TWI401271B - Pre-hardened, coarsened pre-hardened and laminated - Google Patents

Description

Pre-cured material, roughened pre-cured material and laminated body

The present invention relates to a pre-cured product obtained by using an epoxy resin material comprising an epoxy resin, a hardener and cerium oxide, and hardening the epoxy resin material; and a roughening pre-preparation using the pre-cured material Hardened material and laminated body.

Conventionally, various resin compositions have been used to obtain electronic components such as laminates and printed wiring boards. For example, in the multilayer printed wiring board, a resin composition is used in order to form an insulating layer for insulating the inner layers or to form an insulating layer located in the surface layer portion.

As an example of the above resin composition, Patent Document 1 listed below discloses a resin composition comprising an epoxy resin, a curing agent, a phenoxy resin, and an inorganic filler having an average particle diameter of 0.01 to 2 μm. Further, Patent Document 1 discloses a resin composition comprising an epoxy resin, a curing agent, and an inorganic filler having an average particle diameter of 0.1 to 10 μm.

In Patent Document 1, each layer of a multilayer film having a two-layer laminated structure is formed using the above two different resin compositions. It is described that the multilayer film can be satisfactorily embedded in a gap or the like provided on a substrate.

Patent Document 2 listed below discloses at least one of an epoxy resin, a hardener, a phenoxy resin, and a polyvinyl acetal resin, and a phosphorus-containing benzoate. A resin composition of a compound. Patent Document 2 discloses that when the cured product obtained by curing the resin composition is subjected to a roughening treatment, even if the roughness of the roughened surface is relatively small, the roughened surface-plated conductor can be obtained. An insulating layer with high adhesion and excellent flame retardancy.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-302677

[Patent Document 2] WO 2009/038166A1

In Patent Document 1, since a multilayer film is prepared by preparing two kinds of resin compositions, there is a problem that the production of the multilayer film is time consuming and laborious, and the cost is high.

In Patent Document 2, although the resin composition has the above-described composition, the roughness is reduced, but the roughness of the roughened surface is not sufficiently reduced.

Further, in the multilayer film described in Patent Document 1 and the resin composition described in Patent Document 2, when the surface of the cured product obtained by curing the hardened material is formed into a metal layer by a plating treatment, it is difficult to sufficiently form the metal layer. Improve the bonding strength between the hardened material and the metal layer.

An object of the present invention is to provide a surface roughness which can reduce the surface roughness of a roughened pre-cured material, and can improve pre-hardening of the adhesion strength between the cured product and the metal layer which is obtained by hardening the roughened pre-cured material. And a roughened pre-cured material and a laminate using the pre-cured material.

According to a broader aspect of the present invention, there is provided a pre-cured material obtained by curing an epoxy resin material, comprising: a first main surface and a second main surface, wherein the first main surface is a In the roughening treatment, the epoxy resin material comprises an epoxy resin, a curing agent and cerium oxide, and the cerium oxide comprises a first small particle size cerium oxide having a particle diameter of 0.01 μm or more and less than 0.5 μm. And a second largest particle size ceria having a particle diameter of 0.5 μm or more and 20 μm or less; in the pre-cured material, the first small-sized ceria is present in the roughened surface, that is, the above-mentioned The first main surface side is biased, and the second large particle size ceria is present in a manner that is mostly present on the second main surface side.

In a specific aspect of the pre-cured material of the present invention, the roughened surface, that is, 100% by volume of all the cerium oxide contained in the first region having a thickness of 0.3 μm on the surface portion of the first main surface side The content of the second largest particle size ceria is 5% by volume or less.

In another specific aspect of the pre-cured material of the present invention, the epoxy resin material before pre-hardening in a temperature range of 60 to 120 ° C has a minimum melt viscosity of 50 Pa‧s or more and 150 Pa‧s or less.

In other specific aspects of the pre-cured material of the present invention, the epoxy resin material further comprises a phenoxy resin.

The roughened pre-cured material of the present invention is obtained by subjecting the first main surface of the pre-cured material according to the present invention to a roughening treatment.

In a specific aspect of the roughened pre-cured material of the present invention, the pre-cured material is subjected to a swelling treatment before the roughening treatment.

The laminate of the present invention comprises a cured product obtained by curing a roughened pre-cured material obtained by subjecting the first main surface of the pre-cured material according to the present invention to a roughening treatment; and laminating the cured product The metal layer of the roughened surface. The adhesion strength between the cured product and the metal layer is preferably 0.39 N/mm or more.

The pre-cured material of the present invention is obtained by curing an epoxy resin material containing an epoxy resin, a hardener, and ceria, and the ceria contains the first particle having a particle diameter of 0.01 μm or more and less than 0.5 μm. The small-sized cerium oxide and the second large-sized cerium oxide having a particle diameter of 0.5 μm or more and 20 μm or less, and the first small-sized cerium oxide is present in the pre-cured material. The surface of the roughened surface, that is, the first main surface side, is biased, and the second large-sized cerium oxide is present in a manner that is mostly present on the second main surface side, so that the pre-cured material is present. When the first main surface is subjected to the roughening treatment, the surface roughness of the roughened surface of the roughened pre-cured material can be reduced. Further, in the case where a metal layer is formed on the surface of the cured product obtained by curing the roughened pre-cured material, the adhesion strength between the cured product and the metal layer can be improved.

Hereinafter, the present invention will be described with reference to the specific embodiments and examples of the present invention.

The pre-cured material of the present invention is obtained by hardening an epoxy resin material. In Fig. 1, a front cross-sectional view schematically shows a pre-cured product according to an embodiment of the present invention.

The pre-cured material 1 shown in Fig. 1 is laminated on the upper surface 6a of the laminated object member 6. The pre-cured material 1 includes a first main surface 1a and a second main surface 1b. The first main surface 1a is a roughened surface. The second main surface 1b is in contact with the upper surface 6a of the layered object member 6. The above epoxy resin material for obtaining the pre-cured material 1 contains an epoxy resin, a hardener, and ceria 2.

Cerium dioxide 2 includes a first small particle size ceria 2A having a particle diameter of 0.01 μm or more and less than 0.5 μm, and a second large particle size ceria 2B having a particle diameter of 0.5 μm or more and 20 μm or less. .

In the pre-cured material 1, the first small-sized ceria 2A is present in a manner that is mostly present on the roughened surface, that is, on the side of the first main surface 1a. In the pre-cured material 1, the second largest particle size ceria 2B is present in a manner that is mostly present on the second main surface 1b side.

In the pre-cured material 1, when the first small-sized ceria 2A and the second-large-sized ceria 2B are biased as described above, the first main surface 1a can be roughened. On the first main surface 1a, fine pores in which the first small-sized ceria 2A is separated are formed. As a result, the surface roughness of the roughened surface can be lowered. Further, in the case where a metal layer is formed on the surface of the cured product obtained by curing the roughened pre-cured material by the roughening treatment, the adhesion strength between the cured product and the metal layer can be improved. Further, by making the first small particle size ceria 2A and the second large particle size ceria 2B bias as described above, the precured material 1 and the first main body of the precured material 1 can be further improved. The strength of the roughened pre-cured material obtained by roughening the surface 1a. In particular, by using the second largest particle size ceria 2B, the interface between the cerium oxide and the resin can be reduced, the melt viscosity can be lowered, and the embedding processability can be improved, and the pre-cured material 1 and the roughened pre-cured material and The electrical insulation, water absorption and chemical resistance of the cured product are improved.

