced using the said epoxy resin composition, the workability at the time of performing a via opening process using a drill or a laser deteriorates.

  The “100 wt% solid content in the epoxy resin composition” refers to the total of the epoxy resin, the curing agent, the silica, and the maleimide compound, and other solid contents blended as necessary.

(Maleimide compound)
Since the epoxy resin composition according to the present invention contains a maleimide compound, the linear expansion coefficient of the cured product can be remarkably lowered. Furthermore, the glass transition temperature of the cured product can be increased. This is presumably because the rigid skeleton derived from the maleimide compound is introduced into the cured body, and thus the micro-Brownian motion of the molecular chain in the cured body is suppressed. By forming a cured body or a laminate using the epoxy resin composition according to the present invention, an effect that the thermal shock resistance of the cured body or the laminate is significantly increased can be expected.

  The maleimide compound is not particularly limited. Only one type of maleimide compound may be used, or two or more types may be used in combination.

  The maleimide compounds include N, N′-4,4-diphenylmethane bismaleimide, N, N′-1,3-phenylene dimaleimide, N, N′-1,4-phenylene dimaleimide, and 1,2-bis. (Maleimide) ethane, 1,6-bismaleimide hexane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, polyphenylmethanemaleimide, bisphenol A diphenyl ether bismaleimide, 4-methyl-1,3-phenylene It is preferably at least one selected from the group consisting of bismaleimide, 1,6-bismaleimide- (2,2,4-trimethyl) hexane and oligomers thereof, and maleimide skeleton-containing diamine condensate. By using these preferable maleimide compounds, the linear expansion coefficient of the cured product can be further lowered, and the glass transition temperature of the cured product can be further increased. The said oligomer is an oligomer obtained by condensing the maleimide type compound which is a monomer of the maleimide type compounds mentioned above.

  Among these, the maleimide compound is more preferably at least one of polyphenylmethane maleimide and bismaleimide oligomer. The bismaleimide oligomer is preferably an oligomer obtained by condensation of phenylmethane bismaleimide and 4,4-diaminodiphenylmethane. By using these preferable maleimide compounds, the linear expansion coefficient of the cured product can be further lowered, and the glass transition temperature of the cured product can be further increased.

  Examples of commercially available maleimide compounds include polyphenylmethane maleimide (manufactured by Daiwa Kasei Co., Ltd., trade name “BMI-2300”) and bismaleimide oligomer (manufactured by Daiwa Kasei Co., Ltd., trade name “DAIMAID-100H”). .

  BMI-2300 manufactured by Daiwa Kasei Co., Ltd. is a low molecular weight oligomer. DAIMAID-100H manufactured by Daiwa Kasei Co., Ltd. is a condensate using diaminodiphenylmethane as an amine curing agent, and has a high molecular weight. In the case of using the DAIMAID-100H instead of the BMI-2300, the breaking strength and elongation at break of the cured product can be improved. However, when the BMI-2300 is used, the linear expansion coefficient of the cured body tends to be lower than when the DAIMAID-100H is used.

  The maleimide compound is preferably a maleimide compound represented by the following formula (11). By using the maleimide compound represented by the following formula (11), the linear expansion coefficient of the cured product can be further reduced.

  In said formula (11), R11-R13 shows a hydrogen atom, a halogen atom, or an organic group, and x represents the number within the range of 0-1.

  Since the linear expansion coefficient of the cured product can be further reduced, R11 to R13 in the above formula (11) are preferably hydrogen atoms. That is, the maleimide compound represented by the above formula (11) is preferably a maleimide compound represented by the following formula (12).

  In said Formula (12), y represents the integer within the range of 0-1.

  The maleimide compound is a mixture of maleimide compounds represented by the above formulas (11) and (12), and the average value of x or y in the above formulas (11) and (12) of the mixture Is preferably in the range of 0.1 to 0.5. The higher the average value of x or y, the higher the solubility of the mixture. By using a mixture in which the average value of x or y in the above formulas (11) and (12) is in the range of 0.1 to 0.5, the linear expansion can be further reduced and the solubility is increased. Can be increased. By using a mixture in which the average value of x or y in the above formulas (11) and (12) is in the range of 0.2 to 0.3, the dimensional change due to temperature such as linear expansion is further reduced. Can do.

