KR102021641B1 - Laminate,method for producing laminate and multilayer substrate - Google Patents

Abstract

Provided is a laminate capable of increasing the adhesive strength between the cured product and the metal layer. The laminated body 1 which concerns on this invention contains the hardened | cured material 2 which hardened the epoxy resin material containing an epoxy resin, a hardening | curing agent, and an inorganic filler, the metal layer 3 laminated | stacked on the surface of the hardened | cured material 2, etc. And a part of metal layer 3 is embedded in hardened | cured material 2 in several places, and the maximum of the depth in the whole of several metal layer parts 3a-3d buried in hardened | cured material 2 is 0.5. It is a micrometer or more and the maximum of the space | interval in the whole of the some metal layer part 3a-3d embedded in the hardened | cured material 2 is 0.5 micrometer or more.

Description

Laminates, methods for producing laminates and multilayer substrates {LAMINATE, METHOD FOR PRODUCING LAMINATE AND MULTILAYER SUBSTRATE}

This invention relates to the laminated body provided with the hardened | cured material, the metal layer laminated | stacked on the surface of this hardened | cured material, and the manufacturing method of this laminated body. Moreover, this invention relates to the multilayer board which used the said laminated body.

Conventionally, various resin compositions are used in order to obtain electronic components, such as a laminated board and a printed wiring board. For example, a resin composition is used for a multilayer printed wiring board in order to form the insulating layer for insulating the interlayer inside, or to form the insulating layer located in a surface layer part. In the said multilayer printed wiring board, metal wiring is formed in the surface of the said insulating layer in many cases.

As an example of the said resin composition, the following patent document 1 discloses the resin composition containing a cyanate ester resin and a naphthalene ether type epoxy resin. This resin composition may contain the inorganic filler. In the patent document 1, in the wet roughening process, the roughness of the surface of an insulating layer can be reduced, the plating conductor layer which has sufficient peel strength can be formed on an insulating layer, and the dielectric characteristic of an insulating layer further And it is described that it is possible to provide a resin composition that can improve the thermal expansion rate.

Patent Document 1: Japanese Patent Application Laid-Open No. 2011-144361

It is strongly required for the multilayer printed wiring board that peeling between the insulating layer and the metal wiring laminated on the insulating layer is unlikely to occur. For this reason, it is preferable that the adhesive strength of the said insulating layer and the said metal wiring is high. In order to sufficiently hold metal wirings, the adhesive strength is preferably 4N / cm or more. Moreover, in the said insulating layer, it is preferable that the dimension by a heat does not change significantly. That is, it is preferable that the linear expansion rate of the said insulating layer is low.

However, only using the conventional resin composition like patent document 1, it is difficult to fully raise the adhesive strength of the hardened | cured material which hardened this resin composition, and metal wiring. In addition, there is a thing that can not sufficiently reduce the dimensional change due to the heat of the cured product, the line expansion coefficient of the insulating layer can be relatively high.

The objective of this invention is providing the laminated body which can raise the adhesive strength of hardened | cured material and a metal layer, and the manufacturing method of a laminated body, and providing the multilayer substrate using this laminated body.

The limited object of this invention is to provide the laminated body and the manufacturing method of a laminated body which can reduce the dimensional change by the heat of hardened | cured material, and provide the multilayer substrate using this laminated body.

According to the broad aspect of this invention, the hardened | cured material which hardened the epoxy resin containing an epoxy resin, a hardening | curing agent, and an inorganic filler, and the metal layer laminated | stacked on the surface of the said hardened | cured material are provided, and a part of the said metal layer has the said hardening in multiple places. The maximum of the depth in the whole of the some part of the said metal layer buried in the said hardened | cured material, and buried in the said hardened | cured material is 0.5 micrometer or more, and the maximum of the space | interval in the whole of the said some metal layer part buried in the said hardened | cured material is A laminate is provided, which is at least 0.5 μm.

In a specific aspect of the laminate according to the present invention, an average of two depths of two adjacent metal layer portions of the plurality of metal layer portions embedded in the cured product is set to D μm, and an interval between the two metal layer portions is given. When S is set to S µm, the minimum of S / D is 0.15 or more, and the maximum of S / D is 5.0 or less in the entirety of the plurality of the metal layer portions embedded in the cured product.

In a specific aspect of the laminate according to the present invention, the plurality of the metal layer portions embedded in the cured product detach the inorganic filler by the roughening treatment to form a plurality of voids in the cured product, A part of the metal layer is buried in the gap.

In the specific situation of the laminated body which concerns on this invention, the said roughening process is a wet roughening process.

In the specific situation of the laminated body which concerns on this invention, content of the said inorganic filler is 60 weight% or more and 80 weight% or less in 100 weight% of solid content in the said epoxy resin material.

In the specific situation of the laminated body which concerns on this invention, the average particle diameter of the said inorganic filler contained in the said epoxy resin material is 0.1 micrometer or more and 5 micrometers or less.

According to a broad aspect of the present invention, a plurality of voids are formed in the cured product by removing the inorganic filler by a roughening treatment using a cured product obtained by curing an epoxy resin material including an epoxy resin, a curing agent, and an inorganic filler. And a step of forming a metal layer so as to be laminated on the surface of the cured product and embedding a part of the plurality of voids, thereby obtaining a laminate, and the plurality of parts of the metal layer as the laminate. The maximum of the depth in the whole of the said some metal layer part embedded in the said hardened | cured material in said hardened | cured material is 0.5 micrometer or more, and the space | interval in the whole of the some said metal layer part buried in the said hardened | cured material The manufacturing method of a laminated body which obtains the laminated body whose maximum of 0.5 micrometers or more is provided.

In the specific situation of the manufacturing method of the laminated body which concerns on this invention, the said roughening process is a wet roughening process.

According to the broad situation of this invention, the multilayer board which has a circuit board and the laminated body mentioned above, and the said laminated body is arrange | positioned on the surface of the said circuit board from the said hardened | cured material side is provided.

The laminated body which concerns on this invention is equipped with the hardened | cured material which hardened the epoxy resin material containing an epoxy resin, a hardening | curing agent, and an inorganic filler, and the metal layer laminated | stacked on the surface of the said hardened | cured material, and a part of the said metal layer exists in several places. The maximum of the depth in the whole of the some part of the said metal layer buried in the said hardened | cured material is 0.5 micrometer or more, and the space | interval in the whole of the some said metal layer part buried in the said hardened | cured material Since maximum is 0.5 micrometer or more, the adhesive strength of hardened | cured material and a metal layer can be raised.

FIG. 1: is sectional drawing which shows typically the laminated body which concerns on one Embodiment of this invention.
FIG. 2: is sectional drawing which shows typically the multilayer board which used the laminated body which concerns on one Embodiment of this invention.
FIG. 3: is a schematic cross section for demonstrating the depth and space | interval of the metal layer part in the laminated body which concerns on one Embodiment of this invention. FIG.

Hereinafter, the detail of this invention is demonstrated.