Further, in order to further reduce the surface roughness of the roughened surface of the roughened pre-cured material and further improve the adhesion strength between the cured product and the metal layer, the pre-cured material and the roughened pre-cured material are further improved. From the viewpoint of the strength, the surface of the roughened surface, that is, the first region R1 having a thickness of 0.3 μm on the surface of the first main surface 1a side (the region above the dotted line in FIG. 1) In 100% by volume of cerium oxide, the content of the second largest particle size ceria is preferably 5% by volume or less, more preferably 4% by volume or less, still more preferably 3% by volume or less, and particularly preferably 0% by volume. . It is also possible that the first region R1 is completely free of the second largest particle size ceria.

The second main surface 1b side connected to the first region R1 is further reduced from the viewpoint of further reducing the surface roughness of the roughened surface of the roughened pre-cured material and further improving the adhesion strength between the cured product and the metal layer. In the 100% by volume of all the cerium oxide contained in the second region R2 (the region lower than the broken line in FIG. 1), the content of the second large-sized cerium oxide 2B is preferably 95% by volume or more. It is 100% by volume or less, more preferably 96% by volume or more, and still more preferably 97% by volume or more.

Furthermore, the second region R2 is connected to the first region R1. The first region R1 is in contact with the second region R2. The second region R2 is the remaining region excluding the first region R1.

The minimum melt viscosity of the epoxy resin material before pre-hardening in the temperature region of 60 to 120 ° C is preferably 300 Pa‧s or less. The melt viscosity is preferably 10 Pa ‧ or more, more preferably 50 MPa ‧ s or more, still more preferably 50 MPa ‧ s, more preferably 150 MPa ‧ s or less, and still more preferably 120 Pa ‧ s or less It is especially good for 100 Pa‧s or less. When the melt viscosity of the epoxy resin material is not less than the above lower limit and not more than the above upper limit, the surface roughness of the roughened surface of the roughened precured material is further lowered, and the adhesion strength between the cured product and the metal layer is further improved.

The above "melt viscosity" is a value measured by heating the epoxy resin material before pre-curing from 50 ° C to 150 ° C by a rheometer. Examples of the rheometer include "AR-2000" manufactured by TA Instrument Co., Ltd., and the like.

Further, when only the first small particle size ceria 2A and the second large particle size ceria 2B are used in combination, the first small particle size ceria 2A and the second large particle size ceria are present. 2B is not biased as described above. In the pre-cured body 1, the first small-sized ceria 2A and the second-large-sized ceria 2B are partially biased as described above, and specific examples thereof include temperature and pressure depending on the lamination. Further, a method of biasing the resin on the surface; a method of biasing the resin on the surface during flattening and pressurization; and a method of biasing the resin during hardening or the like. In the pre-hardened body 1, in order to make the first small-sized ceria 2A and the second-large-sized ceria 2B biased as described above, it is preferred to soften each of the epoxy resin and the hardener. Or the melting point is close to the lamination temperature, and it is preferred to carry out the lamination process and the planarization process in different steps.

Hereinafter, the details of each component contained in the above epoxy resin material will be described.

(epoxy resin material)

[Epoxy resin]

The epoxy resin contained in the epoxy resin material is not particularly limited. As the epoxy resin, a previously known epoxy resin can be used. The epoxy resin refers to an organic compound having at least one epoxy group. Epoxy resins may be used alone or in combination of two or more.

Examples of the epoxy resin include a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a phenol novolak epoxy resin, and a biphenol novolak epoxy resin. Biphenol type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene novolac type epoxy resin, An epoxy resin having an adamantane skeleton, an epoxy resin having a tricyclodecane skeleton, and a skeleton having three Nuclear epoxy resin, etc.

The epoxy resin is preferably a biphenyl aldehyde varnish type epoxy resin from the viewpoint of further reducing the surface roughness of the roughened surface of the roughened pre-cured material and further improving the adhesion strength between the cured product and the metal layer. Resin or dicyclopentadiene type epoxy resin.

The epoxy resin is preferably a bifunctional or higher epoxy resin, more preferably a polyfunctional epoxy resin. Examples of the polyfunctional epoxy resin include a trifunctional alicyclic epoxy monomer ("Epolead GT301" manufactured by Union Carbide Co., Ltd.), and three in the skeleton. Nuclear trivalent epoxy resin (DENACOL EX-301 manufactured by Nagase ChemteX Corporation, "TEPIC-S" manufactured by Nissan Chemical Industries Co., Ltd.), biphenol aldehyde as a multifunctional epoxy resin Varnish type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd.), dicyclopentadiene novolac type epoxy resin ("HP-7200" manufactured by DIC Corporation), bisphenol A novolak type epoxy resin ( Mitsubishi Chemical "157-S70" and so on.

The melting point or softening point of the epoxy resin is preferably 50 ° C or higher, more preferably 65 ° C or higher, and is preferably 90 ° C or lower, more preferably 85 ° C or lower. When the melting point or softening point of the epoxy resin is not less than the above lower limit and not more than the above upper limit, the first small particle size can be obtained in the pre-cured material obtained by pre-curing the epoxy resin material on the layered member. Cerium oxide and the second largest particle size ceria are present in the above preferred biased state. Therefore, when the surface of the pre-cured material is roughened, the surface roughness of the roughened surface of the roughened pre-cured material is further lowered. Further, when the melting point or softening point of the epoxy resin is not less than the above lower limit and not more than the above upper limit, the strength of the cured product obtained by curing the roughened precured material and the metal layer is also improved.

The epoxy equivalent of the epoxy resin is preferably 90 or more from the viewpoint of further reducing the surface roughness of the roughened surface of the roughened pre-cured material and further improving the adhesion strength between the cured product and the metal layer. More preferably, it is 100 or more, preferably 1000 or less, more preferably 800 or less.

The weight average molecular weight of the above epoxy resin is preferably 5,000 or less. In this case, the content of cerium oxide in the epoxy resin material can be increased. Further, even if the content of cerium oxide is large, a resin composition as an epoxy resin material having high fluidity can be obtained. On the other hand, by using an epoxy resin having a weight average molecular weight of 5,000 or less and a phenoxy resin in combination, it is possible to suppress a decrease in melt viscosity of a B-stage film which is an epoxy resin material. Therefore, in the case where the B-stage semi-cured film is laminated on the substrate, the biased state of the cerium oxide can be made good.

[hardener]

The curing agent contained in the epoxy resin material is not particularly limited. As the hardener, a previously known hardener can be used. The hardener may be used singly or in combination of two or more.

Examples of the curing agent include a cyanate resin (cyanate curing agent), a phenol compound (phenol curing agent), an amine compound (amine curing agent), a thiol compound (thiol curing agent), an imidazole compound, and a phosphine. Compounds, acid anhydrides, active ester compounds, dicyandiamide, and the like. Among them, the curing agent is preferably a cyanate resin or a phenol compound from the viewpoint of obtaining a cured product whose dimensional change is further reduced by heat. The above curing agent is preferably a cyanate resin, and a phenol compound is also preferred. The above curing agent preferably has a functional group reactive with the epoxy group of the above epoxy resin.

The above hardener is preferably a cyanate resin, a phenol compound or the like in terms of further reducing the surface roughness of the roughened surface of the roughened pre-cured material and further improving the adhesion strength between the cured product and the metal layer. Active ester compound. Further, from the viewpoint of imparting good insulation reliability by the curing agent, the above-mentioned curing agent is more preferably a cyanate resin.

By using the above cyanate resin, the workability of the B-stage semi-cured film having a large content of cerium oxide can be improved, and the glass transition temperature of the cured product can be further improved. The cyanate resin is not particularly limited. As the cyanate resin, a previously known cyanate resin can be used. The cyanate resin may be used alone or in combination of two or more.