  The maleimide compound is contained in the range of 2 to 200 parts by weight with respect to 100 parts by weight of the total of the epoxy resin and the curing agent. If the amount of the maleimide compound is too small, the linear expansion coefficient of the cured product cannot be sufficiently lowered, or the glass transition temperature of the cured product cannot be sufficiently increased. The minimum with preferable content of the said maleimide type compound with respect to a total of 100 weight part of the said epoxy resin and the said hardening | curing agent is 5 weight part, and a more preferable minimum is 10 weight part. The upper limit with preferable content of the said maleimide type compound with respect to a total of 100 weight part of the said epoxy resin and the said hardening | curing agent is 150 weight part, and a more preferable upper limit is 100 weight part.

  As the amount of the maleimide compound increases, a larger amount of rigid skeleton is introduced into the cured body, so that the linear expansion coefficient of the cured body decreases and the glass transition temperature of the cured body tends to increase. However, if the amount of the maleimide compound is too large, the effect of reducing the linear expansion coefficient of the cured product and the effect of improving the glass transition temperature of the cured product may be saturated. Furthermore, the surface roughness of the roughened cured body may increase, or the breaking strength may decrease significantly.

  The maleimide compound is preferably contained in the range of 2 to 45% by weight in 100% by weight of the solid content in the epoxy resin composition. The minimum with preferable content of the said maleimide-type compound in 100 weight% of solid content in the said epoxy-type resin composition is 5 weight%, and a more preferable minimum is 10 weight%. The upper limit with preferable content of the said maleimide type compound in 100 weight% of solid content in the said epoxy resin composition is 40 weight%, and a more preferable upper limit is 30 weight%. When the content of the maleimide compound in the solid content of 100% by weight in the epoxy resin composition is within the preferable range, the unevenness of the surface of the cured product can be reduced. Therefore, the electric signal transmission characteristics of the circuit in a high frequency region of 1 GHz or higher can be improved.

  Moreover, it is preferable that the said maleimide type compound and the said silica are contained in 35 to 70 weight% in total in 100 weight% of solid content in an epoxy resin composition. When the total content of the maleimide compound and the silica is within the preferable range, the handling property of the epoxy resin composition and the sheet-like molded body using the epoxy resin composition should be increased. Can do. Furthermore, the unevenness of the surface of the cured body can be further reduced.

(Phenoxy resin)
The epoxy resin composition according to the present invention preferably further contains a phenoxy resin. By using phenoxy resin, the tensile strength of the cured product can be increased, for example, the elongation at break and the strength at break can be increased. This is considered to be because the phenoxy resin plays a role of connecting the inorganic component and the organic component.

  Specifically, the phenoxy resin is, for example, a resin obtained by reacting an epihalohydrin with a divalent phenol compound, or a resin obtained by reacting a divalent epoxy compound with a divalent phenol compound.

  The phenoxy resin is preferably contained in the range of 1 to 50 parts by weight, and in the range of 10 to 30 parts by weight, based on 100 parts by weight of the total of the epoxy resin and the curing agent. More preferably. If the amount of phenoxy resin is too small, the breaking strength of the cured product may not be sufficiently increased. When there is too much quantity of a phenoxy resin, the linear expansion coefficient of a hardening body may become high and a glass transition temperature may fall.

  Moreover, it is preferable that the phenoxy resin is contained within the range of 1 to 10% by weight in the solid content of 100% by weight of the epoxy resin composition. When the content of the phenoxy resin is within this range, the tensile strength of the cured product can be increased, for example, the elongation at break and the strength at break can be increased.

(Other ingredients that can be added)
The epoxy resin composition according to the present invention may contain an organic layered silicate.

  In the epoxy resin composition containing the organic layered silicate, the organic layered silicate exists around the silica. For this reason, when the precured material obtained by precuring the epoxy resin composition is subjected to swelling treatment and roughening treatment, silica existing on the surface of the precured material is more easily detached.

  Examples of the organic layered silicate include organic layered silicates obtained by organically treating layered silicates such as smectite clay minerals, swellable mica, vermiculite, and 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 average particle diameter of the organically modified layered silicate is preferably 500 nm or less. When the average particle diameter of the organic layered silicate exceeds 500 nm, the dispersibility of the organic layered silicate in the epoxy resin composition may be lowered. The average particle diameter of the organically modified layered silicate is preferably 100 nm or more.

  The median diameter (d50) value of 50% can be adopted as the average particle diameter of the organically modified layered silicate. The average particle size can be measured using a laser diffraction / scattering particle size distribution measuring apparatus.