(Laminated body)

The laminated body which concerns on this invention is equipped with the hardened | cured material which hardened the epoxy resin material containing an epoxy resin, a hardening | curing agent, and an inorganic filler, and the metal layer laminated | stacked on the surface of the said hardened | cured material. In the laminated body which concerns on this invention, one part of the said metal layer is buried in the said hardened | cured material in several places, 1) The maximum of the depth in the whole of the some said metal layer parts embedded in the said hardened | cured material is 0.5 micrometer or more, and , 2) The maximum of the spacing in the whole of the plurality of metal layer portions embedded in the cured product is 0.5 µm or more.

The manufacturing method of the laminated body which concerns on this invention detach | desorbs the said inorganic filler by a roughening process using the hardened | cured material which hardened the epoxy resin material containing an epoxy resin, a hardening | curing agent, and an inorganic filler. A process of forming a space | gap, the process of forming a metal layer so that a part may be buried in the some space | gap so that it may be laminated | stacked on the surface of the said hardened | cured material, and a laminated body may be provided. In the manufacturing method of the laminated body which concerns on this invention, as said laminated body, one part of the said metal layer is buried in the said hardened | cured material in several places, and the maximum of the depth in the whole of the some metal layer part buried in the said hardened | cured material is 0.5 The laminated body whose micrometer is more than a micrometer and whose maximum of the space | interval in the whole of the said some metal layer part embedded in the said hardened | cured material is 0.5 micrometer or more is obtained.

By employ | adopting the structure mentioned above in the laminated body which concerns on this invention, and the manufacturing method of the laminated body which concerns on this invention, the adhesive strength of hardened | cured material and a metal layer can be raised. In addition, in the laminate according to the present invention, it becomes possible to sufficiently reduce the dimensional change due to the heat of the cured product, and to sufficiently lower the linear expansion rate of the cured product.

1) the maximum of the depth in the whole of the said some metal layer part embedded in the said hardened | cured material, and 2) the maximum of the space | interval in the whole of the said several metal layer part embedded in the said hardened | cured material is the thickness direction (FIG. 1) can be obtained by evaluating the metal layer portion embedded in the cured layer.

In order to obtain the maximum of the depth of 1), the depth of each of the plurality of metal layer portions embedded in the cured product is the interface between the cured product and the metal layer in the metal layer portion embedded in one of the cured products. The depth to the deepest part buried from (except the part where the said metal layer is buried in the said hardened | cured material) is made deep.

For each gap of the plurality of metal layer portions embedded in the cured product in order to obtain a maximum of the spacing of 2), any buried center in the metal layer portion embedded in the adjacent two cured products The distance from the part to the buried center part next to the buried center part is made into the space | interval of the said some metal layer part embedded in the said hardened | cured material. That is, the said center part is a center part of the said metal layer part in the interface of the said hardened | cured material and the said metal layer. When defining the center portion, the inner metal layer portion that does not appear at the interface between the cured product and the metal layer is not considered. Each interval of the plurality of metal layer portions is a respective interval of two adjacent metal layer portions of the plurality of metal layer portions embedded in the cured product.

1) As a method of controlling the maximum of the depth in the whole of the said some metal layer part embedded in the said hardened | curing material within the above-mentioned range, the method of optimizing the kind and content of an inorganic filler, and the manufacturing conditions of a laminated body (pressing, The method of optimizing hardening conditions), etc. are mentioned.

In regard to the inorganic filler, the depth and the spacing of the buried metal layer can be controlled within the above ranges by setting the average particle diameter to 0.5 to 1.0 µm and the content to 60 to 80%. In addition, by adjusting the crimping conditions, the inorganic filler can be prevented from flowing out, the amount of the inorganic filler in the surface layer can be controlled, and the depth and spacing of the buried metal layer can be set within the above range. About hardening conditions, when it hardens too much, it will not be harmonized, and if hardening does not progress, it will be damage by a roughening process, and the depth and space | interval of a metal layer cannot be controlled in the said range. By adjusting the degree of cure, it is possible to adjust the depth and spacing of the buried metal layer within the above ranges. These methods are 2) a method of controlling the maximum of the space | interval in the whole of the said some metal layer part embedded in the said hardened | cured material within the above-mentioned range, and 3) the minimum and maximum of said S / D in the above-mentioned range It is also considered as a method of controlling inward.

2) As a method of controlling the maximum of the space | interval in the whole of the said some metal layer part embedded in the said hardened | curing material within the above-mentioned range, the method of optimizing the kind and content of an inorganic filler, and the manufacturing conditions of a laminated body (pressing, And curing method).

From the viewpoint of further raising the adhesive strength between the cured product and the metal layer, 1) The maximum of the depth in the entirety of the plurality of the metal layer parts embedded in the cured product is preferably 0.8 µm or more. 1) The maximum upper limit of the depth in the whole of the said some metal layer part embedded in the said hardened | cured material is not specifically limited. The maximum of the depth is preferably 5.0 μm or less. If the maximum of the said depth is below the said upper limit, flash etching property will become more favorable.

From the viewpoint of further increasing the adhesive strength between the cured product and the metal layer, 2) the maximum of the interval in the entirety of the plurality of the metal layer portions embedded in the cured product is preferably 0.7 µm or more. 2) The maximum of the space | interval in the whole of the said some metal layer part embedded in the said hardened | cured material is not specifically limited. The maximum of the interval is preferably 20 µm or less, more preferably 10 µm or less, and still more preferably 5.0 µm or less. If the maximum of the said interval is below the said upper limit, it can respond to refinement | miniaturization of wiring.

Of the plurality of metal layer portions embedded in the cured product, an average of two depths of two adjacent metal layer portions is set to D μm, and a space between the two metal layer portions is set to S μm. 3) In the whole of the said some metal layer part embedded in the said hardened | cured material, minimum of S / D becomes like this. Preferably it is 0.15 or more, and the maximum of S / D becomes like this. Preferably it is 5.0 or less.

3) The minimum and maximum of S / D in the entirety of the plurality of metal layer portions embedded in the cured product are determined by evaluating the metal layer portion embedded in the cured layer in the cross-sectional observation in the thickness direction of the cured product. Can be.

3) With respect to the respective angular depths of the two at the average of the depths of the two of the adjacent two metal layer portions, among the plurality of the metal layer portions embedded in the cured product, to obtain the minimum and maximum of the S / D. In the said metal layer part embedded in the said hardened | cured material, the depth from the interface of hardened | cured material and a metal layer (except the part where the said metal layer is buried in the hardened | cured material) to the deepest part buried.

3) In order to obtain the minimum and the maximum of S / D, among the plurality of metal layer portions embedded in the cured product, with respect to each interval of two metal layer portions adjacent to each other, it is embedded in the adjacent two cured products. In the said metal layer part, the distance from the said buried center part to the buried center part beside the buried center part is made into the space | interval of the said metal layer part embedded in the said hardened | cured material.

As a method of controlling the minimum and maximum of said 3) S / D in the above-mentioned range, the method of optimizing the kind and content of an inorganic filler, the method of optimizing the manufacturing conditions (compression | bonding, hardening conditions) of a laminated body, etc. are mentioned. Can be.

From the viewpoint of further increasing the adhesive strength between the cured product and the metal layer, the minimum of 3) S / D is preferably 0.2 or more. From the viewpoint of further increasing the adhesive strength between the cured product and the metal layer, the maximum of 3) S / D is preferably 2.0 or less.