Examples of the cyanate resin include a novolac type cyanate resin and a bisphenol type cyanate resin. Examples of the bisphenol-type cyanate resin include a bisphenol A type cyanate resin, a bisphenol F type cyanate resin, and a tetramethyl bisphenol F type cyanate resin.

The commercially available product of the cyanate resin may, for example, be a phenol novolac type cyanate resin ("PT-30" and "PT-60" manufactured by Lonza Japan Co., Ltd.), and a bisphenol A dicyanate. three A prepolymer of a terpolymer ("BA230", "BA200", and "BA3000" manufactured by Lonza Japan Co., Ltd.) was formed.

By using the above phenol compound, the adhesion strength between the cured product and the metal layer can be further improved. Further, by using the phenol compound, for example, the surface of the copper provided on the surface of the cured product can be further subjected to a blackening treatment or a Cz treatment to further improve the adhesion between the cured product and the copper.

The phenol compound is not particularly limited. As the phenol compound, a previously known phenol compound can be used. These phenol compounds may be used alone or in combination of two or more.

Examples of the phenol compound include novolac type phenol, biphenol type phenol, naphthalene type phenol, dicyclopentadiene type phenol, and aralkyl type phenol.

The commercially available product of the phenol compound may, for example, be a novolac type phenol ("TD-2091" manufactured by DIC Corporation), a biphenol novolak type phenol ("MEH-7851" manufactured by Mingwa Chemical Co., Ltd.), and an aralkyl group. A phenolic compound ("MEH-7800" manufactured by Minghe Chemical Co., Ltd.).

The phenol compound is preferably a biphenol novolak type phenol or aryl, from the viewpoint of further reducing the surface roughness of the roughened surface of the roughened pre-cured material and further improving the adhesion strength between the cured product and the metal layer. Alkyl phenol compound.

The above active ester compound is not particularly limited. As a commercial item of the above-mentioned active ester compound, "EXB-9460S-65T" manufactured by DIC Corporation, etc. are mentioned.

Further reducing the surface roughness of the roughened surface of the roughened pre-cured material, and further improving the adhesion strength between the cured product and the metal layer, and the hardening by the hardener imparting good insulation reliability The agent preferably contains a hardener having an equivalent weight of 250 or less. The equivalent of the above-mentioned hardener, for example, when the curing agent is a cyanate resin, represents a cyanate group equivalent, when the curing agent is a phenol compound, it represents a phenolic hydroxyl equivalent, and the hardener is an active ester compound. In the case of the case, it represents the active ester group equivalent.

By using a curing agent having a weight average molecular weight of 1,000 or less and a phenoxy resin in combination, the decrease in the melt viscosity of the B-stage semi-cured film as the epoxy resin material can be suppressed. Therefore, in the case where the B-stage semi-cured film is laminated on the substrate, the biased state of the cerium oxide can be made good.

The total content of the epoxy resin and the hardener is preferably 100% by weight of the total solid content (hereinafter sometimes abbreviated as total solid content B) excluding the above-mentioned ceria contained in the epoxy resin material. It is 75% by weight or more, more preferably 80% by weight or more, and 100% by weight or less, preferably 99% by weight or less, and more preferably 97% by weight or less.

When the total content of the epoxy resin and the curing agent is at least the above lower limit and not more than the above upper limit, a more excellent cured product can be obtained, and the melt viscosity can be adjusted, so that the presence of cerium oxide can be improved and prevented. During the hardening process, the B-stage semi-cured film wets and spreads to an area other than expected. Further, it is possible to further suppress the dimensional change caused by heat of the cured product. In addition, when the total content of the epoxy resin and the curing agent is less than the lower limit, it may be difficult to embed the resin composition or the B-stage semi-cured film in the pores or irregularities of the circuit board, and further, the cerium oxide There is a tendency for the state to deteriorate. In addition, when the total content of the epoxy resin and the curing agent exceeds the above upper limit, the melt viscosity is too low, and the B-stage semi-cured film tends to be wetted and diffused in a region other than the expected area during the curing process. The term "total solids component B" means the sum of epoxy resin, hardener and other solid components to be blended as needed. Ceria is not included in total solids component B. The "solid content component" means a non-volatile component and is a component that does not volatilize when formed or heated.

The blending ratio of the epoxy resin to the hardener is not particularly limited. The blending ratio of the epoxy resin and the hardener can be appropriately determined depending on the type of the epoxy resin and the hardener.

[filler]

The above epoxy resin material contains cerium oxide.

The average particle diameter of all of the cerium oxide contained in the epoxy resin material is preferably 0.1 μm or more and 0.8 μm or less.

The average particle diameter of the above cerium oxide may be a value which is 50% of the median diameter (d50). The above average particle diameter can be measured by a particle size distribution measuring apparatus using a laser diffraction type scattering method.

The cerium oxide contained in the epoxy resin material contains the first small particle size ceria having a particle diameter of 0.01 μm or more and less than 0.5 μm, and the second particle having a particle diameter of 0.5 μm or more and 20 μm or less. Large particle size cerium oxide. The first small particle size ceria is the cerium oxide having a particle diameter of 0.01 μm or more and less than 0.5 μm among all the cerium oxide contained in the epoxy resin material. The second largest particle size ceria is cerium oxide having a particle diameter of 0.5 μm or more and 20 μm or less among all of the cerium oxide contained in the epoxy resin material.

Further, the particle diameter of the first small particle size ceria and the second large particle size ceria is a diameter in the case where the ceria is spherical, and the oxidation is In the case of a shape other than a sphere, it means the maximum diameter.

The above-mentioned first small-sized ceria having a relatively small particle diameter is combined with the specific second-large-sized ceria having a relatively large particle diameter, and the epoxy resin and the epoxy resin are used together. In the pre-cured material before the roughening treatment in which the above-mentioned epoxy resin material is pre-cured, the cerium oxide is present in a good state. As a result, when the surface of the pre-cured material is roughened, the surface roughness of the roughened surface of the roughened pre-cured material can be reduced, and the cured product obtained by hardening the roughened pre-cured material can be improved. The strength of the bond with the metal layer.

The above cerium oxide is more preferably molten cerium oxide. By using molten cerium oxide, the surface roughness of the roughened surface of the roughened pre-cured material can be effectively reduced. The shape of the cerium oxide is preferably approximately spherical.

Preferably, the cerium oxide contained in the epoxy resin material, the first small-sized cerium oxide and the second large-sized cerium oxide are surface-treated, respectively, and more preferably a surface is formed by a coupling agent. deal with. Thereby, the surface roughness of the roughened surface of the roughened pre-cured material is further lowered, and the adhesion strength between the hardened material and the metal layer is further improved, and the wiring insulation reliability and interlayer insulation reliability can be further improved. .

Examples of the coupling agent include a decane coupling agent, a titanate coupling agent, and an aluminum coupling agent. The coupling agent used in the above surface treatment is preferably epoxy decane, amino decane, vinyl decane, decyl decane, thiodecane, N-phenyl-3-aminopropyl decane, decyl (meth) acrylate, Isocyanate decane or ureido decane, and the like.

Preferably, the epoxy resin material comprises the first small particle size ceria and the second large particle size ceria in a weight ratio of 5:95 to 50:50, more preferably 10:90. 30:70 comprises the first small particle size ceria and the second large particle size ceria. By subjecting the epoxy resin material to the first small particle size ceria and the second large particle size ceria in the above weight ratio, the roughened pretreated surface can be roughened. The surface roughness is further lowered, and the bonding strength between the hardened material and the metal layer is further increased.