  The organically modified layered silicate is preferably contained within a range of 0.01 to 3 parts by weight with respect to a total of 100 parts by weight of the epoxy resin and the curing agent. If the amount of the organically modified layered silicate is too small, the effect of facilitating detachment of silica may be insufficient. If the amount of the organically modified layered silicate is too large, the surface roughness of the surface of the cured body tends to be relatively large. In particular, when the epoxy resin composition is used for sealant applications, if the amount of the organically modified layered silicate is too large, the rate at which the surface roughness of the surface of the cured body changes due to the roughening treatment is too fast. Therefore, the uniformity of the swelling treatment or the roughening treatment may not be sufficiently ensured.

  In addition, when the content of the organic layered silicate with respect to 100 parts by weight of the total of the epoxy resin and the curing agent exceeds 3 parts by weight, the surface roughness of the surface of the roughened cured body becomes relatively large. Cheap.

  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 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, other thermosetting resins other than epoxy resins, thermoplastic elastomers, crosslinked rubber, oligomers, inorganic compounds, Nucleating agent, antioxidant, anti-aging agent, heat stabilizer, light stabilizer, UV absorber, lubricant, flame retardant aid, antistatic agent, anti-fogging agent, filler, softener, plasticizer or colorant, etc. Additives 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, and polyetherimide resins. Moreover, only 1 type may be used for the said thermoplastic resins and said other thermosetting resin, respectively, and 2 or more types may be used together.

(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, an epoxy resin, a curing agent, silica, a maleimide compound, and components blended as necessary are added to a solvent, and then dried. Examples include a method for removing the solvent. The epoxy resin composition according to the present invention may contain a solvent.

  The epoxy resin composition according to the present invention can be used in a form dissolved in a solvent. For example, the epoxy resin composition according to the present invention can be used as a thermosetting solder resist by being used on the outermost surface of a multilayer laminate.

  The use of the epoxy resin composition according to the present invention is not particularly limited. The epoxy resin composition includes, for example, a substrate material for forming a core layer or a buildup layer of a multilayer substrate, an adhesive sheet, a laminate, a copper foil with resin, a copper clad laminate, a TAB tape, a printed board, It is suitably used for prepreg or varnish.

  Moreover, a fine hole can be formed in the surface of a hardening body by use of the epoxy-type 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 said epoxy resin composition is used suitably for the use as which insulation is requested | required, such as copper foil with resin, a copper clad laminated board, a printed circuit board, a prepreg, an adhesive sheet, or a TAB tape.

  The above epoxy resin composition is applied to a build-up substrate or the like in which a plurality of cured bodies and conductive plating layers are laminated by an additive method or a semi-additive method for forming a circuit after forming a conductive plating layer on the surface of the cured body. Is more preferably used. In this case, the bonding strength between the cured body and the conductive plating layer can be increased. Moreover, since the hole which the silica formed in the surface of the hardening body is small is small, the insulation between patterns can be improved. Furthermore, since the depth of the hole through which the silica is removed is shallow, the insulation between the layers can be improved.

  The epoxy resin composition can also be used for a sealing material or a solder resist. In addition, since the high-speed signal transmission performance of the wiring formed on the surface of the cured body can be improved, the epoxy-based substrate is also used for a component-embedded substrate or the like in which a passive component or an active component is required, which requires high-frequency characteristics. A resin composition can be used.

(Sheet-like molded product)
The sheet-like molded body according to the present invention is formed by molding the epoxy resin composition into a sheet shape.

  The “sheet” is not limited to a thickness or a width, and has a plate shape, and the sheet includes a film. The sheet-like molded body 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.

(Prepreg)
The prepreg according to the present invention is formed by impregnating a porous base material 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)
Formed by impregnating a porous substrate with an epoxy resin composition according to the present invention, a sheet-like molded body formed by molding the epoxy resin composition into a sheet shape, or the epoxy resin composition The cured product can be obtained by heating and pre-curing the prepared prepreg, followed by roughening treatment.

  The obtained cured body is generally in a semi-cured state called a B stage. The “cured body” includes not only a completely cured body but also a semi-cured body in a semi-cured state. A semi-cured product is one that is not completely cured. The semi-cured body is one that can be further cured.

  Specifically, the cured body according to the present invention is obtained as follows.