Next, 1) the maximum of the depth in the entirety of the plurality of metal layer portions buried in the cured product, 2) the maximum of the spacing in the entirety of the plurality of metal layer portions embedded in the cured product, 3) S The minimum and maximum of / D, etc. are demonstrated, referring drawings.

1: is sectional drawing which shows typically the laminated body which concerns on one Embodiment of this invention.

In FIG. 1, the cross section of the lamination direction of the laminated body 1 is shown. The laminated body 1 is equipped with the hardened | cured material 2 and the metal layer 3 laminated | stacked on the surface of the hardened | cured material 2. In FIG. 1, the cross section by the thickness direction of hardened | cured material is shown. A part of metal layer 3 is buried in hardened | cured material 2 in several places (A)-(D). The hardened | cured material 2 has 2 A of resin parts, and inorganic filler part 2B. The metal layer 3 has the metal layer part 3a-3d buried in the inside of hardened | cured material 2 in several places (A)-(D).

The depth D1 at the location A, the depth D2 at the location B, the depth D3 at the location C, and the depth D4 at the location D are shown in FIG. 1. Indicated. Moreover, the space | interval (S1) of the metal layer part between one point (A) and the location (A), the space | interval (S2) of the metal layer part between one point (B) and one point (C), and one point (C) The space | interval S3 of the metal layer part between (D) is shown in FIG. Depth D1-D4 is an interface between hardened | cured material 2 and metal layer 3 in each metal layer part 3a-3d embedded in hardened | cured material 2 (however, metal layer 3 ) To the deepest part buried from the perforated part L1 of FIG. 3 except the part buried in the hardened | cured material 2). The intervals S1 to S3 are embedded in the metal layer portions 3a to 3d buried in the two cured products adjacent to each other, and the buried center portion (tagging portion L2 in Fig. 3). We assume distance from buried center part of the buried center part to from. Each interval of the plurality of metal layer portions 3a to 3d ((3a) and (3b), (3b) and (3c), (3c) and (3d) is embedded in the cured product 2. Of the metal layer portions 3a to 3d of the two adjacent metal layer portions 3a to 3d ((3a) and (3b), (3b) and (3c), (3c) and (3d)). Each interval. In addition, the said center part is a center part of the metal layer parts 3a-3d in the interface of hardened | cured material 2 and the metal layer 3. When defining the center portion, the lower part of the inner metal layer portion 3a that does not appear at the interface between the cured product 2 and the metal layer 3 is not considered (Fig. 3 (X)).

The minimum and maximum of the above-mentioned 3) S / D can also be obtained from the above-described depths D1 to D4 and the above-described intervals S1 to S3.

When the conventional epoxy resin material contains many inorganic fillers, especially when the conventional epoxy resin material contains 60 weight% or more of inorganic fillers as solid content, the dimensional change by the heat of hardened | cured material becomes small, There exists a problem that the adhesive strength of hardened | cured material and a metal layer becomes low.

 On the other hand, as mentioned above, 1) the maximum of the depth in the whole of the said some metal layer part embedded in the said hardened | cured material, and 2) the maximum of the space | interval in the whole of the said some metal layer parts embedded in the said hardened | cured material By controlling, in order to reduce the dimensional change by the heat of hardened | cured material, even if it contains many content of an inorganic filler, even if the inorganic filler contains 60 weight% or more as solid content, the adhesive strength of hardened | cured material and a metal layer can be improved. Moreover, by controlling the minimum and maximum of said 3) S / D as mentioned above, the adhesive strength of hardened | cured material and a metal layer can be raised more effectively.

When content of the said inorganic filler in 100 weight% of solid content (henceforth described as solid content A) contained in the said epoxy resin material is 60 weight% or more, the dimensional change by the heat of hardened | cured material becomes considerably small.

Moreover, the pattern formation method represented by a semi additive process (SAP) etc. is known. In the semi-etching method, a circuit (Cu plating or the like) pattern is formed on the convex surface on the surface of the insulating layer. Next, another insulating layer is laminated on the insulating layer and the circuit pattern. When the content of the inorganic filler in the conventional epoxy material is increased in the semi-etching method, the content of the resin component is relatively small, and the contact area between the resin component and the circuit decreases, and the adhesive strength between the cured product and the circuit is increased. Tends to be lowered.

On the other hand, as mentioned above, 1) the maximum of the depth in the whole of the said some metal layer part embedded in the said hardened | cured material, and 2) the maximum of the space | interval in the whole of the said some metal layer parts embedded in the said hardened | cured material By controlling, even when the insulating layer and the circuit pattern (metal layer) are formed by SAP, even if the content of the inorganic filler contained in the epoxy resin material used for SAP is increased, the adhesive strength between the cured product and the metal layer is increased. Can be. Moreover, by controlling the minimum and maximum of said 3) S / D as mentioned above, the adhesive strength of hardened | cured material and a metal layer can be raised more effectively.

The average linear expansion rate of the said hardened | cured material becomes like this. Preferably it is 30 ppm / degrees C or less, More preferably, it is 20 ppm / degrees C or less. When the said average linear expansion rate is below the said upper limit, the deformation | transformation of a circuit board itself is suppressed by reduction of the average hot wire expansion rate of a circuit board, and the adhesive strength of the said hardened | cured material and a metal layer becomes further more favorable.

The glass transition temperature of the said hardened | cured material becomes like this. Preferably it is 150 degreeC or more, More preferably, it is 180 degreeC or more, Preferably it is 250 degrees C or less, More preferably, it is 200 degrees C or less. Impact resistance becomes further more favorable that the said glass transition temperature is more than the said minimum and below the said upper limit.

The minimum melt viscosity in 50-150 degreeC of the said epoxy resin material becomes like this. Preferably it is 5 Pa.s or more, More preferably, it is 10 Pa.s or more, Preferably it is 300 Pa.s or less, More preferably, it is 250 Pa. S or less, More preferably, it is 100 Pa * s or less. When the said minimum melt viscosity is more than the said minimum and below the said upper limit, the handling property of a B stage film will become more favorable. Moreover, when the said minimum melt viscosity is more than the said minimum and below the said upper limit, when performing swelling process on the swelling processing conditions mentioned later, for example, or roughening on the roughening conditions mentioned later, 1), 2 ) It is much easier to obtain a cured product in which the maximum of the depth and the maximum of the spacing in the whole of the plurality of metal layer parts buried in the cured product are 0.5 µm or more, respectively, and 3) the minimum of S / D is 0.15. It becomes easier to obtain the hardened | cured material by which the above and the maximum becomes 5.0 or less, and the presence state of the inorganic filler part near the interface of a resin part and a metal layer becomes still more favorable, As a result, hardened | cured material and a metal layer It is easy to make adhesive strength with and 4N / cm or more.

The melt viscosity is measured in the temperature range of 50-150 ° C. of the epoxy resin material using a rheometer apparatus. As said rheometer apparatus, "AR-2000" by TA Instruments Corporation etc. are mentioned.

The epoxy resin material may be in a paste form or in a film form. A resin composition may be sufficient as the said epoxy resin material, and the B stage film in which the resin composition was formed in the film form may be sufficient as it.

Hereinafter, the detail of each component, such as an epoxy resin, a hardening | curing agent, and an inorganic filler contained in the said epoxy resin material, is demonstrated.