The content of the above cerium oxide is not particularly limited. All of the above-mentioned ceria (including the first small particle size ceria and the second one) in 100% by weight of the total solid content (hereinafter sometimes abbreviated as total solid content A) contained in the epoxy resin material The content of the large-sized cerium oxide is preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, more preferably 85% by weight or less, still more preferably 80% by weight or less. When the content of the cerium oxide is not less than the above lower limit and not more than the above upper limit, the linear thermal expansion coefficient of the resin can be suppressed, and the difference in expansion coefficient between copper and bismuth can be relaxed, and the thermal shock reliability can be improved, and the warpage suppressing effect can be obtained. The processing precision is improved, and the cerium oxide can be removed by the roughening treatment, and the adhesion strength to the metal is improved by forming the roughened pores. The term "total solids component A" means the sum of epoxy resin, hardener, cerium oxide and solid components as needed. The "solid content component" means a non-volatile component and is a component that does not volatilize when formed or heated.

The total content of the first small particle diameter ceria and the second large particle size ceria is preferably 60% by weight or more, more preferably 80% by weight based on 100% by weight of the total content of the cerium oxide. More preferably, it is 90% by weight or more, and more preferably 95% by weight or more and 100% by weight or less. Further, all of the above-mentioned ceria may be the first small particle size ceria and the second large particle size ceria.

[Details of other ingredients and epoxy materials]

The above epoxy resin material may also contain a hardening accelerator as needed. The hardening speed can be further accelerated by using a hardening accelerator. By rapidly hardening the epoxy resin material, the crosslinked structure of the cured product can be made uniform, and the number of unreacted functional groups can be reduced, with the result that the crosslinking density can be increased. The hardening accelerator is not particularly limited. As the hardening accelerator, a conventionally known hardening accelerator can be used. These hardening accelerators may be used alone or in combination of two or more.

Examples of the curing accelerator include an imidazole compound, a phosphorus compound, an amine compound, and an organometallic compound.

Examples of the imidazole compound include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-benzene. 4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole , 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl- 2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl -(1')]-ethyl-all three 2,4-Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-all three 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-all three 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-all three Iso-cyanuric acid adduct, 2-phenylimidazolium isocyanurate adduct, 2-methylimidazolium isocyanurate adduct, 2-phenyl-4,5-dihydroxymethyl Imidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole.

Examples of the phosphorus compound include triphenylphosphine and the like.

Examples of the amine compound include diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, and 4,4-dimethylaminopyridine.

Examples of the organometallic compound include zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octoate, cobalt(II) diacetate, and cobalt (III) triacetate.

The hardening accelerator is preferably an imidazole compound from the viewpoint of improving the insulation reliability of the cured product.

The content of the above hardening accelerator is not particularly limited. From the viewpoint of effectively curing the epoxy resin material, the content of the curing accelerator is preferably 0.01% by weight or more, preferably 3% by weight or less, based on 100% by weight of the total solid content component B. Further, the total solid content component B includes the above-described hardening accelerator.

The above epoxy resin material preferably contains a thermoplastic resin. By using a thermoplastic resin, the followability of the epoxy resin material to the unevenness of the circuit can be improved, and the surface roughness of the roughened surface of the roughened pre-cured material can be further reduced, and the roughened surface can be further obtained. The roughness is more uniform.

Examples of the thermoplastic resin include a phenoxy resin and a polyvinyl acetal resin. The thermoplastic resin is preferably used in view of the fact that the cerium oxide is favorably biased to further reduce the surface roughness of the roughened surface of the roughened pre-cured material and further improve the adhesion strength between the cured product and the metal layer. Phenoxy resin.

Examples of the phenoxy resin include a phenoxy resin having a skeleton such as a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a biphenyl skeleton, a novolac skeleton, and a naphthalene skeleton.

After the surface of the pre-cured material is subjected to a roughening treatment and the plating treatment is performed to form a metal layer, the adhesion strength between the cured product and the metal layer can be improved. Therefore, the phenoxy resin preferably has a biphenyl skeleton. More preferably, it has a biphenol skeleton.

Specific examples of the phenoxy resin include "YP50", "YP55" and "YP70" manufactured by Dongdu Chemical Co., Ltd., and "1256B40", "4250" and "4256H40" manufactured by Mitsubishi Chemical Corporation. 4275", "YX6954BH30", "YX8100BH30", "YL7600DMAcH25" and "YL7213BH30".

The weight average molecular weight of the phenoxy resin is preferably 5,000 or more, preferably 100,000 or less.

The content of the above thermoplastic resin is not particularly limited. The content of the thermoplastic resin (in the case where the thermoplastic resin is a phenoxy resin, the content of the phenoxy resin) is preferably 0.1% by weight or more, more preferably 100% by weight of the total solid content B. It is 0.5% by weight or more, more preferably 1% by weight or more, preferably 40% by weight or less, more preferably 30% by weight or less, still more preferably 20% by weight or less, and still more preferably 15% by weight or less. When the content of the thermoplastic resin is not less than the above lower limit and not more than the above upper limit, the dimensional change due to heat of the cured product is further reduced. In addition, when the content of the thermoplastic resin is at most the above upper limit, the embedding property of the epoxy resin material in the holes or irregularities of the circuit board becomes good. Further, the total solid content component B contains the above thermoplastic resin.

In order to improve impact resistance, heat resistance, resin compatibility, workability, etc., a coupling agent, a coloring agent, an antioxidant, an ultraviolet deterioration preventing agent, an antifoaming agent, an adhesion promoter, and the like may be added to the epoxy resin material. The thixotropic agent and other resins other than the above resins.

Examples of the coupling agent include a decane coupling agent, a titanium coupling agent, and an aluminum coupling agent. Examples of the decane coupling agent include amino decane, imidazolium, vinyl decane, phenylamino decane, and epoxy decane.

The content of the above coupling agent is not particularly limited. The content of the coupling agent is preferably 0.01% by weight or more and 5% by weight or less based on 100% by weight of the total solid content component B.

Examples of the other resin include a polyphenylene ether resin, a divinyl benzyl ether resin, a polyarylate resin, a diallyl phthalate resin, a polyimine resin, and a benzo compound. Resin, benzo An azole resin, a bis-xenylenediamine resin, an acrylate resin, or the like. Further, the total solid content component B contains the above coupling agent.

The above epoxy resin material may also contain a solvent. Examples of the solvent include acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, and 2-acetamidine. Oxy-1-methoxypropane, toluene, xylene, methyl ethyl ketone, N,N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, n-hexane, ring Hexane, cyclohexanone, and a mixture of naphtha. These solvents may be used alone or in combination of two or more.

A resin composition containing a solvent can be used as the varnish. The viscosity of the varnish can be adjusted by adjusting the content of the solvent according to the use. In the epoxy resin material, the content of the solvent is preferably 10 parts by weight or more and 1000 parts by weight or less based on 100 parts by weight of the total solid content component A.

(Details of B-stage semi-cured film, laminated film, pre-cured material, roughened pre-cured material, and laminated body)

The epoxy resin material may be a resin composition, and the resin composition may be a B-stage semi-cured film formed into a film. The B-stage semi-cured film can be obtained by molding the above resin composition into a film shape.

As a method of forming the resin composition into a film shape, for example, the resin composition is melt-kneaded using an extruder, and after extrusion, a film-like extrusion is formed by a T-die or a circular die. A molding method; a casting molding method in which a resin composition is dissolved or dispersed in a solvent such as an organic solvent, and then cast into a film; and other conventional film forming methods and the like are known. Among them, an extrusion molding method or a casting molding method is preferred because it can promote thinning. The film includes a sheet.

The resin composition is molded into a film shape, and is heated and dried at 90 to 200 ° C for 10 to 180 minutes to the extent that heat hardening is not excessively performed, whereby a B-stage semi-cured film can be obtained.