  The epoxy resin composition is pre-cured (semi-cured) to obtain a pre-cured product. The heating temperature at the time of making the said epoxy resin composition react is not specifically limited. The minimum with a preferable heating temperature is 130 degreeC, a more preferable minimum is 150 degreeC, and a preferable upper limit is 190 degreeC. If the heating temperature is too low, the epoxy resin composition is not sufficiently cured, so that the surface roughness of the cured body after the roughening treatment tends to increase. If the heating temperature is too high, 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 surface roughness of the cured body increases.

  The heating time for reacting the epoxy resin composition is not particularly limited. The heating time is preferably 30 minutes or more. When the heating time is shorter than 30 minutes, the epoxy resin composition is not sufficiently cured, so that the surface roughness of the cured body after the roughening treatment increases. Since heating time can improve productivity, it is preferable that it is 1 hour or less.

  In order to form fine irregularities on the surface of the cured body, the epoxy resin composition is pre-cured and then roughened. The epoxy resin composition is preferably swelled after being precured and before being roughened. However, the swelling treatment is not necessarily performed.

  As the swelling treatment method, for example, a method of treating the preliminary-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. For the swelling treatment, a 40% by weight ethylene glycol aqueous solution is suitably used.

  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. For the roughening treatment, for example, 30 to 90 g / L permanganic acid or permanganate solution or 30 to 90 g / L sodium hydroxide solution is preferably used.

  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 silica is detached from the surface of the cured body. It becomes difficult to form holes having a shape. For this reason, it is preferable that a roughening process is performed once or twice.

  The preliminary-cured product is preferably roughened at 50 to 80 ° C. for 5 to 30 minutes. When the pre-cured product is subjected to the swelling treatment, the pre-cured product is preferably subjected to a swelling treatment at 50 to 80 ° C. for 5 to 30 minutes. When the roughening treatment or the swelling treatment is performed a plurality of times, the time for the roughening treatment or the swelling treatment indicates the total time. By roughening or swelling the precured product obtained by precuring the epoxy resin composition under the above conditions, the surface roughness of the surface of the cured product can be further reduced. Specifically, a hardened body 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 can be obtained more easily. .

  In FIG. 1, the hardening body which concerns on one Embodiment of this invention is typically shown with a partial notch front sectional drawing.

  As shown in FIG. 1, holes 1 b formed by detachment of spherical silica are formed on the surface 1 a of the cured body 1. The hole 1b may be a hole in which about several spherical silicas, for example, about 2 to 10 are separated and removed.

  The arithmetic average roughness Ra of the roughened surface of the cured body 1 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 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 ANSI Standard B46.1-1985 and JIS B0601-1994.

  The average diameter of the plurality of holes formed on the surface of the cured body 1 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.

  If necessary, the cured body 1 can be subjected to electroplating after being applied with a known plating catalyst or electroless plating. 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 upper surface 1a of the cured body 1 by plating. As shown in FIG. 2, the metal layer 2 reaches the fine holes 1 b formed in the upper 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 detachment of the spherical silica, the resin component is not removed 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 spherical silica is smaller, fine irregularities can be formed on the surface of the cured body 1. By using spherical silica having an average particle diameter of 1 μm or less, the pores 1b can be further reduced, and therefore finer irregularities can be formed on the surface of the cured body 1. For this reason, L / S which shows the fineness of the wiring of a circuit can be made small.

  When wiring of copper or the like having a small L / S is formed on the surface 1a of the cured body 1, the signal processing speed of the wiring can be increased. For example, when a high-frequency signal is transmitted, since the surface roughness of the cured body 1 is small, the loss of an electrical signal at the interface between the cured body 1 and the metal layer 2 can be reduced.

  As a material for forming the metal layer 2, 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. The metal layer 2 is preferably a copper plating layer formed by a copper plating process.

  The adhesive strength between the cured body 1 and the metal layer 2 is preferably 0.5 kgf / cm or more. The adhesive strength between the cured body 1 and the metal layer 2 is more preferably 0.7 kgf / cm or more.

  Moreover, it is preferable that average linear expansion coefficient (alpha) 1 (23-150 degreeC) of the hardening body 1 is 50 ppm / degrees C or less. The average linear expansion coefficient α1 is more preferably 40 ppm / ° C. or less. If the average linear expansion coefficient α1 is too large, the thermal shock resistance is lowered, and when an epoxy resin composition is used as a printed circuit board material, there is a possibility that the substrate will crack due to expansion and contraction during thermal cycling. There is.

