JP2010229227A - Epoxy resin composition, sheet-like formed article, prepreg, cured product and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition which can lower the coefficient of linear expansion of a cured product, even when the content of an inorganic substance is small, can reduce the surface roughness of a roughed cured product, and can enhance the peel strength of a metal layer from the cured product, and to provide the3 cured product. <P>SOLUTION: The epoxy resin composition comprises an epoxy resin having at least two epoxy groups, a curing agent having an aminotriazine skeleton and a phenolic hydroxyl group, silica, and a maleimide compound having at least two maleimide skeletons, wherein the nitrogen content of the curing agent is ≤13 wt.%. The cured product 1 is formed by thermally preliminarily curing the epoxy resin composition and then roughening the product. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition used for obtaining a cured product having a copper plating layer or the like formed on the surface, and more specifically, an epoxy resin composition containing an epoxy resin, a curing agent, silica and a maleimide compound, In addition, the present invention relates to a sheet-like molded body, a prepreg, a cured body and a 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 the crosslinking points of the insulating resin determined from the shear modulus of elasticity of the insulating resin above the glass transition temperature is 300 to 1,000 at the stage after the laminate is manufactured. Moreover, as the insulating resin having the aromatic ring, an epoxy resin is cited.

JP 2006-022179 A JP 2007-314782 A

  When the cured body is formed by pre-curing the thermosetting resin composition described in Patent Documents 1 and 2 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 peel strength between the cured body and the metal layer may be lowered.

  Furthermore, the linear expansion coefficient of the cured product obtained by curing the thermosetting resin composition described in Patent Documents 1 and 2 may be high, and the glass transition temperature may be low.

  The object of the present invention is to reduce the linear expansion coefficient of the cured body even if the content of the inorganic substance is small, and further to reduce the surface roughness of the surface of the cured body that has been roughened and cured. An object of the present invention is to provide an epoxy resin composition capable of increasing the peel strength between the body and the metal layer, and a sheet-like molded body, prepreg, cured body and laminate using the epoxy resin composition.

According to a broad aspect of the invention, an epoxy resin having at least two epoxy groups;
An epoxy resin composition comprising a curing agent having an aminotriazine skeleton and a phenolic hydroxyl group, silica, and a maleimide compound having at least two maleimide skeletons, wherein the content of nitrogen in the curing agent is 13% by weight or less. Provided.

  On the specific situation with the epoxy resin composition which concerns on this invention, content of the said silica exists in the range of 20-60 weight% in 100 weight% of solid content of an epoxy resin composition.

  In another specific aspect of the epoxy resin composition according to the present invention, the content of the maleimide compound is in the range of 2 to 40% 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 silica is spherical silica having an average particle diameter of 1 μm or less.

  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 (maleimide) ethane, 1,6-bismaleimide hexane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, polyphenylmethanemaleimide, The group consisting of bisphenol A diphenyl ether bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide- (2,2,4-trimethyl) hexane and oligomers thereof, and a maleimide skeleton-containing diamine condensate Is at least one selected from

  In still another specific aspect of the epoxy resin composition according to the present invention, a phenoxy resin is further included.

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

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

  The cured body according to the present invention includes an epoxy resin composition configured 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 is a porous group. The prepreg impregnated in the material is heated and precured, and then a roughened cured body, the arithmetic average roughness Ra of the roughened surface is 0.3 μm or less, ten-point average roughness The thickness 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.

  The epoxy resin composition according to the present invention includes an epoxy resin having at least two epoxy groups, a curing agent having an aminotriazine skeleton and a phenolic hydroxyl group, silica, and a maleimide compound having at least two maleimide skeletons, Since the nitrogen content of the curing agent is 13% by weight or less, the linear expansion coefficient of the cured product can be lowered even if the inorganic content is small. Furthermore, the surface roughness of the roughened cured body can be reduced, and the peel strength between the cured body and the metal layer can be increased.