The film-like resin composition obtainable by the drying step as described above is referred to as a B-stage semi-cured film.

The above-mentioned B-stage semi-cured film is a semi-cured material in a semi-hardened state. The semi-hardened material is not completely hardened and can be further hardened.

The above resin composition is suitably used for forming a laminated film comprising a substrate and a B-stage semi-cured film laminated on one surface of the substrate. The B-stage semi-cured film of the laminated film is formed of the above resin composition.

The base material of the laminated film may be a polyester resin film such as a polyethylene terephthalate film or a polybutylene terephthalate film, an olefin resin film such as a polyethylene film or a polypropylene film, or a poly A metal foil such as a ruthenium imide resin film, a copper foil or an aluminum foil. The surface of the above substrate may also be subjected to a mold release treatment as needed.

In the case where the above epoxy resin material is used as an insulating layer of a circuit, the thickness of the layer formed of the epoxy resin material is preferably greater than the thickness of the conductor layer forming the circuit. The thickness of the layer formed of the epoxy resin material is preferably 5 μm or more, more preferably 6 μm or more, still more preferably 10 μm or more, more preferably 200 μm or less, still more preferably 65 μm or less, and still more preferably It is 50 μm or less.

The epoxy resin material is a B-stage semi-cured film, and it is preferred that the B-stage semi-cured film is laminated on the laminated object member by lamination, and then the B-stage semi-cured film is cured to obtain a pre-cured product. The lamination temperature is preferably 55 ° C or higher, more preferably 65 ° C or higher, and is preferably 130 ° C or lower, more preferably 120 ° C or lower. The lamination pressure is preferably 0.5 MPa or more, more preferably 0.8 MPa or more, more preferably 1.5 MPa or less, still more preferably 1.2 MPa or less. By laminating a B-stage semi-cured film as an epoxy resin material under the above-mentioned appropriate conditions, the first small particle size ceria and the second large particle size ceria can be present in the pre-cured material. The status has become even better. In the B-stage semi-cured film composed of the epoxy resin material as described above, the melt viscosity in the vicinity of the lamination temperature is lowered. In particular, the B-stage semi-cured film composed of a phenoxy resin having a low melt viscosity, a liquid epoxy resin, and a cyanate curing agent has a melt viscosity of 150 Pa‧s or less, and the fluidity of the resin component. improve. By performing the lamination treatment in this state, the first small particle size ceria can be selectively moved at the point of melting of the resin, and the first small particle size is oxidized on the outermost surface of the B-stage semi-cured film. The crucible moves with the resin to make it flat during lamination. By this movement, the first small-sized cerium oxide is often biased to exist on the surface side of the first roughening treatment. That is, in the upper layer portion of the pre-cured material, the first small-diameter ceria having a relatively small particle diameter is often present, and in the lower portion, the second-largest-diameter ceria having a relatively large particle diameter is often present. As a result, when the surface of the pre-cured material is roughened, the surface roughness of the roughened surface of the roughened pre-cured material is lowered. Further, the bonding strength between the cured product and the metal layer is also improved.

A well-known method can be used for the method of laminating the above-mentioned B-stage semi-cured film by lamination, and it is not specifically limited. For example, the B-stage semi-cured film is laminated on a circuit board, and it is preferable to laminate the laminated film from the B-stage semi-cured film side, and pressurize it by a press bonding machine. At this time, heating or heating may not be performed. Next, the laminated object member and the B-stage semi-cured film or the laminated film are heated and pressurized by a parallel plate press type heating and press machine. The B-stage semi-cured film may also be pre-cured by heating and pressurization to form a pre-cured product. The temperature of the heating and the pressure of the pressurization can be appropriately changed, and are not particularly limited.

As a more specific lamination method, for example, using a roll laminator, the roll temperature is set to 20 to 120 ° C at a roll diameter of 60 mm and a roll peripheral speed of 0.1 to 10 m/min. The pressure of 6 MPa is applied, and the B-stage semi-cured film is laminated on the circuit board, or the laminated film is laminated on the layered object from the B-stage semi-cured film side.

Preferably, the B-stage semi-cured film or the laminated film is laminated on the laminated object member, and then heat-treated at 160 to 200 ° C for 20 minutes to 180 minutes. The B-stage semi-cured film can be pre-cured by heat treatment to obtain a pre-cured product. The substrate of the laminated film may be removed before the pre-cured material is formed, or may be removed after the pre-cured material is formed. By laminating under the above conditions, the roughening treatment is performed to form fine irregularities on the surface of the roughened pre-cured material. The pre-cured material is preferably hardened at a temperature 10 to 60 ° C lower than the glass transition temperature of the final cured product.

If necessary, it is also possible to heat and pressurize the roll using a parallel plate heating press to improve the smoothness of the surface of the pre-cured material. For example, a laminate of a circuit board and a B-stage semi-cured film or a laminated film may be heated and pressurized on a stainless steel plate having a thickness of 1 mm by a parallel plate heating press.

Further, a commercially available apparatus can be used as a pressurizing machine such as a pressurizing laminating machine such as a heat and pressure type roll laminator or a parallel plate heating press machine. The laminate using the roll laminator is preferably carried out under vacuum. The material of the roll of the roll laminating machine can be appropriately selected from rubber rolls having a soft surface and a metal roll having a hard surface. The flat plate of the parallel plate heating press is made of hard metal.

It is also possible to use a roll of a roll laminator and the above-mentioned laminated object member, a B-stage semi-cured film or a laminated film, or a flat plate heating press plate and the above-mentioned laminated object member, a B-stage semi-cured film or a laminated film. A film having a mold release function such as an aluminum foil, a copper foil, a polyester resin film, a fluororesin film or the like is used.

In order to improve the adhesion between the circuit board and the B-stage semi-cured film or the laminated film, a material having flexibility such as a rubber sheet may be used.

Preferably, the pre-cured material is formed by laminating the laminated film from the B-stage semi-cured film side on a circuit board, pressurizing it by a roll laminator, and heating it by a parallel plate press type heating and press machine. Pressurization to form a pre-cured product. Further, in the step of forming the pre-cured material, the laminated film is laminated on the layered pre-cured film side from the B-stage semi-cured film side, and is pressurized by a roll laminator, and then a parallel plate press type heating and press machine is used. Heating and pressurizing to form a pre-cured product, and after being pressurized by a roll laminator and before being heated and pressurized by a parallel plate press type heating and press machine, or by roll bonding After the machine is pressurized and heated and pressurized by a parallel plate press type heating and press machine, the substrate is removed.

The roughened pre-cured material of the present invention is obtained by subjecting the first main surface of the pre-cured material to a roughening treatment. In order to form fine irregularities on the surface of the pre-cured material, it is preferred that the roughened pre-cured material is subjected to a swelling treatment of the pre-cured material before the roughening treatment.

The roughened pre-cured material is preferably subjected to a swelling treatment after pre-curing and before the roughening treatment. Among them, the pre-cured material may not be subjected to swelling treatment.

The layered product of the present invention includes a cured product obtained by curing a roughened pre-cured material obtained by subjecting the first main surface of the pre-cured material to a roughening treatment, and a roughened layer laminated on the cured product. The metal layer on the surface. The adhesion strength between the cured product and the metal layer is preferably 0.39 N/mm or more. The metal layer is preferably a copper layer, more preferably a copper plating layer.

(printed wiring board)

The above epoxy resin material is suitable for forming an insulating layer in a printed wiring board.

The printed wiring board can be obtained, for example, by using a B-stage semi-cured film formed of the above resin composition, and subjecting the B-stage semi-cured film to heat and pressure molding.

