JP2010215858A - Epoxy resin composition, sheet-like molding, laminated sheet, prepreg, cured product and multilayer laminated sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition capable of allowing a cured product made thereof to have lower linear expansion coefficient even when the content of inorganic substances is low, have higher glass transition temperature and have higher tensile strength and to provide the cured product. <P>SOLUTION: The epoxy resin composition contains an epoxy resin, a curing agent, silica and melamine and has 1-8 wt.% melamine content based on 100 wt.% solid content of the epoxy resin composition. The cured product 1 is obtained by heating the epoxy resin composition, curing the heated composition preliminarily and subjecting the preliminarily-cured composition to roughening treatment. <P>COPYRIGHT: (C)2010,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 particularly, an epoxy resin composition containing an epoxy resin, a curing agent, silica and melamine, and The present invention relates to a sheet-like molded product, a laminate, a prepreg, a cured product and a multilayer laminate using the epoxy resin composition.

  Conventionally, various thermosetting resin compositions have been used to form laminated plates 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.

JP 2006-022179 A

  In recent years, in order to increase the reliability of the laminated board against thermal shock, the cured body of the thermosetting resin composition is required to have high heat resistance and small dimensional change at high temperatures.

  The cured product obtained by curing the thermosetting resin composition described in Patent Document 1 has a high linear expansion coefficient, and thus may have a large dimensional change at high temperatures.

  An object of the present invention is to provide an epoxy resin composition capable of reducing the linear expansion coefficient of a cured product even when the inorganic content is small, and increasing the glass transition temperature and tensile strength of the cured product, and the It is providing the sheet-like molded object, laminated board, prepreg, hardened | cured body, and multilayer laminated board using an epoxy resin composition.

  According to a wide aspect of the present invention, the epoxy resin, the curing agent, silica, and melamine are included, and the content of the melamine is in the range of 1 to 8% by weight in 100% by weight of the solid content of the epoxy resin composition. An epoxy resin composition is provided.

  In a specific aspect of the epoxy resin composition according to the present invention, a maleimide compound is further included, and 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. Is within.

  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 another specific aspect of the epoxy resin composition according to the present invention, the curing agent is a phenol compound.

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

  The other specific situation of the epoxy resin composition which concerns on this invention is content of the said silica in the range of 5 to 60 weight% in 100 weight% of solid content of an epoxy resin composition.

  Still another specific aspect of the epoxy resin composition according to the present invention is that the silica is spherical silica, and the average particle diameter of the spherical silica measured by a laser diffraction method is 1 μm or less.

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

  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.

  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.

  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 cured.

  A multilayer laminate according to the present invention comprises a plurality of laminated cured bodies and a metal layer disposed between the cured bodies, and the cured body cures a sheet-like molded body configured according to the present invention. Cured body.

  The epoxy resin composition according to the present invention contains an epoxy resin, a curing agent, silica and melamine, and the content of melamine in the solid content of 100% by weight of the epoxy resin composition is in the range of 1 to 8% by weight. Even if the content of the inorganic substance is small, the linear expansion coefficient of the cured product can be lowered. Therefore, the dimensional change when the cured body is exposed to a high temperature can be reduced. Furthermore, the glass transition temperature and tensile strength of the cured product can be increased.

FIG. 1 is a partially cutaway front sectional view showing a cured body using an epoxy resin composition according to an embodiment of the present invention. FIG. 2 is a partially cutaway front 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 employ a composition containing an epoxy resin, a curing agent, silica and melamine, and further having a melamine content in the solid content of 100% by weight of the epoxy resin composition in the range of 1 to 8% by weight. By doing, it discovered that the linear expansion coefficient of a hardening body can be made low and the glass transition temperature and tensile strength of a hardening body can be made high.

  The epoxy resin composition according to the present invention includes an epoxy resin, a curing agent, silica, and melamine. 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 1 or more. The number of epoxy groups is preferably 2 or more. Epoxy resins also include epoxy resin derivatives or epoxy resin hydrogenated products.

  The epoxy resin composition according to the present invention includes a liquid epoxy resin and an epoxy resin having an anthracene skeleton as the 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 polyester type epoxy resins. .