  Moreover, it is preferable that the glass transition temperature Tg of the hardening body 1 is 190 degreeC or more, and it is more preferable that it is 220 degreeC or more. When the glass transition temperature is increased, heat resistance is improved, and when an epoxy resin composition is used as a printed circuit board material, it can be expected to improve dimensional stability during solder reflow and to suppress plating layer swelling. . In addition, the tensile strength of the cured body at high temperatures is improved.

(Laminated board and multilayer laminated board)
The laminated board which concerns on this invention is equipped with the hardening body which hardened the said sheet-like molded object, and the metal layer laminated | stacked on the at least single side | surface of this hardening body.

  The multilayer laminated board which concerns on this invention is equipped with the laminated | stacked hardening body and the at least 1 metal layer arrange | positioned between this hardening body. The cured body is a cured body obtained by curing the sheet-like molded body. The multilayer laminate may further include a metal layer laminated on the outer surface of the outermost cured body.

  An adhesive layer may be disposed in at least a part of the cured body of the laminate. Moreover, the adhesive body may be arrange | positioned at least in one part area | region in the hardening body laminated | stacked on the said multilayer laminated board.

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

  For example, when a wiring pattern having an L / S of 15 μm / 15 μm is formed as a metal layer on the surface of the cured body, the average height between adjacent deep portions and top portions of the surface of the cured body derived from the lower layer pattern The distance is preferably 3 μm or less, preferably 2.5 μm or less, and preferably 2.0 μm or less. By forming the cured body using the epoxy resin composition in which the content of the maleimide compound in the solid content of 100% by weight in the epoxy resin composition is in the range of 2 to 45% by weight, a cured body is obtained. The surface unevenness can be reduced, and for example, the height average distance between the deep part and the top part of the surface unevenness can be 3 μm or less.

  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)
Bisphenol A type epoxy resin 1 (manufactured by DIC, trade name “850S”, liquid epoxy resin)
Bisphenol A type epoxy resin 2 (trade name “828US”, liquid epoxy resin, manufactured by JER)
Anthracene type epoxy resin (made by Japan Epoxy Resin Co., Ltd., trade name “YX8800”, solid type epoxy resin)
Bisphenol F type epoxy resin (manufactured by DIC, trade name “830-S”, liquid epoxy resin)

(Curing agent)
A phenolic curing agent having a biphenyl structure (Madewa Kasei Co., Ltd., trade name “MEH7851-4H”, corresponding to the phenol compound represented by the above formula (7))
Phenolic curing agent having aminotriazine structure (manufactured by DIC, trade name “LA-1356”, solid content 60 wt% MEK (methyl ethyl ketone) solution)

(Curing accelerator)
Imidazole-based curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name “2PZ-CN”, 1-cyanoethyl-2-phenylimidazole)
Peroxide curing accelerator (trade name “PERKADOX BC-FF”, dicumyl peroxide, manufactured by Kayaku Akzo)

(Maleimide compound)
Polyphenylmethane maleimide (trade name “BMI-2300”, manufactured by Daiwa Kasei Co., Ltd.), which corresponds to a mixture of maleimide compounds represented by the above formula (11), and an average value of x in the above formula (11) of the mixture 0.2-0.3)

Bismaleimide oligomer (manufactured by Daiwa Kasei Co., Ltd., trade name “DAIMAID-100H”, condensate of N, N′-4,4-diphenylmethane bismaleimide and 4,4-diaminodiphenylmethane)
Bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (manufactured by Daiwa Kasei Co., Ltd., trade name “BMI-5100”)

(Silica slurry)
Slurry containing 50% by weight of spherical silica 1:
A slurry containing 50% by weight of spherical silica (average particle size 0.3 μm, specific surface area 18 m ² / g by BET method) and 50% by weight of DMF (N, N-dimethylformamide)

Slurry 2 containing 50% by weight of spherical silica:
50% by weight of spherical silica (average particle size 0.3 μm, specific surface area 18 m ² / g by BET method) surface-treated with epoxysilane (KBM-403, manufactured by Shin-Etsu Silicone) and DMF (N, N-dimethyl) 50% by weight of spherical silica containing 50% by weight of formamide)

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

(Phenoxy resin)
Modified biphenol skeleton-containing phenoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name “YX6954BH30”, solid content 30% by weight, solvent is a mixed solvent of MEK (methyl ethyl ketone) and cyclohexanone)

Example 1
248 parts by weight of the slurry 1 containing 50% by weight of spherical silica and 151 parts by weight of DMF were mixed and stirred at room temperature until a uniform solution was obtained. Thereafter, 1 part by weight of the above imidazole-based curing accelerator (trade name “2PZ-CN”, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was further added and stirred at room temperature until a uniform solution was obtained.