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

  The inventors of the present invention include an epoxy resin having at least two epoxy groups, a curing agent having an aminotriazine skeleton and a phenolic hydroxyl group, silica, and a maleimide compound having at least two maleimide skeletons, and a nitrogen of the curing agent. By adopting a composition having a content of 13% by weight or less, the linear expansion coefficient of the cured product can be lowered even when the inorganic content is small, and the surface of the surface of the cured product that has been roughened It has been found that the roughness can be reduced and the peel strength between the cured body and the metal layer can be increased. That is, in the present invention, both a small surface roughness of the surface of the cured body and a high peel strength between the cured body and the metal layer can be achieved.

  The epoxy resin composition according to the present invention includes an epoxy resin having at least two epoxy groups, a curing agent having an aminotriazine skeleton and a phenolic hydroxyl group, silica, and a maleimide compound having at least two maleimide skeletons. The nitrogen content of the curing agent is 13% by weight or less.

  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 two epoxy groups (oxirane rings). The number of epoxy groups per molecule of the epoxy resin is 2 or more.

  A conventionally well-known epoxy resin can be used as said epoxy resin. As for an epoxy resin, only 1 type may be used and 2 or more types may be used together. Epoxy resins also include epoxy resin derivatives or epoxy resin hydrogenated products.

  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 polyester type epoxy resins. .

  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 novolak. Novolak type epoxy resins such as 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 above epoxy resins include 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, a bisphenol A type epoxy resin, and bisphenol F. It is preferably at least one selected from the group consisting of a 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 also 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 particularly preferably at least one of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin. By using this preferable epoxy resin, the handling property and flatness of the B-stage sheet and the flatness of the film embedded at the time of heat press can be further enhanced.

  The content of the epoxy resin is preferably in the range of 20 to 50% by weight in 100% by weight of the solid content of the epoxy resin composition. When content of the said epoxy resin exists in the said range, the handleability of a sheet-like molded object using the epoxy resin composition and this epoxy resin composition can be made still higher. Furthermore, the unevenness of the surface of the cured body can be further reduced. The more preferable lower limit of the content of the epoxy resin in the solid content of 100% by weight of the epoxy resin composition is 25% by weight, and the more preferable upper limit is 40% by weight.

  The solid content of the epoxy resin composition is a component excluding the solvent contained in the epoxy resin composition, and the liquid epoxy resin is also included in the solid content. The above-mentioned “100 wt% solid content of epoxy resin composition” means an epoxy resin, a curing agent, silica and a maleimide compound, and a non-volatile content that does not volatilize during molding and heating among other components blended as necessary The sum of Therefore, the above “100 wt% solid content of the epoxy resin composition” indicates “100 wt% solid content of the epoxy resin composition including the liquid epoxy resin”.

(Curing agent)
The epoxy resin composition according to the present invention includes a curing agent having an aminotriazine skeleton and a phenolic hydroxyl group (hereinafter also referred to as curing agent A). The curing agent A is a phenol compound having an aminotriazine skeleton. Moreover, content of nitrogen of the hardening | curing agent A in 100 weight% of hardening | curing agents A is 13 weight% or less. By using the curing agent A having such a structure and the nitrogen content satisfying the above value, the linear expansion coefficient of the cured body can be lowered, and the surface of the surface of the cured body that has been further roughened. The roughness can be reduced and the peel strength between the cured body and the metal layer can be increased. The minimum with preferable content of nitrogen in the said hardening | curing agent A100weight% is 10 weight%.

  Examples of the aminotriazine skeleton include a melamine skeleton, a substituted melamine skeleton, a melam skeleton, a melem skeleton, a benzoguanamine skeleton, an acetoguanamine skeleton, and a spiroguanamine skeleton.

  The curing agent A has, for example, a phenol novolak resin skeleton, an o-cresol novolak resin skeleton, a p-cresol novolak resin skeleton, a t-butylphenol novolak resin skeleton, or a dicyclopentadiene cresol resin skeleton.