  Examples of the aromatic epoxy resin include a biphenyl type epoxy resin, an epoxy resin having a naphthalene skeleton, an epoxy resin having an anthracene skeleton, an epoxy resin having a dicyclopentadiene skeleton, an epoxy resin having an adamantane skeleton, and an epoxy having a triazine skeleton. Resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol type epoxy resin such as bisphenol AD type epoxy resin or bisphenol S type epoxy resin, or novolac type epoxy resin such as phenol novolac type epoxy resin or cresol novolac type epoxy resin Etc.

  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.

  It is preferable that liquid epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin are contained within a range of 15 to 50% by weight in 100% by weight of the solid content in the epoxy resin composition. When content of a liquid epoxy resin exists in the said range, the handleability of an epoxy resin composition and a sheet-like molded object using 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 20% 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. Liquid epoxy resin is also included in the solid content. The above “100 wt% solid content of the epoxy resin composition” refers to the total of the epoxy resin, the curing agent, silica and melamine, and other solid contents blended as necessary.

(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, amine compound derivatives, hydrazide compounds, acid anhydrides, phenol compounds, active ester compounds, thermal latent cationic polymerization catalysts, photolatent cationic polymerization initiators, and cyanate ester resins. Etc. 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.

  The curing agent is particularly preferably a phenol compound having a skeleton represented by the following formula (1). 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 (1), 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. As a commercial item of the said active ester compound, the brand name "EPICLON EXB9451-65T" by Dainippon Ink & Chemicals, Inc. etc. are mentioned, for example.

  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 skeleton, a phenol compound having a dicyclopentadiene skeleton, a phenol compound having a biphenyl skeleton, and a phenol compound having an aminotriazine skeleton. preferable. When these preferable curing agents are used, when the roughening treatment is performed 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 skeleton is preferable.

  A cured product using a phenolic compound having a biphenyl skeleton or a phenolic compound having a naphthalene skeleton 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.

  It is preferable that content of the said hardening | curing agent exists in the range of 1-200 weight part with respect to 100 weight part of said epoxy resins. The minimum with more preferable content of the said hardening | curing agent with respect to 100 weight part of epoxy resins is 30 weight part, and a more preferable upper limit is 140 weight part. When there is too little content of a hardening | curing agent, an epoxy resin composition may not fully harden | cure. When there is too much content of a hardening | curing agent, the effect of hardening an epoxy resin may be saturated.

(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 triphenylphosphine, phenol salt of DBU, DBN, DBU, 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.

  When a maleimide compound is contained, 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 peroxide curing accelerator may be used alone or in combination with another curing accelerator such as an imidazole curing accelerator.

  The content of the curing accelerator is preferably in the range of 0.01 to 3% by weight with respect to 100 parts by weight of the epoxy resin. When the content of the curing accelerator is within the above preferable range, the epoxy resin composition can be cured more efficiently. The minimum with preferable content of the said hardening accelerator with respect to 100 weight part of said epoxy resins is 0.5 weight part, and a preferable upper limit is 2.0 weight part.

  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 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 is 1 μm or less, the spherical silica can be more easily detached.

  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. By using spherical silica having an average particle size of several tens of nanometers, the viscosity of the epoxy resin composition can be increased and the thixotropy can be controlled. The maximum particle size 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 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 spherical 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 adhesive 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 spherical silica, crystalline spherical silica obtained by pulverizing natural spherical silica raw material, crushed fused spherical silica obtained by flame melting and pulverizing natural spherical silica raw material, Examples include spherical fused spherical silica obtained by flame melting, fumed spherical silica (Aerosil), or synthetic spherical silica such as sol-gel spherical silica.

  Because of its high purity, fused spherical silica is preferably used. The spherical silica may be used as a spherical silica slurry in a state dispersed in a solvent. By using the spherical silica slurry, workability and productivity can be improved during the production of the epoxy resin composition. The spherical 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. Moreover, the spherical 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.

  As a method of surface-treating the spherical silica with a silane coupling agent, for example, by adding a silane coupling agent while stirring a spherical silica slurry containing a spherical method and a dry method and a wet method, a heating reflux treatment is performed. Examples thereof include a method for proceeding with dehydration condensation. By using spherical 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.

  In the solid content of 100% by weight of the epoxy resin composition, the content of the spherical silica is preferably in the range of 5 to 60% by weight. The minimum with more preferable content of the said spherical silica in 100 weight% of solid content of the said epoxy resin composition is 15 weight%, and a more preferable upper limit is 50 weight%. When the content of the spherical silica is too small, the total surface area of the pores formed by the desorption of the spherical 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 content of spherical silica, the lower the linear expansion coefficient of the cured product. However, if the amount of spherical silica is too large, the cured body tends to become brittle and the surface roughness of the roughened cured body 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.