[Epoxy resin]

The epoxy resin contained in the said epoxy resin material is not specifically limited. As this epoxy resin, a conventionally well-known epoxy resin can be used. The epoxy resin refers to an organic compound having at least one epoxy group. Only 1 type may be used for an epoxy resin, and 2 or more types may be used together.

As said epoxy resin, bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, phenol novolak-type epoxy resin, biphenyl type epoxy resin, biphenyl novolak-type epoxy resin, biphenol type epoxy resin, Naphthalene type epoxy resin, fluorene type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclo pentadiene type epoxy resin, anthracene type epoxy resin, epoxy resin having adamantane skeleton, tricyclodecane skeleton The epoxy resin which has, and the epoxy resin which has a triazine nucleus as frame | skeleton etc. are mentioned.

It is preferable that the said epoxy resin has a biphenyl skeleton, and it is preferable that it is a biphenyl type epoxy resin. Since the said epoxy resin has a biphenyl skeleton, the adhesive strength of hardened | cured material and a metal layer becomes still higher.

From the viewpoint of making the surface roughness of the surface of the roughened cured product smaller by one layer and further increasing the adhesive strength between the cured product and the metal layer, the epoxy equivalent of the epoxy resin is preferably 90 or more, more preferably 100 or more, Preferably it is 1000 or less, More preferably, it is 800 or less.

It is preferable that the molecular weight of the said epoxy resin is 1000 or less. In this case, even if content of the inorganic filler in an epoxy resin material is 60 weight% or more, the epoxy resin material which is a resin composition with high fluidity can be obtained. For this reason, when a B stage film is laminated on a board | substrate, an inorganic filler can be uniformly present.

The molecular weight of the said epoxy resin and the molecular weight of the hardening | curing agent mentioned later mean the molecular weight which can be computed from the said structural formula, when the said epoxy resin or hardening | curing agent is not a polymer, and the structural formula of the said epoxy resin or hardening agent can be specified. do. Moreover, when the said epoxy resin or hardening | curing agent is a polymer, a weight average molecular weight is meant. The said weight average molecular weight shows the weight average molecular weight in polystyrene conversion calculated | required by gel permeation chromatography (GPC) measurement.

[Curing agent]

The hardener contained in the said epoxy resin material is not specifically limited. As the curing agent, a conventionally known curing agent can be used. Only 1 type may be used for the said hardening | curing agent, and 2 or more types may be used together.

Examples of the curing agent include cyanate ester compounds (cyanate ester curing agents), phenol compounds (phenol curing agents), amine compounds (amine curing agents), thiol compounds (thiol curing agents), imidazole compounds, phosphine compounds, acid anhydrides, and active ester compounds. And dicyandi diamide. Especially, it is preferable that the said hardening | curing agent is a cyanate ester compound or a phenolic compound from a viewpoint of obtaining the hardened | cured material which is further smaller in dimension change by heat. It is preferable that it is a cyanate ester compound, and it is preferable that it is a phenol compound. It is preferable that the said hardening | curing agent has a functional group which can react with the epoxy group of the said epoxy resin.

From the viewpoint of reducing the surface roughness of the surface of the roughened cured product by one more layer, increasing the adhesive strength between the cured product and the metal layer by one more layer, and forming a further finer wiring on the surface of the cured product, It is preferable that it is a nate ester compound, a phenol compound, or an active ester compound.

By use of the said cyanate ester compound, the glass transition temperature of the hardened | cured material of the B stage film with many content of an inorganic filler becomes still higher. The cyanate ester compound is not particularly limited. As the cyanate ester compound, a conventionally known cyanate ester compound can be used. Only 1 type may be used for the said cyanate ester compound, and 2 or more types may be used together.

As said cyanate ester compound, a novolak-type cyanate ester resin, bisphenol-type cyanate ester resin, the prepolymer etc. which these were partially trimerized are mentioned. As said novolak-type cyanate ester resin, a phenol novolak-type cyanate ester resin, an alkyl phenol type cyanate ester resin, etc. are mentioned. As said bisphenol-type cyanate ester resin, bisphenol-A cyanate ester resin, bisphenol-E cyanate ester resin, tetramethyl bisphenol F-type cyanate ester resin, etc. are mentioned.

As a commercial item of the said cyanate ester compound, phenol novolak-type cyanate ester resin ("PT-30" and "PT-60" by Lon Japan Japan), and the prepolymer (Lonza Japan) which the bisphenol type cyanate ester resin was trimerized "BA-230S", "BA-3000S", "BTP-1000S", and "BTP-6020S" by the company) etc. are mentioned.

By use of the said phenolic compound, the adhesive strength of hardened | cured material and a metal layer becomes still higher. Moreover, by use of the said phenol compound, when blackening or Cz-processing the surface of the copper provided on the surface of the hardened | cured material of a resin composition, for example, the adhesive strength of hardened | cured material and copper becomes still higher.

The said phenolic compound is not specifically limited. As this phenolic compound, a conventionally well-known phenolic compound can be used. Only 1 type may be used for the said phenol compound, and 2 or more types may be used together.

As said phenolic compound, a novolak-type phenol, a biphenol type phenol, a naphthalene type phenol, a dicyclopentadiene type phenol, an aralkyl type phenol, a dicyclopentadiene type phenol, etc. are mentioned.

As a commercial item of the said phenolic compound, a novolak-type phenol ("TD-2091" made by DIC Corporation), a biphenyl novolak-type phenol ("MEH-7851" made by Meiwa Kasei Co., Ltd.), an aralkyl type phenolic compound (" MEH-7800 "), and the phenol (" LA1356 "and" LA3018-50P "by DIC Corporation) which have an amino triazine frame | skeleton, etc. are mentioned.

From the viewpoint of reducing the surface roughness of the surface of the roughened cured product by one more layer, increasing the adhesive strength between the cured product and the metal layer by one more layer, and forming a further finer wiring on the surface of the cured product, the phenolic compound is, It is preferable that it is a biphenyl novolak-type phenol compound or an aralkyl phenol compound.

By use of the said active ester compound, the induction tangent of the hardened | cured material with a comparatively large content of an inorganic filler falls, and the transmission loss of a circuit board improves.

The said active ester compound is not specifically limited. As the active ester compound, a conventionally known active ester compound can be used. Only 1 type may be used for the said active ester compound, and 2 or more types may be used together.

As a commercial item of the said active ester compound, "HPC-800" by DIC Corporation, etc. are mentioned.

The surface roughness of the surface of the roughened cured product is further reduced, the adhesive strength between the cured product and the metal layer is further increased, and further finer wiring is formed on the surface of the cured product. From a viewpoint to provide, it is preferable that the said hardening | curing agent contains the hardening | curing agent whose equivalent is 250 or less. The equivalent of the curing agent represents, for example, cyanate ester group equivalents when the curing agent is a cyanate ester compound, phenolic hydroxyl group equivalents when the curing agent is a phenolic compound, and active when the curing agent is an active ester compound. Ester group equivalent is shown.