For the above-mentioned B-stage semi-cured film, a single-sided or double-area layer metal foil can be used. The method of laminating the above-described B-stage semi-cured film and metal foil is not particularly limited, and a known method can be used. For example, the B-stage semi-cured film may be laminated on the metal foil by a device such as a parallel plate press or a roll bonding machine while being pressurized with or without heating.

(copper foil laminate and multilayer substrate)

The above epoxy resin material is suitable for obtaining a copper foil laminate. An example of the copper foil laminate is a copper foil laminate including a copper foil and a B-stage semi-cured film laminated on one surface of the copper foil. The B-stage semi-cured film of the copper foil laminate can be formed of the above epoxy resin material. By pre-curing the B-stage semi-cured film, a copper foil laminate comprising a pre-cured material can be obtained.

The thickness of the copper foil of the copper foil laminate is not particularly limited. The thickness of the copper foil is preferably in the range of 1 to 50 μm. Further, in order to increase the adhesion strength between the cured product obtained by curing the epoxy resin material and the copper foil, it is preferable that the copper foil has fine irregularities on the surface. The method of forming the unevenness is not particularly limited. Examples of the method for forming the unevenness include a method of forming a treatment using a known chemical solution, and the like.

Further, the above precured material is suitable for obtaining a multilayer substrate. An example of the multilayer substrate is a circuit board including a circuit board and a cured layer laminated on the surface of the circuit board. The cured layer of the multilayer substrate is formed by subjecting the pre-cured material to a roughening treatment, followed by curing the roughened pre-cured material. Preferably, the cured layer is laminated on a surface of the circuit substrate on which the circuit is provided. A portion of the cured layer is preferably buried between the circuits.

More preferably, the multilayer substrate is subjected to a roughening treatment on a surface of the cured layer which is opposite to a surface on which the circuit board is laminated. The roughening treatment method can be a conventionally known roughening treatment method, and is not particularly limited. The surface of the cured layer may also be subjected to a swelling treatment before the roughening treatment.

Moreover, it is preferable that the multilayer substrate further includes a copper plating layer laminated on the roughened surface of the cured layer.

Further, as another example of the multilayer substrate, a circuit board, a cured layer laminated on the surface of the circuit board, and a surface laminated on the surface of the cured layer adjacent to the surface on which the circuit board is laminated may be mentioned. A circuit board of copper foil. Preferably, the cured layer and the copper foil are pre-cured by using a copper foil laminate comprising a copper foil and a B-stage semi-cured film laminated on one surface of the copper foil, and the B-stage semi-cured film is pre-hardened. It is formed by roughening treatment and hardening treatment. Further, the copper foil is preferably an etching process and is a copper circuit.

As another example of the multilayer substrate, a circuit board including a circuit board and a cured layer of a plurality of layers laminated on the surface of the circuit board can be cited. At least one of the cured layers of the plurality of layers is formed of the pre-cured material. Preferably, the multilayer substrate further includes an electric circuit formed by laminating at least one surface of the cured layer formed by curing the epoxy resin material.

In Fig. 2, a laminated body using a pre-cured material according to an embodiment of the present invention is schematically shown in a partially missing front cross-sectional view.

In the laminated body 11 shown in FIG. 2, a plurality of layers of the cured layers 13 to 16 are laminated on the upper surface 12a of the circuit board 12. The cured layer 13 to 16 is an insulating layer. A metal layer 17 is formed in a partial region of the upper surface 12a of the circuit substrate 12. In the cured layers 13 to 16 of the plurality of layers, the cured layers 13 to 15 other than the cured layer 16 on the surface opposite to the side of the circuit substrate 12 are each formed with a metal layer 17 in a partial region of the upper surface. Metal layer 17 is an electrical circuit. A metal layer 17 is disposed between each of the circuit board 12 and the cured material layer 13 and between the layers of the cured layers 13 to 16 which are laminated. The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of a via hole connection and a through hole connection (not shown).

In the laminated body 11, the cured material layers 13 to 16 are formed by curing the epoxy resin material of the present invention. In addition, in FIG. 2, the hole which the cerium oxide and the cerium oxide of the hardened material layers 13-16 are isolate|separated is abbreviate|omitted for convenience of illustration. In the present embodiment, since the surfaces of the cured material layers 13 to 16 are roughened, fine holes (not shown) are formed on the surfaces of the cured material layers 13 to 16. Further, the metal layer 17 reaches the inside of the fine hole. Further, in the laminated body 11, the dimension (L) in the width direction of the metal layer 17 and the dimension (S) in the width direction of the portion where the metal layer 17 is not formed can be made small. Further, in the laminated body 11, good insulation reliability can be imparted between the upper metal layer and the lower metal layer which are not connected by the via hole connection and the via hole connection (not shown).

(swelling treatment and roughening treatment)

As a method of the swelling treatment, for example, a method of treating a pre-cured material by using an aqueous solution of a compound containing a main component such as ethylene glycol or an organic solvent dispersion solution or the like can be used. The swelling liquid used in the swelling treatment usually contains a base as a pH adjuster or the like. The swelling liquid preferably contains sodium hydroxide. Specifically, the swelling treatment can be carried out, for example, by using a 40% by weight aqueous solution of ethylene glycol or the like at a treatment temperature of 30 to 85 ° C for 1 to 30 minutes. The temperature of the above swelling treatment is preferably in the range of 50 to 85 °C. When the temperature of the swelling treatment is too low, the swelling treatment takes a long time, and the roughening of the cured product and the metal layer tends to decrease.

For the above-described roughening treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound or a persulfate compound is used. These chemical oxidizing agents are used as an aqueous solution or an organic solvent dispersion solution after adding water or an organic solvent. The roughening liquid used in the roughening treatment usually contains a base as a pH adjuster or the like. The roughening liquid preferably contains sodium hydroxide.

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 persulfuric acid compound include sodium persulfate, potassium persulfate, and ammonium persulfate.

The method of the above roughening treatment is not particularly limited. As a method of the above roughening treatment, for example, a permanganic acid or permanganate solution of 30 to 90 g/L and a sodium hydroxide solution of 30 to 90 g/L are preferably used at a treatment temperature of 30 to 85 ° C and A method of treating the pre-cured material once or twice for 1 to 30 minutes. The temperature of the above roughening treatment is preferably in the range of 50 to 85 °C.

The arithmetic mean roughness Ra of the roughened surface of the roughened pre-cured material is preferably 50 nm or more, more preferably 350 nm or less, and still more preferably 300 nm or less. In this case, the adhesion strength between the cured product and the metal layer can be further increased, and a finer circuit can be formed on the surface of the cured layer.

(excluding slag treatment)

Further, a through hole may be formed in the pre-cured material or the cured product. In the multilayer substrate or the like, a via hole, a via hole, or the like is formed as a through hole. For example, the via holes may be formed by irradiation of a laser such as a CO ₂ laser. The diameter of the pilot hole is not particularly limited and is about 60 to 80 μm. Due to the formation of the through-holes, a resin residue which is a resin residue derived from a resin component contained in the cured layer is often formed at the bottom of the passage.

In order to remove the above-mentioned dross, it is preferred to subject the surface of the pre-cured material to desmear treatment. There is also a case where the desmear treatment also serves as a roughening treatment. The desmear treatment is sometimes referred to as roughening treatment.

In the desmear treatment, a chemical oxidizing agent such as a manganese compound, a chromium compound or a persulfate compound can be used in the same manner as the above-described roughening treatment. These chemical oxidizing agents are used as an aqueous solution or an organic solvent dispersion solution after adding water or an organic solvent. The desmear treatment liquid used in the desmear treatment usually contains a base. The desmear treatment liquid preferably contains sodium hydroxide.