  The curing agent A is preferably an aminotriazine novolak phenol type curing agent having an aminotriazine skeleton and a phenol novolac resin skeleton. By using a curing agent having an aminotriazine skeleton and a phenol novolac resin skeleton, the linear expansion coefficient of the cured product can be further reduced.

  As a commercial item of the said hardening | curing agent A, brand name "LA-7052", brand name "LA-7054" (above, all are the DIC company make), etc. are mentioned. As for the hardening | curing agent A, only 1 type may be used and 2 or more types may be used together.

  The content of the curing agent A is preferably in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin. The minimum with more preferable content of the said hardening | curing agent A with respect to 100 weight part of epoxy resins is 30 weight part, and a more preferable upper limit is 85 weight part. When there is too little content of the hardening | curing agent A, an epoxy resin composition may not fully harden | cure. When there is too much content of the hardening | curing agent A, the effect of hardening an epoxy resin may be saturated.

  The epoxy resin composition may further contain another conventionally known curing agent (hereinafter also referred to as curing agent B) in addition to the above-described curing agent having an aminotriazine skeleton and a phenolic hydroxyl group.

  Examples of the other curing agent B include, for example, dicyandiamide, an amine compound, a derivative of an amine compound, a hydrazide compound, an acid anhydride, a phenol compound, an active ester compound, a thermal latent cationic polymerization catalyst, a photolatent cationic polymerization initiator, or Examples include cyanate ester resins. These derivatives may be used as the curing agent B. As for the hardening | curing agent B, only 1 type may be used and 2 or more types may be used together. A curing catalyst such as acetylacetone iron may be used together with these curing agents.

  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 B. 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 B, 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 B, 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.

  Especially, it is a phenol compound represented by the said Formula (3), Comprising: R4 in the said Formula (3) is a group represented by the said Formula (5c), and the phenol compound which has a biphenyl skeleton 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.

  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 other curing agent B 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.

  The other curing agent B is particularly preferably at least one selected from the group consisting of a phenol compound having a naphthalene skeleton, a phenol compound having a dicyclopentadiene skeleton, and a phenol compound having a biphenyl skeleton. When these preferable curing agents B are used in combination with the curing agent A, the resin component is more unlikely to be adversely affected by the roughening treatment when the roughening treatment is performed after reacting the epoxy resin composition. Specifically, during the roughening treatment, fine pores can be formed by selectively desorbing silica without the surface of the resulting cured body becoming too rough. For this reason, the fine unevenness | corrugation whose surface roughness is very small can be formed in the surface of a hardening body. Furthermore, the peel strength between the cured body and the metal layer can be increased. Of these, a phenol compound having a biphenyl skeleton is preferable.

  When a phenolic compound having a biphenyl skeleton or a phenolic compound having a naphthalene skeleton is used, the electrical characteristics of the cured body, particularly the dielectric loss tangent of the cured body is increased. Further, the strength of the cured body is increased and the linear expansion coefficient is further decreased.

(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.

  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 content of the curing accelerator is preferably in the range of 0.01 to 3 parts by weight with respect to 100 parts by weight of the epoxy resin. The minimum with more preferable content of the said hardening accelerator with respect to 100 weight part of said epoxy resins is 0.5 weight part, and a more preferable upper limit is 2.0 weight part. When there is too little content of a hardening accelerator, an epoxy resin composition may not fully harden | cure. When there is too much content of a hardening accelerator, the effect of hardening an epoxy resin may be saturated.

(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 or aromatic polyvalent ester compound having any one of a naphthalene skeleton, a dicyclopentadiene skeleton, a biphenyl skeleton, and an aminotriazine skeleton is used as a curing agent, a roughening treatment can be performed on the spherical silica. The surrounding resin component is hard to be scraped off. 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 peel strength between the cured body and the metal layer is likely to be lowered.