It is preferable that the molecular weight of the said hardening | curing agent is 1000 or more. In this case, even if content of the inorganic filler in an epoxy resin material is 60 weight% or more, the epoxy resin material which is a resin composition with high fluidity can be obtained. For this reason, when a B stage film is laminated on a board | substrate, an inorganic filler can be uniformly present.

Content of the sum total of the said epoxy resin and the said hardening | curing agent in 100 weight% of solids except the said inorganic filler contained in the said epoxy resin material (henceforth described as solid content B) becomes like this. Preferably it is 80 weight% or more, Preferably it is 99 weight% or less, More preferably, it is 97 weight% or less.

When content of the system of the said epoxy resin and the said hardening | curing agent is more than the said minimum and below the said upper limit, since a more favorable hardened | cured material can be obtained and a melt viscosity can be adjusted, inorganic filler dispersibility becomes favorable and also in the hardening process It is possible to prevent the B stage film from getting wet and expanding in an unintentional area. Furthermore, the dimensional change by heat of hardened | cured material can be suppressed further. Moreover, when content of the sum total of the said epoxy resin and the said hardening | curing agent is more than the said minimum, melt viscosity will become low, and there exists a tendency for the epoxy resin material to become excessively wet and to expand in the unintentional area | region in the hardening process, and it becomes difficult to expand. Moreover, when content of the sum total of the said epoxy resin and the said hardening | curing agent is below the said upper limit, it will become easy to bury in the hole or the unevenness | corrugation of a circuit board, and also there exists a tendency for an inorganic filler to become non-uniform. "Solid content B" means the sum total of an epoxy resin, a hardening | curing agent, and other solid content mix | blended as needed. The inorganic filler is not included in the solid content B. "Solid content" is a non-volatile component and means the component which does not volatilize at the time of shaping | molding or heating.

The compounding ratio of an epoxy resin and a hardening | curing agent is not specifically limited. The compounding ratio of an epoxy resin and a hardening | curing agent is suitably determined by the kind of epoxy resin and a hardening | curing agent.

[Weapon filler]

The inorganic filler contained in the said epoxy resin material is not specifically limited. As the inorganic filler, a conventionally known inorganic filler can be used. Only 1 type may be used for the said inorganic filler, and 2 or more types may be used together.

Examples of the inorganic fillers include silica, talc, clay, mica, hydrotarcite, alumina, magnesium oxide, aluminum hydroxide, aluminum nitride, boron nitride, and the like. The surface roughness of the surface of the roughened cured product is reduced, the adhesive strength between the cured product and the metal layer is further increased, and further finer wiring is formed on the surface of the cured product, and the cured product is provided with better insulation reliability. From a viewpoint, it is preferable that the said inorganic filler is silica or alumina, It is more preferable that it is silica, It is further more preferable that it is fused silica. By use of silica, the linear expansion rate of hardened | cured material becomes further lower, the surface roughness of the surface of roughening hardened | cured material becomes small effectively, and the adhesive strength of hardened | cured material and a metal layer becomes high effectively. It is preferable that the shape of the silica is almost spherical.

The average particle diameter of the said inorganic filler becomes like this. Preferably it is 0.1 micrometer or more, Preferably it is 10 micrometers or less, More preferably, it is 5 micrometers or less. It is especially preferable that the average particle diameter of the said inorganic filler is 0.1 micrometer or more and 5 micrometers or less. If the average particle diameter is more than the said minimum, the embedding property of an epoxy resin material can be improved. If average particle diameter is more than the said upper limit, the smoothness of the surface of the epoxy resin material which is a B stage film can be improved. Moreover, when the said average particle diameter is more than the said minimum and below the said upper limit, for example, when performing swelling process on the rinse process conditions mentioned later, or roughening process on the roughening process conditions mentioned later, 1), 2) It is further easier to obtain a cured product in which the maximum of the depth and the maximum of the spacing in the entirety of the plurality of metal layer portions buried in the cured product are each 0.5 µm or more, and 3) the minimum of S / D is 0.15 or more. And obtaining a cured product having a maximum of 5.0 or less becomes easier, and as a result, it is easy to make the adhesive strength between the cured product and the metal layer 4N / cm or more. 0.5 micrometer or more of the average particle diameter of the said inorganic filler may be sufficient.

As an average particle diameter of the said inorganic filler, the value of the median diameter (d50) which becomes 50% is employ | adopted. The said average particle diameter can be measured using the particle size distribution measuring apparatus of a laser diffraction scattering system.

It is preferable that it is surface-treated, and, as for the said inorganic filler, it is more preferable that it is surface-treated with a coupling agent. Thereby, the surface roughness of the surface of a roughened hardened | cured material becomes further smaller, the adhesive strength of hardened | cured material and a metal layer is further increased, and further finer wiring is formed in the surface of hardened | cured material, Good interlayer insulation reliability and interlayer insulation reliability can be imparted to the cured product.

As said coupling agent, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, etc. are mentioned. Examples of the silane coupling agent include amino silane, imidazole silane, vinyl silane, epoxy silane, and the like.

In 100 weight% of solid content A contained in the said epoxy resin material, content of the said inorganic filler becomes like this. Preferably it is 50 weight% or more, More preferably, it is 60 weight% or more, Preferably it is 85 weight% or less, More preferably, 80 wt% or less. If content of the said inorganic filler is more than the said minimum, the dimensional change by the heat of hardened | cured material will become quite small. Moreover, when content of the said inorganic filler is more than the said minimum and below the said upper limit, the surface roughness of the surface of a roughening hardened | cured material will become further lower, the adhesive strength of hardened | cured material and a metal layer will become further higher, and hardened | cured material A finer wiring can be formed on the surface, and the amount of the inorganic filler can reduce the linear expansion rate of the metal copper and the cured product. "Solid content A" means the sum total of an epoxy resin, a hardening | curing agent, an inorganic filler, and solid content mix | blended as needed. "Solid content" is a non-volatile component and means the component which does not volatilize at the time of shaping | molding or heating.

[Details of Other Components and Epoxy Resin Materials]

The said epoxy resin material may contain the hardening accelerator as needed. By use of a hardening accelerator, the hardening rate of an epoxy resin material becomes it much faster. By rapidly curing the epoxy resin material, the crosslinked structure of the cured product becomes uniform, and the number of unreacted functional groups decreases, resulting in a high crosslink density. The hardening accelerator is not specifically limited, A conventionally well-known hardening accelerator can be used. Only 1 type may be used for said hardening accelerator, and 2 or more types may be used together.

As said hardening accelerator, an imidazole compound, a phosphorus compound, an amine compound, an organometallic compound, etc. are mentioned, for example.

As said imidazole compound, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl -4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimida Sol, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyano Ethyl-2-undecylimidazolium trimeryltate, 1-cyanoethyl-2-phenylimidazolium trimeryltate, 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-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1') ] -Ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methyl Imidazole, and the like are SOCCIA press acid adduct, 2-phenyl-4,5-dihydroxy-methylimidazole and 2-phenyl-4-methyl-5-dihydroxy-methylimidazole.

Triphenyl phosphine etc. are mentioned as said phosphorus compound.

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

Examples of the organometallic compound include zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bis acetyl acetonate cobalt (II), tris acetyl acetonate cobalt (III), and the like.

It is especially preferable that the said hardening accelerator is an imidazole compound from a viewpoint of improving the insulation reliability of hardened | cured material.