The method of the above-described desmear treatment is not particularly limited. As the method for treating the desmear, it is preferred to use, for example, a permanganic acid or permanganate solution of 30 to 90 g/L and a sodium hydroxide solution of 30 to 90 g/L at a treatment temperature of 30 to 85 ° C. And a method of treating the pre-cured or cured product once or twice in 1 to 30 minutes. The temperature of the above desmear treatment is preferably in the range of 50 to 85 °C.

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

The materials shown below were used in the examples and comparative examples.

(epoxy resin)

Epoxy resin 1 (bisphenol F type epoxy resin, "830-S" manufactured by DIC Corporation, liquid at room temperature (23 ° C))

Epoxy resin 2 (biphenol novolak type epoxy resin, "NC3000H" manufactured by Nippon Kayaku Co., Ltd., solid at room temperature (23 ° C), softening point is 70 ° C)

Epoxy Resin 3 (dicyclopentadiene type epoxy resin, "HP-7200" manufactured by DIC, solid at room temperature (23 ° C), softening point is 61 ° C)

(hardener)

Active ester compound solution ("EXB-9460S-65T" manufactured by DIC Corporation, active ester equivalent of 223, including active ester compound (solid content) 65% by weight and toluene 35% by weight)

Cyanate resin solution (cyanate hardener, bisphenol A dicyanate III A prepolymer formed as a terpolymer, "BA230S-75" manufactured by Lonza Japan Co., Ltd., having a cyanate equivalent of 230, containing cyanate resin (solid content) of 75 wt% and methyl ethyl ketone 25 weight%)

Phenolic compound (phenolic hardener, "MEH7851-4H" manufactured by Minghe Chemical Co., Ltd., phenolic hydroxyl equivalent of 242)

Phenol compound solution (having amine group III) The phenolic curing agent of the skeleton, "LA3018-50P" manufactured by DIC Corporation, has a phenolic hydroxyl equivalent of 151, and contains 50% by weight of a phenol compound (solid content) and 50% by weight of propylene glycol monomethyl ether)

(hardening accelerator)

Imidazole compound 1 (2-ethyl-4-methylimidazole, "2E4MZ" manufactured by Shikoku Chemicals Co., Ltd.)

Imidazole compound 2 (2-phenyl-4-methyl-5-hydroxymethylimidazole, "2P4MHZ-PW" manufactured by Shikoku Chemicals Co., Ltd.)

(cerium oxide component)

Slurry A containing the first small particle size ceria: contains the first small particle size ceria a (using phenyl decane (phenyl trimethoxy decane, "KBM-103" manufactured by Shin-Etsu Chemical Co., Ltd.) 1% of the granules containing 65% by weight of cerium oxide ("YA050C-MMK" manufactured by Admatech Co., Ltd., having an average particle diameter of 0.05 μm) and 35% by weight of methyl ethyl ketone) A slurry of cerium oxide.

Slurry B containing the first small particle size ceria: containing the first small particle size c2 (using imidazolium ("IM-1000" manufactured by Nippon Mining Co., Ltd.) for cerium oxide (Electrical Chemistry) "UFP-30" manufactured by Industrial Co., Ltd., having an average particle diameter of 0.1 μm), 30% by weight, and 70% by weight of N,N-dimethylformamide, containing the first small particle diameter A slurry of cerium oxide.

Slurry X containing both the first small particle size ceria and the second largest particle size ceria: containing the first small particle size ceria and the second largest particle size x2 (utilizing Epoxy decane (3-glycidoxypropyltrimethoxy decane, "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.) p-cerium oxide ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 μm A slurry containing 70% by weight and 30% by weight of methyl ethyl ketone containing both the first small particle size ceria and the second large particle size ceria.

Slurry X has a broad particle size distribution including cerium oxide from a particle size of 0.01 μm to a particle size of 20 μm. In the slurry X, the content of the first small particle diameter ceria is 50% by volume in the total of 100% by volume of the first small particle size ceria and the second largest particle size ceria. The content of the large particle size cerium oxide x of 2 is 50% by volume.

Slurry Y containing the second largest particle size ceria: contains the second largest particle size yttrium y (using imidazolium ("IM-1000" manufactured by Nippon Mining Co., Ltd.) for cerium oxide (Deshan) Manufactured "UF-320" with an average particle size of 3.5 μm, a coarse cut point of 20 μm), 50% by weight, and 50 parts by weight of N,N-dimethylformamide % of a slurry containing a second largest particle size ceria.

(thermoplastic resin)

Phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation)

(Example 1)

(1) Production of resin composition and laminated film

5 parts by weight of the slurry A containing the first small particle size ceria and 55 parts by weight of the solid content of the slurry Y containing the second largest particle size of cerium oxide in terms of the solid content 10 parts by weight of epoxy resin 1 (bisphenol F type epoxy resin, "830-S" manufactured by DIC Corporation), 10 parts by weight of epoxy resin 2 (biphenol novolac type epoxy resin, Japanese chemical) "NC3000H" manufactured by the company, 10 parts by weight of a cyanate resin solution (cyanate curing agent, "BA230S-75" manufactured by Lonza Japan Co., Ltd.) and 0.5 part by weight of an imidazole compound 1 (solid content) "2E4MZ" manufactured by Shikoku Chemicals Co., Ltd.) and 9.5 parts by weight of phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation) were stirred at 1200 rpm for 1 hour using a stirrer to obtain a resin composition.

A release-treated polyethylene terephthalate (PET) film (PET5011 550, manufactured by Lintec) having a thickness of 50 μm was prepared. The obtained resin composition was applied onto the release-treated surface of the PET film by using an applicator so that the thickness after drying became 50 μm. Next, it was dried in a Geer oven at 100 ° C for 2 minutes to prepare an uncured material (B-stage semi-cured film) and polyparaphenylene of a resin sheet having a length of 200 mm × a width of 200 mm × a thickness of 50 μm. A laminate film of a film of ethylene dicarboxylate. Then, the polyethylene terephthalate film was peeled off from the laminated film, and the uncured material of the resin sheet was heated in a Geer aging incubator at 180 ° C for 80 minutes to prepare a pre-cured product of the resin sheet.

(2) Production of laminate containing pre-cured material

The obtained laminated film was provided so that the B-stage semi-cured film became the side of a glass epoxy substrate (FR-4, product number "CS-3665", manufactured by Lichang Industrial Co., Ltd.). The laminated film and the glass epoxy substrate were heated under pressure for 0.5 minutes at 0.5 MPa under reduced pressure using a parallel plate presser heated to 100 ° C to obtain a laminate including a pre-cured material of the resin sheet. Thereafter, the polyethylene terephthalate film was peeled off to obtain a laminate A of a glass epoxy substrate and a pre-cured product. The obtained pre-cured material has a second main surface on the glass epoxy substrate side, and has a roughened surface, that is, a first main surface on the opposite side of the glass epoxy substrate.

(Examples 2 to 10 and Comparative Examples 1 to 2)

A resin composition, a laminated film of a PET film and a B-stage semi-cured film, and a glass epoxy resin were obtained in the same manner as in Example 1 except that the type and the amount of the material to be used were changed as shown in the following Table 1. a laminate of a substrate and a pre-cured material.

(Evaluation)

(1) The lowest melt viscosity of epoxy resin materials

The uncured material (B-stage semi-cured film) of the obtained resin sheet was measured at 50 to 150 ° C under the conditions of a deformation of 21.6% and a frequency of 1 Hz using a Rheometer apparatus ("AR-2000" manufactured by TA Instrument Co., Ltd.). The viscosity of the temperature region is the lowest viscosity as the lowest melt viscosity.