(melamine)
The epoxy resin composition according to the present invention contains melamine. The content of melamine is in the range of 1 to 8% by weight in 100% by weight of the solid content of the epoxy resin composition. In addition to the epoxy resin, curing agent and silica, melamine is contained within the above range, so that the linear expansion coefficient of the cured product can be lowered, and the glass transition temperature and tensile strength of the cured product are increased. can do. The minimum with preferable content of the melamine in 100 weight% of solid content of the said epoxy resin composition is 2 weight%, and a preferable upper limit is 6 weight%.

(Maleimide compound)
The epoxy resin composition according to the present invention preferably contains a maleimide compound. The maleimide compound has a maleimide skeleton. 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 laminated board using the epoxy resin composition according to the present invention, an effect that the thermal shock resistance of the cured body or the laminated board 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”).

  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 (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 is in the range of 0.1 to 0.5, linear expansion can be further reduced and solubility can be increased. By using a mixture in which the average value of x is in the range of 0.2 to 0.3, a 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. When the content of the maleimide compound is within the above range, the linear expansion coefficient of the cured product can be sufficiently lowered, and the glass transition temperature of the cured product can be sufficiently increased. The minimum with more preferable content of the said maleimide compound in solid content of 100 weight% of the said epoxy resin composition is 5 weight%, and a more preferable upper limit is 30 weight%. 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. Furthermore, the linear expansion coefficient of the cured body can be lowered and the glass transition temperature 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.

(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, the above-mentioned epoxy resin, the above curing agent, silica and melamine, and components to be blended as necessary are added to a solvent, and then dried to remove the solvent. Etc. 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. 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.

  When the epoxy resin composition contains a solvent, the solid content is preferably in the range of 50 to 70% by weight in 100% by weight of the epoxy resin composition. In this case, the coating property of the epoxy resin composition can be improved, and the thickness of the sheet-like molded body can be made uniform.

  The epoxy resin composition according to the present invention may contain conventionally known additives such as inorganic fillers other than silica, pigments, and organically modified layered silicates.

  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 spherical silica formed in the surface of the hardening body removed is small, the insulation between patterns can be improved. Furthermore, since the depth of the hole through which the spherical silica is removed is shallow, the insulation between the layers can be enhanced.

  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.

  The content of the solvent is preferably in the range of 0 to 5% by weight in 100% by weight of the sheet-like molded body. In the said sheet-like molded object, a solvent is an arbitrary component.

  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)
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 formed by impregnating a porous substrate with the epoxy resin composition Is heated, precured, and then roughened to obtain a cured product.

  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, if 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 spherical silica is detached from the surface of the cured body. It becomes difficult to form holes having the 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.

  FIG. 1 shows a cured body 1 according to an embodiment of the present invention.

  On the upper surface 1a of the cured body 1 shown in FIG. 1, holes 1b formed by the removal of spherical silica are formed. A metal layer 2 is formed on the upper surface 1a of the cured body 1 by plating. The metal layer 2 reaches the fine holes 1b formed in the upper surface 1a 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.

  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.

  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 average linear expansion coefficient α1 (23 to 150 ° C.) of the cured body 1 is preferably 50 ppm / ° C. or less, and more preferably 40 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 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 several hardening body laminated | stacked and the at least 1 metal layer arrange | positioned between this hardening body. The said hardening body is a hardening body which hardened the said sheet-like molded object. 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 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 adhesive strength between the cured body and the metal layer is high, the reliability of the circuit can be increased.

  FIG. 2 shows a multilayer laminate using the epoxy resin composition according to one embodiment of the present invention.

  In the multilayer laminated plate 11 shown in FIG. 2, 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 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.