Content of the said hardening accelerator is not specifically limited. From the viewpoint of efficiently curing the epoxy resin material, the content of the curing accelerator in the solid content B 100% by weight is preferably 0.01% by weight or more, more preferably 0.5% by weight or more, preferably 3% by weight or less. More preferably, it is 2 weight% or less.

For the purpose of improving impact resistance, heat resistance, compatibility of resins and workability, epoxy resin materials include coupling agents, colorants, antioxidants, ultraviolet ray deterioration inhibitors, antifoaming agents, thickeners, thixotropic agents and other than the resins mentioned above. You may add another resin.

As said coupling agent, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, etc. are mentioned. Examples of the coupling agent include vinyl silane, amino silane, imidazole silane, epoxy silane and the like.

 As resin other than the above, phenoxy resin, polyvinyl acetal resin, polyphenylene ether resin, divinyl benzyl ether resin, poly arylate resin, diaryl phthalate resin, polyimide resin, amide imide resin, benzo jade Photographic resins, benzoxazole resins, bismaleimide resins, acrylate resins and the like.

(Epoxy resin material which is B stage film)

As a method of forming the said resin composition into a film form, for example, melt-kneading and extruding a resin composition using an extruder, and shape | molding into a film form by T-die or a circular die etc. The extrusion molding method, the casting molding method which casts the resin composition containing a solvent, and shape | molds into a film form, the other conventionally well-known film molding method, etc. are mentioned. Among them, an extrusion molding method or a casting molding method is preferable because it can cope with thinning. The film includes a sheet.

The B stage film can be obtained by shape | molding the said resin composition to a film form and heat-drying for 1 to 180 minutes, for example at 90-200 degreeC so that hardening by heat does not progress too much.

As mentioned above, the resin composition on the film obtained by a drying process is called B stage film. The said B stage film is a semi-cargo which is a semi-hardened state. The semi-hardened material is not completely cured, so that curing may proceed further.

It is preferable that the said B stage film is not a prepreg. In the case where the B-stage film is not a prepreg, migration does not occur depending on glass fibers or the like. Moreover, when laminating or precuring a B stage film, the unevenness | corrugation by glass fiber disappears on the surface. Moreover, when the said epoxy resin material is made into the B stage film which does not contain a prepreg, the dimensional change by the heat of hardened | cured material becomes small, shape retention property becomes high, and semi additive process suitability becomes high.

The said resin composition can be used suitably in order to form the laminated film provided with a base material and the B stage film etc. laminated | stacked on one surface of this base material. The B stage film of a laminated film is formed of the said resin composition.

As said base material of the said laminated | multilayer film, polyester resin films, such as a polyethylene terephthalate film and a polybutylene terephthalate film, olefin resin films, such as a polyethylene film and a polypropylene film, a polyimide resin film, copper foil, aluminum foil, etc. Metal foil, and the like. The surface of the said base material may be release-processed as needed.

When using the said epoxy resin material as an insulating layer of a circuit, it is preferable that the thickness of the layer formed with the epoxy resin material is more than the thickness of the conductor layer which forms a circuit. The thickness of the layer formed of the said epoxy resin material becomes like this. Preferably it is 5 micrometers or more, Preferably it is 200 micrometers or less.

(Printed wiring board)

The said epoxy resin material is used suitably in order to form the insulating layer in a printed wiring board.

The said printed wiring board can be obtained by heat-press-molding this B stage film using the B stage film formed by the said resin composition, for example.

Metal foil can be laminated | stacked on the single side | surface or both surfaces with respect to the said B stage film. The method of laminating the said B stage film and metal foil is not specifically limited, A well-known method can be used. For example, the said B stage film can be laminated | stacked on metal foil, using a device, such as a parallel flat plate press or a roll laminator, pressurizing with or without heating.

(Copperclad laminates and multilayer substrates)

The said epoxy resin material is used suitably in order to obtain a copper clad laminated board. As an example of the said copper clad laminated board, the copper clad laminated board provided with copper foil and the B stage film laminated | stacked on one surface of this copper foil is mentioned. The B stage film of this copper clad laminated board is formed of the said epoxy resin material.

The thickness of the said copper foil of the said copper clad laminated board is not specifically limited. It is preferable that the thickness of the said copper foil exists in the range of 1-50 micrometers. Moreover, in order to raise the adhesive strength of the hardened | cured material and copper foil which hardened the epoxy resin material, it is preferable that the said copper foil has fine unevenness | corrugation on the surface. The formation method of unevenness | corrugation is not specifically limited. As a formation method of the said unevenness | corrugation, the formation method by the process using a well-known chemical liquid is mentioned.

Moreover, the said epoxy resin material is used suitably in order to obtain a multilayer board | substrate. As an example of the said multilayer board | substrate, the multilayer board | substrate provided with a circuit board and the laminated body laminated | stacked on the surface of this circuit board is mentioned. The laminated body in this multilayer substrate is equipped with hardened | cured material and the metal layer laminated | stacked on the surface of this hardened | cured material. The laminated body is arrange | positioned on the surface of the said circuit board from the said hardened | cured material side. The said hardened | cured material is formed by hardening the said epoxy resin material. It is preferable that the said hardened | cured material is laminated | stacked on the surface in which the circuit of the circuit board was provided. It is preferable that a part of said hardened | cured material is buried between the said circuits. The said hardened | cured material is obtained by heating for 1 to 180 minutes at 100-200 degreeC, for example, for 30 to 100 minutes at 100-200 degreeC to such an extent that hardening by heat does not progress too much. When hardened | cured by said preferable heating conditions, when the swelling process is performed in the swelling process conditions mentioned later, for example, or the roughening process is performed on the roughening process conditions mentioned later, 1), 2) the some embedded in hardened | cured material It is further easier to obtain a cured product in which the maximum of the depth and the maximum of the spacing in the entire metal layer portion are 0.5 µm or more, and 3) the minimum of S / D is 0.2 or more and the maximum is 5.0 or less. It becomes easier to obtain the hardened | cured material made into the layer, and the presence state of the inorganic filler part near the interface of a resin part and a metal layer becomes one more favorable, As a result, the adhesive strength of hardened | cured material and a metal layer is 4N. It is easy to make more than / cm.

In the said multilayer board | substrate, it is preferable that the surface on the opposite side to the surface on which the said circuit board of the said hardened | cured material was laminated | stacked is roughened.

In FIG. 2, the multilayer board which used the laminated body which concerns on one Embodiment of this invention is typically shown with partial cutaway front sectional drawing.

On the multilayer board 11 shown in FIG. 2, the hardened | cured material 13-16 of several layers is laminated | stacked on the upper surface 12a of the circuit board 12. As shown in FIG. Hardened | cured material 13-16 is an insulating layer. The metal layer 17 is formed in a part of the upper surface 12a of the circuit board 12. In hardened | cured material 13-15 other than hardened | cured material 16 located in the outer surface on the opposite side to the circuit board 12 side among the hardened | cured material 13-16 of multiple layers, The metal layer 17 is formed in some area. The metal layer 17 is a circuit. The metal layer 17 is arrange | positioned between the circuit board 12 and the hardened | cured material 13, and between each layer of the laminated hardened | cured material 13-16. The lower metal layer 17 and the upper metal layer 17 are mutually connected by at least one of via hole connection and through hole connection which are not shown in figure.