(2) The existence state of cerium oxide 1

The pre-cured materials in the layered product A obtained in the examples and the comparative examples were observed in cross section. The presence state 1 of the cerium oxide in the pre-hardened material is determined according to the following criteria.

[Criteria for the determination of the presence state of cerium oxide]

○: in the pre-cured material, the first small-sized cerium oxide is present in a manner that is mostly present on the first main surface side, and the second large-sized cerium oxide is mostly present in the first 2 The way of the main side is biased.

X: the first small-sized cerium oxide is not present in a manner that is often present on the first main surface side, or the second large-sized cerium oxide is not present in the second main surface side. The way is biased to exist.

××: the first small-sized cerium oxide is not present in a manner that is often present on the first main surface side, and the second large-sized cerium oxide is not present in the second main surface. The side way is biased to exist.

(3) The existence state of cerium oxide 2

In the case where the determination result of the presence state 1 of the above-mentioned ceria is "○", the roughened surface, that is, the surface of the first main surface side having a thickness of 0.3 μm is included in the first region. The ratio (% by volume) of the content of the second largest particle size ceria in 100% by weight of all cerium oxide was evaluated. Moreover, the thickness of the second region was also evaluated.

(4) Subsequent strength (peel strength) and arithmetic mean roughness Ra

[Production of hardened material B]

After the (a) swelling treatment of the pre-cured material in the layered product A described above, the following (b) permanganate treatment, that is, the roughening treatment, is carried out, and the following (c) copper plating treatment is further carried out.

(a) Swelling treatment:

The layered product A was added to a swelling liquid (Swelling Dip Securiganth P, manufactured by Atotech Japan Co., Ltd.) at 60 ° C, and shaken for 20 minutes. Thereafter, it is washed with pure water.

(b) Permanganate treatment:

The layered product was added to a roughened aqueous solution of potassium permanganate (Concentrate Compact CP, manufactured by Atotech Japan Co., Ltd.) at 75 ° C, and shaken for 20 minutes to obtain a roughened pre-cured product obtained by roughening on a glass epoxy substrate. The obtained roughened pre-cured product was washed with a cleaning solution (Reduction Securiganth P, manufactured by Atotech Japan Co., Ltd.) at 23 ° C for 2 minutes, and then further washed with pure water.

After drying in a Gil aging incubator at 120 ° C for 2 hours and cooling, the arithmetic mean roughness Ra of the roughened surface of the roughened pre-cured material was measured in accordance with JIS B0601-1994.

(c) Copper plating:

Next, according to the following procedure, the roughened pre-cured material on the glass epoxy substrate is subjected to electroless copper plating and electrolytic copper plating.

The surface of the above roughened pre-cured material was treated with a 55 ° C alkali cleaning solution (Cleaner Securiganth 902) for 5 minutes to perform degreasing cleaning. After washing, the above roughened pre-cured material was treated with a pre-dip solution (Pre-dip Neoganth B) at 23 ° C for 2 minutes. Thereafter, the roughened pre-cured material was treated with an activation solution (Activator Neoganth 834) at 40 ° C for 5 minutes, and a palladium catalyst was charged. Next, the roughened pre-cured material was treated with a reducing solution (Reducer Neoganth WA) at 30 ° C for 5 minutes.

Then, the roughened pre-cured material was added to a chemical copper solution (Basic Printganth MSK-DK, Basic Printganth MSK, Stabilizer Printganth MSK), and electroless plating was performed until the plating thickness was about 0.5 μm. After electroless plating, in order to remove residual hydrogen, it was annealed at a temperature of 120 ° C for 30 minutes. All the steps before the electroless plating step were carried out by setting the treatment liquid to 1 L on a beaker scale while shaking the cured product.

Then, the roughened pre-cured material subjected to the electroless plating treatment was subjected to electrolytic plating until the plating thickness became 25 μm. Copper sulfate (Reducer Cu) was used as electrolytic copper plating, and a current of 0.6 A/cm ^{2 was} passed. After the copper plating treatment, the roughened pre-cured material was heated at 190 ° C for 1 hour to be hardened to obtain a cured product B in which a copper plating layer was formed.

[Method of measuring the strength]

A slit having a width of 10 mm was cut out from the surface of the copper plating layer on which the hardened material B of the copper plating layer was formed. Then, the tensile strength (peel strength) of the copper plating layer and the cured product was measured under the conditions of a crosshead speed of 5 mm/min using a tensile tester (trade name "Autograph", manufactured by Shimadzu Corporation). ).

The results are shown in Table 1 below. In the following Table 1, "total solid content component A" indicates the total solid content contained in the epoxy resin material, and "-" indicates that evaluation was not performed.

1. . . Pre-hardened

1a. . . First main face

1b. . . Second main face

2. . . Cerium oxide

2A. . . The first small particle size cerium oxide

2B. . . The second largest particle size of cerium oxide

6. . . Multi-layer object component

6a, 12a. . . Upper surface

11. . . Laminated body

12. . . Circuit substrate

13~16. . . Hardened layer

17. . . Metal layer

R1. . . First area

R2. . . Second area

Fig. 1 is a partially broken front cross-sectional view schematically showing a pre-cured material according to an embodiment of the present invention.

Fig. 2 is a partially broken front cross-sectional view schematically showing a laminate using a pre-cured material according to an embodiment of the present invention.

1. . . Pre-hardened

1a. . . First main face

1b. . . Second main face

2. . . Cerium oxide

2A. . . The first small particle size cerium oxide

2B. . . The second largest particle size of cerium oxide

6. . . Multi-layer object component

6a. . . Upper surface

R1. . . First area

R2. . . Second area

Claims (9)

A pre-cured material obtained by curing an epoxy resin material, comprising: a first main surface and a second main surface, wherein the first main surface is a roughened surface, and the epoxy resin material comprises An epoxy resin, a curing agent, and cerium oxide, wherein the cerium oxide comprises a first small particle size ceria having a particle diameter of 0.01 μm or more and less than 0.5 μm, and a particle diameter of 0.5 μm or more and 20 μm or less. In the second pre-cured material, the first small-sized cerium oxide is present in the pre-cured material in such a manner that the first small-sized cerium oxide is present on the surface of the roughened surface, that is, the first main surface side. The second largest particle size ceria is present in a manner that is mostly present on the second main surface side. The pre-cured material of claim 1, wherein the second surface of the surface of the first main surface side of the roughened surface has a thickness of 0.3 μm in all of the cerium oxide contained in the first region of 0.3 μm, the second portion The content of the large particle size cerium oxide is 5% by volume or less. The pre-cured material of claim 1 or 2, wherein the epoxy resin material before pre-hardening in a temperature region of 60 to 120 ° C has a minimum melt viscosity of 50 Pa‧s or more and 150 Pa‧s or less. The pre-cured material of claim 1 or 2, wherein the epoxy resin material further comprises a phenoxy resin. The pre-cured material of claim 3, wherein the epoxy resin material further comprises Phenoxy resin. A roughened pre-cured product obtained by subjecting the first main surface of the pre-cured material according to any one of claims 1 to 5 to a roughening treatment. The roughened pre-cured material of claim 6, wherein the pre-cured material is subjected to a swelling treatment before the roughening treatment. A layered body comprising a cured product obtained by hardening a roughened pre-cured material obtained by subjecting the first main surface of the pre-cured material according to any one of claims 1 to 5 to a roughening treatment; A metal layer laminated on the roughened surface of the cured product. The laminate according to claim 8, wherein the cured product and the metal layer have a bonding strength of 0.39 N/mm or more.