  The average particle diameter of the spherical silica is measured by a laser diffraction method. 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 thixotropic properties 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 the epoxy resin composition is precured. Furthermore, relatively large holes are hardly formed on the surface of the cured body, and uniform and fine irregularities can be formed.

  When a phenol compound or aromatic polyvalent ester compound having any one of a naphthalene skeleton, a dicyclopentadiene skeleton, a biphenyl skeleton, and an aminotriazine skeleton is used as a curing agent, the epoxy resin composition is preliminarily used. The roughening liquid hardly penetrates into the precured product from the surface of the cured 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, the peel strength 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.

  Since the purity is high, fused silica is preferably used. 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. 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 silane coupling agent is not only added by surface treatment of silica, but a silane coupling agent can be added separately to the epoxy resin composition. The epoxy resin composition of the present invention may contain a silane coupling agent added separately. In particular, it is possible to reduce the surface roughness of the roughened cured body by further adding an imidazole silane coupling agent. The amount of the silane coupling agent to be added is desirably 5 parts by weight or less in 100% by weight of the epoxy resin composition. If it exceeds 5 parts by weight, the viscosity of the epoxy resin composition may change, or the physical properties of the cured product may be adversely affected.

  It is preferable that content of the said silica exists in the range of 20 to 60 weight% in 100 weight% of solid content of the said epoxy resin composition. The upper limit with more preferable content of the said silica in 100 weight% of solid content of the said epoxy resin composition is 50 weight%. If the silica content 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 peel strength between the cured body and the metal layer may not be sufficiently increased. The greater the silica content, the lower the linear expansion coefficient of the cured product. 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.

(Maleimide compound)
The maleimide compound contained in the epoxy resin composition according to the present invention has at least two maleimide skeletons. By using this 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. 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-phenylenebismaleimide 1,6-bismaleimide- (2,2,4-trimethyl) hexane and oligomers thereof, and at least one selected from the group consisting of maleimide skeleton-containing diamine condensates are preferable. 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 compound which is a monomer in the maleimide compound mentioned above. As for a maleimide compound, only 1 type may be used and 2 or more types may be used together.

  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 reduced, 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. When the DAIMAID-100H is used 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 that when the DAIMAID-100H is used.

  Moreover, it is preferable that the said maleimide compound is a maleimide compound represented by 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 (11A).

  In the formula (11A), x represents an integer in the range of 0-1.

  The maleimide compound is a mixture of maleimide compounds represented by the formula (11) or formula (11A), and the average value of x in the formula (11) and formula (11A) of the mixture is 0.1. It is preferable that it exists in the range of -0.5. The greater the average value of x, the higher the solubility of the mixture. By using a mixture in which the average value of x in the above formula (11) and formula (11A) is in the range of 0.1 to 0.5, the linear expansion can be further reduced and the solubility is increased. be able to. By using a mixture in which the average value of x in the above formula (11) and formula (11A) is in the range of 0.2 to 0.3, the dimensional change due to temperature such as linear expansion can be further reduced. .

  The content of the maleimide compound in the solid content of 100% by weight of the epoxy resin composition is preferably in the range of 2 to 40% by weight. The minimum with more preferable content of the said maleimide compound in solid content of 100 weight% of the said epoxy resin composition is 10 weight%, and a more preferable upper limit is 30 weight%. When there is too little content of a maleimide compound, the linear expansion coefficient of a hardening body cannot be made low enough, or the glass transition temperature of a hardening body cannot be made high enough. As the content of the maleimide compound is larger, more rigid skeleton is introduced into the cured body, so that the linear expansion coefficient of the cured body is lowered and the glass transition temperature of the cured body tends to be higher. However, when there is too much content of a maleimide compound, the effect of reducing the linear expansion coefficient of a hardening body and the effect of improving the glass transition temperature of a hardening body may be saturated. Furthermore, the surface roughness of the roughened cured body may increase, or the breaking strength may decrease significantly.

(Phenoxy resin)
The epoxy resin composition according to the present invention preferably 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 resin with a divalent phenol compound.