In the multilayer substrate 11, hardened | cured material 13-16 is formed by hardening the said epoxy resin material. In this embodiment, since the surface of hardened | cured material 13-16 is roughened, the fine hole which is not shown in figure is formed in the surface of hardened | cured material 13-16. In addition, the metal layer 17 reaches inside the fine hole. Moreover, 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 in the multilayer board | substrate 11 can be reduced. In addition, good insulation reliability is imparted to the multilayer substrate 11 between an upper metal layer and a lower metal layer which are not connected by a via hole connection and a through hole connection (not shown).

(Harmonic treatment and swelling treatment)

It is preferable that the said epoxy resin material is used in order to obtain the hardened | cured material to be roughened. The said hardened | cured material also contains the precured material which can be further hardened.

In order to form fine unevenness | corrugation on the surface of the pre hardened | cured material obtained by precuring the said epoxy resin material, it is preferable that a precured material is roughened. Before the roughening treatment, the precured product is preferably swelled. It is preferable that the hardened | cured material is swelling after precure and before roughening, and also hardening after roughening. However, the precured product does not necessarily need to be swelled.

It is preferable that the said roughening process is a wet roughening process from a viewpoint of raising the adhesive strength of hardened | cured material and a metal layer more effectively.

As the method of the swelling treatment, for example, a method of treating the precured product with an aqueous solution or an organic solvent dispersion solution of a compound containing ethylene glycol or the like as a main component can be used. Swelling liquid used for a swelling process generally contains alkali as a pH adjuster. It is preferable that a swelling liquid contains sodium hydroxide. Specifically, for example, the swelling treatment is performed by treating the precured product at a treatment temperature of 30 to 85 ° C. for 1 to 30 minutes using a 40 wt% aqueous solution of ethylene glycol or the like. It is preferable that the temperature of the said swelling process exists in the range of 50-85 degreeC. When the temperature of the swelling treatment is too low, it takes a long time for the swelling treatment, and the adhesive strength between the cured product and the metal layer tends to be lowered.

For the roughening treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound or a persulfate compound can be used. These chemical oxidizing agents can be used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added. The roughening liquid which can be used for a roughening process contains alkali as a pH adjuster etc. generally. It is preferable that a roughening liquid contains sodium hydroxide.

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

The method of the said roughening process is not specifically limited. By the method of the said roughening process, using the 30-90g / L permanganic acid or a permanganate solution, and 30-90g / L sodium hydroxide solution, on the conditions of processing temperature 30-85 degreeC and 1-30 minute, The method of processing hardened | cured material is suitable. It is preferable that the said roughening process is performed once or twice. It is preferable that the temperature of the said roughening process exists in the range of 50-85 degreeC.

By performing a roughening process on said conditions, a resin surface is shaved in 0.3 micrometer or more and 1.5 micrometers or less in the direction perpendicular to a surface. When the roughening treatment is performed in the above range, it is easier to obtain a cured product in which the maximum of the depth and the maximum of the spacing in the entirety of the plurality of metal layer portions buried in the cured product are respectively 0.5 µm or more. In addition, it is easier to obtain a cured product having a minimum of 0.2 or more and a maximum of 5.0 or less of S / D. As a result, the adhesive strength between the cured product and the metal layer is 4 N / cm or more. It is easy to make.

When a swelling process is performed using a swelling liquid and a roughening process is next performed using a roughening liquid, it is preferable that arithmetic mean roughness Ra of the surface of a roughened hardened | cured material is 20 nm or more and 350 nm or less. In this case, the adhesive strength of hardened | cured material and a metal layer or wiring becomes high, and it can form a finer wiring further on the surface of hardened | cured material.

Preferably the adhesive strength of hardened | cured material and a metal layer is 4 N / cm or more. When adhesive strength is 4 N / cm or more, metal layers, such as a metal wiring, can be kept favorable on the surface of hardened | cured material.

(Desmear processing)

Moreover, there exist some through-holes formed in the pre-hardened | cured material or hardened | cured material obtained by pre-hardening the said epoxy resin material. In the multilayer substrate or the like, vias, through holes, or the like are formed as through holes. For example, the via can be formed by irradiation of a laser such as a CO ₂ laser. The diameter of the via is not particularly limited, but is about 60 to 80 µm. By formation of the said through hole, the smear which is a residue of resin derived from the resin component contained in hardened | cured material is formed in the bottom part in a via in many cases.

In order to remove the smear, the surface of the cured product is preferably desmeared. The desmear process may also serve as a roughening process.

 As the desmearing treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound or a persulfate compound can be used for the desmearing treatment. These chemical oxidizing agents can be used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added. The desmear process liquid which can be used for a desmear process generally contains alkali. It is preferable that a desmear process liquid contains sodium hydroxide.

The method of the said desmear process is not specifically limited. In the desmear treatment method, for example, using a 30 to 90 g / L permanganic acid or a permanganate solution and a 30 to 90 g / L sodium hydroxide solution, at a treatment temperature of 30 to 85 ° C. and 1 to 30 minutes, Once or twice, a method of treating the precured or cured product is suitable. It is preferable that the temperature of the said desmear process exists in the range of 50-85 degreeC.

By use of the said epoxy resin material, the surface roughness of the surface of the desmearized hardened | cured material becomes small enough.

Hereinafter, this invention is demonstrated concretely by giving an Example and a comparative example. The present invention is not limited to the following examples.

The following components were used for the Example and the comparative example.

(Epoxy resin)

Bisphenol A type epoxy resin ("RE-410S" by Nihon Chemical Co., Ltd., epoxy equivalent 178)

Biphenyl type epoxy resin ("NC-3000H" by Nihon Chemical Co., Ltd., epoxy equivalent 288)

Dicyclopentadiene type epoxy resin ("XD-1000" by Nihon Chemical Co., Ltd., epoxy equivalent 254)

(Hardener)

Active ester compound-containing liquid (including "HPC8000-65T" manufactured by DIC Corporation, 65% by weight of solids and 35% by weight of toluene)

Phenolic compound containing liquid (The phenol hardener which has an amino triazine frame | skeleton, "LA3018-50P" by DIC Corporation, hydroxyl group equivalent 151, weight average molecular weight 1000 or less, 50 weight% of solid content, 50 weight% of propylene glycol monomethyl ether, etc.)

Cyanate ester resin containing liquid (cyanate ester hardener, bisphenol A dicyanate tripolymerized tripolymer, Lonza Japan company "BA230S-75", cyanate group equivalent 230, weight average molecular weight 1000 or less, solid content 75 Weight percent and 25 weight percent methyl ethyl ketone, etc.)

(Weapon filler)

Silica-containing slurry 1 ("SC4050" by admatechs company, the fused silica of an average particle diameter of 0.5 micrometer, contains 70 weight% of solid content, 30 weight% of cyclohexane, etc.)

Silica-containing slurry 2 ("SC4050" made by Admatex company, the fused silica of 1.0 micrometer of average particle diameters contains 70 weight% of solid content, 30 weight% of cyclohexane, etc.)