  Next, 100 parts by weight of bisphenol A type epoxy resin 1 (trade name “850S”, manufactured by DIC Corporation) as an epoxy resin was added and stirred at room temperature until a uniform solution was obtained. In the obtained solution, 106 parts by weight of a phenolic curing agent having a biphenyl structure as a curing agent (trade name “MEH7851-4H” manufactured by Meiwa Kasei Co., Ltd.) and polyphenylmethanemaleimide (Daiwa Kasei Co., Ltd.) as a maleimide compound (Trade name “BMI-2300”) was added in an amount of 83 parts by weight, and the mixture was stirred at room temperature until a uniform solution was obtained, to prepare an epoxy resin composition.

(Examples 2-7 and Comparative Examples 1-4)
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 Table 1 below.

(Evaluation of Examples 1-7 and Comparative Examples 1-4)
(Preparation of sheet-like molded product)
A release-treated transparent polyethylene terephthalate (PET) film (trade name “PET5011 550”, thickness 50 μm, manufactured by Lintec Corporation) was prepared. The obtained epoxy resin composition was applied onto the prepared PET film using an applicator so that the thickness after drying was 40 μm. Next, by drying in a gear oven at 100 ° C. for 2 minutes, a sheet-like molded body having an uncured size of 200 mm in length, 200 mm in width, and 40 μm in thickness was produced.

(Preparation of cured product A)
The obtained sheet-like molded body was vacuum-laminated on a glass epoxy substrate (FR-4, product number “CS-3665”, manufactured by Risho Kogyo Co., Ltd.) and heated in a gear oven at 170 ° C. for 1 hour to be precured. I let you. In this way, a precured material was formed on the glass epoxy substrate, and a laminated sample of the glass epoxy substrate and the precured material was obtained. Then, after the following swelling treatment, the following roughening treatment (permanganate treatment) was performed.

Swelling treatment:
The above laminated sample was put in a swelling liquid (Swelling Dip Securigant P, manufactured by Atotech Japan Co., Ltd.) at 80 ° C. and rocked at a swelling temperature of 80 ° C. for 20 minutes. Thereafter, it was washed with pure water.

Roughening treatment (permanganate treatment):
The above-mentioned layered sample that had been swollen was placed in a roughened aqueous solution of potassium permanganate (Concentrate Compact CP, manufactured by Atotech Japan) at 80 ° C. and rocked at a roughening temperature of 80 ° C. for 20 minutes. Then, after washing | cleaning for 10 minutes with the washing | cleaning liquid (Reduction securigant P, Atotech Japan company make) of 25 degreeC, it wash | cleaned further with the pure water. In this way, a roughened cured body A was formed on the glass epoxy substrate.

(Production of laminate)
After the roughening treatment, the following copper plating treatment was performed.

Copper plating treatment:
The cured body A formed on the glass epoxy substrate was subjected to electroless copper plating and electrolytic copper plating in the following procedure.

  The surface of the roughened cured body A was treated with an alkali cleaner (cleaner securigant 902) at 60 ° C. for 5 minutes and degreased and washed. After washing, the cured body was treated with a 25 ° C. pre-dip solution (Pre-dip Neogant B) for 2 minutes. Thereafter, the cured product was treated with an activator solution (activator neogant 834) at 40 ° C. for 5 minutes to attach a palladium catalyst. Next, the cured body was treated with a reducing solution (reducer Neogant WA) at 30 ° C. for 5 minutes.

  Next, the cured body 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 using a beaker scale with a treatment liquid of 1 L and rocking the cured body.

Next, electrolytic plating was performed on the cured body subjected to the electroless plating treatment until the plating thickness became 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, the cured body was heated at 180 ° C. for 1 hour to further cure the cured body. Thus, the laminated body in which the copper plating layer was formed on the hardening body was obtained.

(Preparation of cured product B)
The obtained sheet-like molded body was heated in a gear oven at 170 ° C. for 1 hour, then heated in a gear oven at 180 ° C. for 1 hour and cured to obtain a cured body B.