  The content of the phenoxy resin in the solid content of 100% by weight of the epoxy resin composition is preferably in the range of 1 to 10% by weight. When the content of the phenoxy resin is within this preferable 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. The more preferable lower limit of the content of the phenoxy resin in the solid content of 100% by weight of the epoxy resin composition is 3% by weight, and the more preferable upper limit is 7% by weight. When there is too little content of a phenoxy resin, the breaking strength of a hardening body may not fully be raised. When there is too much content of a phenoxy resin, the linear expansion coefficient of a hardening body will become high easily and glass transition temperature may fall.

(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 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. As the copolymerizable resin, only one type may be used, or two or more types may be used in combination.

  The copolymerizable resin is not particularly limited. Examples of the copolymerizable resin include thermosetting modified polyphenylene ether resin or benzoxazine resin.

  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. 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 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, Examples thereof include 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. 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 may contain an additive as necessary. Additives include thermoplastic resins, other thermosetting resins other than epoxy resins, thermoplastic elastomers, cross-linked rubbers, oligomers, inorganic compounds, nucleating agents, antioxidants, anti-aging agents, thermal stability Agents, light stabilizers, ultraviolet absorbers, lubricants, flame retardant aids, antistatic agents, antifogging agents, fillers, softeners, plasticizers or colorants. As for an additive, 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.

(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, the curing agent A, silica, a maleimide compound, and components to be blended as necessary are added to a solvent, and then dried. The method etc. which remove | eliminate are mentioned. 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 state dissolved in a solvent.

  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 build-up 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, and a prepreg. Or it is used suitably for a varnish etc.

  Moreover, a fine hole can be formed in the surface of a hardening body by use of the epoxy resin composition which concerns on this invention. For this reason, fine wiring can be formed on the surface of the cured body, and the signal transmission speed in the wiring can be increased. Therefore, the 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 board or the like in which a plurality of cured bodies and conductive plating layers are laminated by an additive method for forming a circuit after forming a conductive plating layer on the surface of the cured body or a semi-additive method. 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 enhanced, the epoxy resin is also applied to a component-embedded substrate or the like in which a passive component or an active component is built that requires high-frequency characteristics Compositions 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, an extruder is used to melt-knead and extrude the epoxy resin composition, and then extrusion to form a film with a T-die or a circular die. Examples thereof include a 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)
In the prepreg according to the present invention, the porous base material is impregnated with the epoxy resin composition. A prepreg is obtained by impregnating a porous substrate with an 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)
Heating the epoxy resin composition according to the present invention, a sheet-like molded body formed by molding the epoxy resin composition into a sheet, or a prepreg impregnated with a porous substrate of the epoxy resin composition; A hardened body can be obtained by roughening after pre-curing.

  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 is increased. 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 peel strength between the cured body 1 and the metal layer 2 can be increased by the physical anchor effect. Moreover, since the resin component is not shaved more than necessary in the vicinity of the hole 1b formed by the detachment of the spherical silica, the peel 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 peel strength between the cured body 1 and the metal layer 2 is preferably 0.5 kgf / cm or more. The peel 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 the average linear expansion coefficient (alpha) 1 (23-100 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, and further preferably 34 ppm / ° C. or less. When the average linear expansion coefficient α1 is too large, the thermal shock resistance is lowered, and when the epoxy resin composition is used as a printed circuit board material, there is a possibility that the substrate may be cracked due to expansion and contraction during a thermal cycle. is there.

  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, the heat resistance is improved, and when the epoxy resin composition is used as a printed circuit board material, improvement in dimensional stability during solder reflow, suppression of blistering of the plating layer, and the like can be expected. In addition, the tensile strength of the cured body at high temperatures is improved.

(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 laminate may be a multilayer laminate comprising a plurality of laminated cured bodies and at least one metal layer disposed between the cured bodies. The said hardening body is a hardening body which hardened the said sheet-like molded object. In the case of a multilayer laminate, a metal layer laminated on the outer surface of the outermost cured body may be further provided.