  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 liquid epoxy resin (manufactured by DIC, trade name “850S”)
Epoxy resin having a triazine skeleton (manufactured by Nissan Chemical Co., Ltd., trade name “TEPIC-SP”)

(Curing agent)
Phenol curing agent having a biphenyl skeleton (product name “MEH7851-4H” manufactured by Meiwa Kasei Co., Ltd., a curing agent corresponding to the phenol compound represented by the above formula (1))

(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)

(Spherical silica slurry)
Slurry containing 50% by weight of spherical silica:
Epoxy silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”, spherical silica (average particle size 0.3 μm, specific surface area 18 m ² / g by BET method) 50% by weight, A slurry containing 50% by weight of spherical silica containing 50% by weight of DMF (N, N-dimethylformamide)

(melamine)
Melamine (made by Wako Pure Chemical Industries, trade name “Melamine Wako Special Grade”)
Benzoguanamine

(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 containing 50% by weight of spherical silica and 22.0 parts by weight of N, N-dimethylformamide were mixed and stirred at room temperature until a uniform solution was obtained. Thereafter, 0.2 part by weight of the 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, 18.8 parts by weight of a bisphenol A type liquid epoxy resin (manufactured by DIC, trade name “850S”) as an epoxy resin was added and stirred at room temperature until a uniform solution was obtained. In the obtained solution, 21.2 parts by weight of a phenol curing agent having a biphenyl skeleton (Maywa Kasei Co., Ltd., trade name “MEH7851-4H”), and melamine as an aminotriazine compound (manufactured by Wako Pure Chemical Industries, Ltd., trade name “ An epoxy resin composition was prepared by adding 1.8 parts by weight of “Melamine Wako Special Grade”) and stirring at room temperature until a uniform solution was obtained.

(Examples 2-8 and Comparative Examples 1-3)
An epoxy resin composition was prepared in the same manner as in Example 1 except that the type and blending amount of the materials used were changed as shown in Tables 1 and 2 below. In addition, when the epoxy resin composition contains a maleimide compound and a phenoxy resin, the maleimide compound and the phenoxy resin were added when the epoxy resin, the curing agent, and the aminotriazine compound were added.

(Evaluation)
(Preparation of evaluation sample)
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, an uncured product as a sheet-like molded body having a size of length 200 mm × width 200 mm × thickness 40 μm was produced.

  The obtained uncured product was heated in an oven gear oven at 170 ° C. for 1 hour to prepare a semi-cured product. Further, the obtained semi-cured product was heated in a gear oven at 180 ° C. for 1 hour and cured to obtain a cured product.

(1) Dielectric constant and dielectric loss tangent The obtained cured product was cut into a size of 15 mm × 15 mm. Ten pieces of the cut cured bodies were overlapped to obtain a laminate having a thickness of 400 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 said hardening body was cut | judged to the magnitude | size of 3 mm x 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 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 body 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.

  The results are shown in Tables 1 and 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 (14)

Including epoxy resin, curing agent, silica, and melamine,
The epoxy resin composition whose content of the said melamine exists in the range of 1 to 8 weight% in solid content of 100 weight% of an epoxy resin composition. Further comprising a maleimide compound,
The epoxy resin composition according to claim 1, wherein 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. The epoxy resin composition according to claim 2, 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 epoxy resin composition according to claim 1, wherein the curing agent is a phenol compound.   The phenol compound is at least one selected from the group consisting of a phenol compound having a naphthalene skeleton, a phenol compound having a dicyclopentadiene skeleton, a phenol compound having a biphenyl skeleton, and a phenol compound having an aminotriazine skeleton. The epoxy resin composition of any one of 1-4.   The epoxy resin composition according to any one of claims 1 to 5, wherein a content of the silica is within a range of 5 to 60% by weight in a solid content of 100% by weight of the epoxy resin composition.   The epoxy resin composition according to any one of claims 1 to 6, wherein the silica is spherical silica, and an average particle diameter of the spherical silica measured by a laser diffraction method is 1 µm or less. Further comprising phenoxy resin,
The epoxy resin composition according to any one of claims 1 to 7, wherein a content of the phenoxy resin is within a range of 1 to 10% by weight in a solid content of 100% by weight of the epoxy resin composition.   The sheet-like molded object formed by shape | molding the epoxy resin composition of any one of Claims 1-8 in a sheet form.   A laminate comprising: a cured body obtained by curing the sheet-like molded body according to claim 9; and a metal layer laminated on at least one surface of the cured body.   The laminated board according to claim 10, wherein the metal layer is formed as a circuit.   A prepreg in which a porous substrate is impregnated with the epoxy resin composition according to any one of claims 1 to 8.   The epoxy resin composition according to any one of claims 1 to 8, a sheet-like molded body formed by molding the epoxy resin composition into a sheet, or the epoxy resin composition is a porous substrate. A cured product formed by heating and curing a prepreg impregnated in the above. A plurality of laminated cured bodies, 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 9.

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