(1) Dielectric constant and dielectric loss tangent The obtained cured body B was cut into a size of 15 mm × 15 mm. Eight pieces of the cured body cut were overlapped to obtain a laminate having a thickness of 320 μm. The dielectric constant and dielectric loss tangent of the laminate 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 body B was cut into a size of 3 mm × 25 mm. Using linear expansion meter (manufactured by part number "TMA / SS120C", Seiko Instruments Inc.), tensile load 2.94 × ^{10 -2} N, at a Atsushi Nobori rate of 5 ° C. / min conditions, the shredded cured body 23 The average linear expansion coefficient (α1) at ˜150 ° C. and the average linear expansion coefficient (α2) at 150-240 ° C. were measured.

(3) Glass transition temperature (Tg)
The obtained cured body B was cut into a size 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 was measured, and the temperature at which the loss rate tan δ reached the maximum value (glass transition temperature Tg) was determined.

(4) Breaking strength and elongation at break The obtained cured product B was cut into a size of 10 mm × 80 mm. Two cured bodies cut were laminated to obtain a test sample having a thickness of 80 μm. 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 degree (%) was measured.

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

(6) Surface roughness (arithmetic average roughness Ra and ten-point average roughness Rz)
Arithmetic average roughness Ra and ten points of the surface of the cured body A subjected to the roughening treatment in a measuring region of 94 μm × 123 μm using a non-contact three-dimensional surface shape measuring device (product number “WYKO NT1100”, manufactured by Veeco). The average roughness Rz was measured.

  The results are shown in Table 1 below.

(Example 8)
36 parts by weight of the slurry 2 containing 50% by weight of spherical silica and 22 parts by weight of DMF were mixed and stirred at room temperature until a uniform solution was obtained. Then, 0.2 parts by weight of the imidazole-based curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name “2PZ-CN”) and a peroxide-based curing accelerator (made by Kayaku Akzo, trade name “PERKADOX BC-FF”). ) 0.2 part by weight was further added and stirred at room temperature until a uniform solution was obtained.

  Next, 7.4 parts by weight of bisphenol A type epoxy resin 2 (trade name “828US” manufactured by JER Co.) as an epoxy resin and bisphenol F type epoxy resin (trade name “830-S” manufactured by DIC) 6 And 8 parts by weight were added and stirred at room temperature until a uniform solution was obtained. In the obtained solution, 15.6 parts by weight of a phenolic curing agent having a biphenyl structure as a curing agent (trade name “MEH7851-4H” manufactured by Meiwa Kasei Co., Ltd.) and polyphenylmethanemaleimide (Yamato as a maleimide compound) 12 parts by weight of Kasei Co., Ltd., trade name “BMI-2300”) was added and stirred at room temperature until a uniform solution was obtained, to prepare an epoxy resin composition.

(Examples 9-14 and Comparative Examples 5-8)
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 Table 2 below.

(Evaluation of Examples 8 to 14 and Comparative Examples 5 to 8)
(Preparation of sheet-like molded product)
In the same manner as in Examples 1 to 7 and Comparative Examples 1 to 4, laminates were obtained.

(Preparation of cured product A)
The swelling treatment conditions were changed from a swelling temperature of 80 ° C. for 20 minutes to a swelling temperature of 80 ° C. for 15 minutes, and the roughening treatment conditions were changed from a roughening temperature of 80 ° C. for 20 minutes to a roughening temperature of 80 ° C. for 15 minutes. Except having changed into minutes, the hardening body A was formed like Example 1-7 and Comparative Examples 1-4.

(Production of laminate)
In the same manner as in Examples 1 to 7 and Comparative Examples 1 to 4, laminates were obtained.

(Preparation of cured product B)
The obtained sheet-like molded body was heated in a gear oven at 170 ° C. for 1 hour, then heated in a gear oven at 180 ° C. for 3 hours and cured to obtain a cured body B.

  Similar to the evaluation of Examples 1 to 7 and Comparative Examples 1 to 4, the evaluation items (1) to (6) were evaluated. Furthermore, the following evaluation items (7) and (8) were also evaluated.

(7) Surface unevenness A single-sided copper clad laminate (product number “CS-3282”, copper foil thickness 30 μm, manufactured by Risho Kogyo Co., Ltd.) is coated with a photoresist by a known method, exposed, developed, A pattern was formed in which 20 copper wirings having a width of 100 μm, a height of 25 μm, and a length of 10 mm were arranged in parallel at intervals of 100 μm. The sheet-like molded body, which is an uncured product obtained, is vacuum-laminated on this laminated board and cured by heating in a gear oven at 170 ° C. for 1 hour to obtain a laminated body of the laminated board and the cured product layer. Obtained. The upper surface of the cured product layer of the obtained laminate was measured so as to cross the lower copper wiring, and the height between the deep part and the top part of the unevenness was measured with a surface roughness meter (trade name “SJ-301”, Mitutoyo Corporation). Manufactured). In the concave portion adjacent to one concave portion, the one having the larger difference was adopted, the difference of 19 points was obtained, and the average value was defined as the surface unevenness.