  An adhesive layer may be disposed in at least a partial region of the cured body of the laminate. Moreover, the adhesive layer may be arrange | positioned in the at least one part area | region of 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 peel strength between the cured body and the metal layer is high, the reliability of the circuit can be increased.

  FIG. 3 shows a laminate using the epoxy resin composition according to one embodiment of the present invention. The laminated board shown in FIG. 3 is a multilayer laminated board.

  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. . 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 peel 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. In addition, the film may be subjected to a release treatment in order to improve the release property as necessary. Furthermore, in order to protect the film, a protective 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 epoxy resin (product name “850S”, manufactured by DIC Corporation)
Bisphenol F epoxy resin (Nippon Kayaku Co., Ltd., trade name “RE410S”)
Anthracene skeleton-containing epoxy resin (made by Japan Epoxy Resin Co., Ltd., trade name “YX8800”, epoxy equivalent 181)

(Curing agent)
Phenol curing agent 1 having aminotriazine skeleton and phenolic hydroxyl group (manufactured by DIC, trade name “LA-7052”, solid content 61 wt% MEK (methyl ethyl ketone) solution, nitrogen content 8 wt%, weight average molecular weight 1,754 )
Phenol curing agent 2 having aminotriazine skeleton and phenolic hydroxyl group (manufactured by DIC, trade name “LA-7054”, solid content 60 wt% MEK (methyl ethyl ketone) solution, nitrogen content 12 wt%, weight average molecular weight 1,420 )
Phenol curing agent 3 having aminotriazine skeleton and phenolic hydroxyl group (manufactured by DIC, trade name “LA-7751”, solid content 60 wt% MEK (methyl ethyl ketone) solution, nitrogen content 14 wt%, weight average molecular weight 1,597 )
Phenol curing agent 4 having a biphenyl skeleton and a phenolic hydroxyl group (Maywa Kasei Co., Ltd., trade name “MEH7851-4H”, a curing agent corresponding to the phenol compound represented by the above formula (7))

(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)

(Silica slurry)
Slurry containing 50% by weight of spherical silica 1:
50% by weight of spherical silica (average particle size 0.3 μm, specific surface area 18 m ² / g by BET method) treated with imidazolesilane (manufactured by Nikko Metals, trade name “IM-1000”), DMF (N, N— Slurry containing 50% by weight of spherical silica containing 50% by weight of dimethylformamide) slurry 2 containing 50% by weight of spherical silica:
50% by weight of spherical silica (average particle size 0.5 μm, specific surface area 7 m ² / g by BET method) treated with imidazolesilane (manufactured by Nikko Metals, trade name “IM-1000”), DMF (N, N— 50% by weight of spherical silica containing 50% by weight of dimethylformamide)

(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 the average value of x in the above formula (11) of the mixture is 0.2-0.3)

(Phenoxy resin)
Phenoxy resin having a modified biphenol skeleton (made 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)

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

Example 1
36.0 parts by weight of the slurry 1 containing 50% by weight of spherical silica and 11.6 parts by weight of N, N-dimethylformamide were mixed and stirred at room temperature until a uniform solution was obtained. Thereafter, 0.3 parts by weight of the imidazole-based curing accelerator (trade name “2PZ-CN” manufactured by Shikoku Kasei Kogyo Co., Ltd.) and a peroxide-based curing accelerator (trade name “Perkadox BC-FF” manufactured by Kayaku Akzo) ) 0.3 parts by weight were further added and stirred at room temperature until a uniform solution was obtained.

  Next, 11.5 parts by weight of bisphenol A type epoxy resin (manufactured by DIC, trade name “850S”) as an epoxy resin and bisphenol F type epoxy resin (trade name “RE410S”, manufactured by Nippon Kayaku Co., Ltd.) 6.4 A part by weight was added and stirred at room temperature until a uniform solution was obtained to obtain a solution. In the obtained solution, 15.9 parts by weight of a phenol curing agent 1 having an aminotriazine skeleton and a phenolic hydroxyl group as a curing agent (manufactured by DIC, trade name “LA-7052”) and polyphenylmethanemaleimide as a maleimide compound 12.0 parts by weight (trade name “BMI-2300” manufactured by Daiwa Kasei Co., Ltd.) and 6.0 parts by weight of phenoxy resin having a modified biphenol skeleton (trade name “YX6954BH30” manufactured by Japan Epoxy Resin Co., Ltd.) are added. The epoxy resin composition was prepared by stirring at room temperature until a uniform solution was obtained.

(Examples 2 to 7 and Comparative Examples 1 and 2)
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)
(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 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, which was an uncured product having a size of 200 mm long × 200 mm wide × 40 μm thick, 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-mentioned laminated sample was put in a swelling liquid at 80 ° C. (Swelling Dip Securigant P, manufactured by Atotech Japan Co., Ltd .: organic solvent-containing aqueous solution) 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 laminated sample subjected to the swelling treatment was placed in a roughening aqueous solution of alkaline potassium permanganate (Concentrate Compact CP, manufactured by Atotech Japan Co.) 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) (an aqueous solution containing an alkaline surfactant) for 5 minutes and degreased and washed. After washing, the cured body was treated with a pre-dip solution (pre-dip neogant B), which is a pretreatment agent at 25 ° C., 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 product is placed in a chemical copper solution (an aqueous solution of copper sulfate stabilizer and copper sulfate) (basic print gantt MSK-DK, copper print gantt MSK, stabilizer print gantt MSK), and electroless plating is performed. It implemented until thickness became about 0.5 micrometer. 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. 23 of the cured product cut using a linear expansion coefficient meter (product number “TMA / SS120C”, manufactured by Seiko Instruments Inc.) under the conditions of a tensile load of 2.94 × 10 ⁻² N and a heating rate of 5 ° C./min. The average linear expansion coefficient (α1) at ˜100 ° 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 adhesion strength (peel strength)
The surface of the copper plating layer of the obtained laminate was cut into a 10 mm width. Thereafter, using a tensile tester (trade name “Autograph”, manufactured by Shimadzu Corporation), the peel 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.

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 (10)

An epoxy resin having at least two epoxy groups;
A curing agent having an aminotriazine skeleton and a phenolic hydroxyl group;
Silica,
A maleimide compound having at least two maleimide skeletons,
The epoxy resin composition whose nitrogen content of the said hardening | curing agent is 13 weight% or less.   The epoxy resin composition according to claim 1, wherein the content of the silica is in the range of 20 to 60% by weight in 100% by weight of the solid content of the epoxy resin composition.   The epoxy resin composition of Claim 1 or 2 whose content of the said maleimide compound exists in the range of 5 to 40 weight% in solid content of 100 weight% of an epoxy resin composition.   The epoxy resin composition according to any one of claims 1 to 3, wherein the silica is spherical silica having an average particle diameter of 1 µm or less.   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-phenylenebismaleimide 1,6-bismaleimide- (2,2,4-trimethyl) hexane and oligomers thereof, and at least one selected from the group consisting of maleimide skeleton-containing diamine condensates The epoxy resin composition according to item 1.   The epoxy resin composition according to claim 1, further comprising a phenoxy resin.   The sheet-like molded object formed by shape | molding the epoxy resin composition of any one of Claims 1-6 in a sheet form.   A prepreg in which a porous substrate is impregnated with the epoxy resin composition according to any one of claims 1 to 6. The epoxy resin composition according to any one of claims 1 to 6, a sheet-like molded body formed by molding the epoxy resin composition into a sheet, or the epoxy resin composition is a porous substrate The prepreg impregnated in is heated, precured, and then a roughened cured body,
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 7; and a metal layer laminated on at least one surface of the cured body.

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