(8) Handling The obtained sheet-like molded product, which was an uncured product, was stored for 1 hour under constant temperature and humidity conditions of 24 ° C. and a relative humidity of 60%. Thereafter, the sheet-like molded body was cut with an NT cutter (L blade, 0.45 mm). At that time, the handling was evaluated as “×” when the chips were generated and “◯” when the chips were not generated.

  The results are shown in Table 2 below.

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)

Contains an epoxy resin, a curing agent, silica, and a maleimide compound,
The maleimide compound is included in a range of 2 to 200 parts by weight with respect to a total of 100 parts by weight of the epoxy resin and the curing agent,
The epoxy resin composition which contains the said silica in the range of 5 to 50 weight% in 100 weight% of solid content in an epoxy resin composition.   2. The epoxy resin composition according to claim 1, wherein the maleimide compound is contained within a range of 2 to 45 wt% in a solid content of 100 wt% in the epoxy resin composition.   The maleimide compound is N, N′-4,4-diphenylmethane bismaleimide, N, N′-1,3-phenylene dimaleimide, N, N′-1,4-phenylene dimaleimide, 1,2-bis. (Maleimide) ethane, 1,6-bismaleimide hexane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, polyphenylmethanemaleimide, bisphenol A diphenyl ether bismaleimide, 4-methyl-1,3-phenylene The at least one selected from the group consisting of bismaleimide, 1,6-bismaleimide- (2,2,4-trimethyl) hexane and oligomers thereof, and a maleimide skeleton-containing diamine condensate. The epoxy resin composition described in 1. The epoxy resin composition according to claim 1, wherein the maleimide compound is a maleimide compound represented by the following formula (11).

In said formula (11), R11-R13 shows a hydrogen atom, a halogen atom, or an organic group, and x represents the number within the range of 0-1.   The maleimide compound is a mixture of maleimide compounds represented by the formula (11), and the average value of x in the formula (11) of the mixture is within a range of 0.1 to 0.5. The epoxy resin composition according to claim 4, wherein   The solid content in the epoxy resin composition is 100% by weight, and the maleimide compound and the silica are contained within a total range of 35 to 70% by weight according to any one of claims 1 to 5. Epoxy resin composition.   The curing agent is at least one selected from the group consisting of a phenol compound having a naphthalene structure, a phenol compound having a dicyclopentadiene structure, a phenol compound having a biphenyl structure, and a phenol compound having an aminotriazine structure. The epoxy resin composition according to any one of 1 to 6.   The epoxy resin is an epoxy resin having an anthracene skeleton, an epoxy resin having a naphthalene skeleton, an epoxy resin having a dicyclopentadiene skeleton, an epoxy resin having an adamantane skeleton, an epoxy resin having a triazine skeleton, bisphenol A The epoxy resin composition according to any one of claims 1 to 7, which is at least one selected from the group consisting of a type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol S type epoxy resin.   The epoxy resin composition according to any one of claims 1 to 8, comprising a liquid epoxy resin within a range of 20 to 50% by weight in a solid content of 100% by weight in the epoxy resin composition.   The epoxy resin composition according to any one of claims 1 to 9, further comprising a phenoxy resin in a range of 1 to 10% by weight in a solid content of 100% by weight in the epoxy resin composition.   The sheet-like molded object formed by shape | molding the epoxy resin composition of any one of Claims 1-10 in a sheet form.   A prepreg formed by impregnating a porous substrate with the epoxy resin composition according to any one of claims 1 to 10. The epoxy resin composition according to any one of claims 1 to 10, a sheet-like molded body formed by molding the epoxy resin composition into a sheet, or the porous epoxy resin composition The prepreg formed by impregnating the porous substrate is heated, precured, and then a cured body that is roughened,
A cured body 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.   A laminate comprising: a cured body obtained by curing the sheet-like molded body according to claim 11; and a metal layer laminated on at least one surface of the cured body.   The laminate according to claim 14, wherein the metal layer is formed as a circuit. A laminated cured body, and a metal layer disposed between the cured bodies,
The multilayer laminated board whose said hardening body is a hardening body which hardened the sheet-like molded object of Claim 11.

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