Silica-containing slurry 3 ("SC1050" made by Admatex Inc., including fused silica having an average particle diameter of 0.1 µm, and containing 70% by weight of solid content and 30% by weight of cyclohexane)

(Hardening accelerator)

Imidazole compound ("2P4MZ", 2-phenyl-4-methylimidazole by Shikoku Kasei Kogyo Co., Ltd.)

(Other ingredients)

Phenoxy resin-containing liquid (including "YX6954-BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 39000 in terms of polystyrene, 30 weight% of solid content, 35 weight% of methyl ethyl ketone, 35 weight% of cyclohexane, etc.)

Amide imide skeletal resin ("SOXR-C" made by Nippon Kochido Co., Ltd.)

(Example 1)

[Preparation of epoxy resin material]

62.47 parts by weight (43.73 parts by weight of solids) of the silica-containing slurry 2 (" SC4050 " manufactured by Admatex), 16.27 parts by weight (10.58 parts by weight of solids) of the active ester compound-containing liquid (" HPC8000-65T " , 2.68 parts by weight of phenol compound-containing liquid ("LA3018-50P" manufactured by DIC Corporation) (1.34 parts by weight of solid content), 6.65 parts by weight of bisphenol A type epoxy resin ("RE-410S" manufactured by Nihon Chemical Co., Ltd.), and biphenyl-type epoxy 8.42 parts by weight of resin (`` NC-3000H '' manufactured by Nihon Chemical Co., Ltd.), 0.50 part by weight of imidazole compound (`` 2P4MZ '' manufactured by Shikoku Chemical Co., Ltd.), and phenoxy resin-containing liquid (`` YX6954-BH30 '' manufactured by Mitsubishi Chemical Corporation) 3.01 weight The part (0.90 weight part by solid content) was mixed, and it stirred at normal temperature until it became a uniform liquid, and obtained the resin composition varnish.

[Preparation of uncured product (B stage film) of resin sheet and precured product A]

The release-processed transparent polyethylene terephthalate (PET) film ("PET5011 550" by Lintech, 50 micrometers in thickness) was prepared. The obtained resin composition varnish was coated on this PET film using an applicator so that the thickness after drying might be 40 micrometers. Next, it dried in the gear oven of 100 degreeC for 2 minutes, and produced the laminated film of the unhardened | cured material (B stage film) of 40-micrometer-thick resin sheet which has an area of 200 mm x 200 mm, and polyethylene terephthalate.

Next, the polyethylene terephthalate film was removed from the laminated film, and the uncured material of the resin sheet was heated in a gear oven at 180 ° C. for 80 minutes to prepare a precured product A (epoxy resin material) of the resin sheet.

[Production of Light Cargo A]

The prehardened | cured material A of the obtained resin sheet was heated at 190 degreeC for 90 minutes, and it hardened further, and hardened | cured material A was obtained.

(Production of pre-cured product B)

The unhardened | cured material of the obtained resin composition on the sheet was vacuum-laminated on the glass epoxy board | substrate (FR-4, "CS-3665" by the Risho industry company), and it was made to react at 150 degreeC for 60 minutes. In this way, the reactant was formed on the glass epoxy substrate, and the laminated sample of the glass epoxy substrate and the reactant was obtained. Thereafter, the following swelling treatment was performed, followed by the following roughening treatment (permanganate treatment).

Swelling Treatment:

The laminated sample was placed in an swelling liquid at 80 ° C. (“Swelling Dip Securiganth P” manufactured by Atotech Japan Co., Ltd.), and stirred at a swelling temperature of 80 ° C. for 10 minutes. It washed with.

Harmonic treatment (permanganate treatment):

The above-mentioned swelling laminated sample was put into 80 degreeC potassium permanganate ("concentrate compact CP" made from Atotech Japan) roughening aqueous solution, and it stirred for 30 minutes at 80 degreeC of roughening temperature. Thereafter, the mixture was washed with a washing solution at 25 ° C. (“Reduction Securiganth P” manufactured by Admatex Co., Ltd.) for 2 minutes, and further washed with pure water. Precured material B was formed.

[Production of Laminate A]

After the roughening treatment, the following plating treatment was performed.

Plating:

The precured product B formed on the glass epoxy substrate was subjected to electroless plating and electrolytic plating in the following procedures.

The surface of the roughened precured product B was treated for 5 minutes with an alkali cleaner at 60 ° C. (“Cleaner Secure Gand 902” manufactured by Atotech Japan), and degreased and washed. After washing, the precured product B was treated with a 25 ° C. pre-dip liquid (“pre-dip neo gant B” manufactured by Atotech Japan) for 2 minutes. Thereafter, the preliminary cured product B was treated with an activator solution at 40 ° C. (“Activator Neo Gant 834” manufactured by Atotech Japan Co., Ltd.) for 5 minutes to attach a palladium catalyst. Next, the said prehardened | cured material B was processed for 5 minutes with 30C degreeC reducing liquid ("reducer neo Gantt WA" by Atotech Japan).

Subsequently, the pre-cured product B is chemical copper liquid ("Bato-printoganth MSK-DK" manufactured by Atotech Japan, "Kappa-Printtogand MSK" manufactured by Atotech Japan, "Stableizer Printto" manufactured by Atotech Japan) (Stabilizer printoganth MSK ") and electroless plating was performed until plating thickness was about 0.5 micrometer. After electroless plating, annealing was applied at a temperature of 120 ° C. for 30 minutes to remove residual hydrogen gas. All the steps up to the electroless plating step were performed while the preliminary cured product B was shaken with the treatment liquid being 1 L on a beaker scale.

Next, electrolytic plating was performed to the precured product B subjected to the electroless plating until the plating thickness was 25 μm. An electric current of 0.6 A / cm ² was flowed using copper sulfate (Reducer-Cu) by electroplating. After the copper plating treatment, the pre-cured product B was heated at 180 ° C. for 1 hour to further cure the pre-cured product B. Thus, the laminated body A with which the copper plating layer was formed on hardened | cured material was obtained.

(Examples 2 to 8 and Comparative Examples 1 to 3)

The epoxy resin material (preliminary hardened | cured material A), hardened | cured material A, pre hardened | cured material B, and laminated | stacking were carried out similarly to Example 1 except having set the kind, compounding quantity, and roughening time of the used compounding component as shown in Table 1 below. Made sieve A.

(evaluation)

(1) The maximum lamination | stacking of the whole depth of the some metal layer part embedded in hardened | cured material in laminated body A, and the largest lamination | stacking of the space | interval in the whole of the some metal layer part buried in hardened | cured material in laminated body A. By observing the cross section of sieve A with "JSM-6700F" by MXOL, MX3000, the reflective electron image of the size of 40 micrometers x 30 micrometers was obtained. This observation was performed in one field of view in the vicinity of the center in the area | region of 5 mm x 5 mm of the surface of laminated body A, and the field of view 5 of each field of view in 4 stage vicinity. In addition, the obtained reflection electron image is an electron image in the direction shown in FIG. By the measurement on the image image of five views, the part of 40 micrometers in length of the interface of the hardened | cured material and the metal layer in the reflection electron image obtained in the said laminated body A was evaluated. As a result, the maximum of the depth in the whole of the said several metal layer part embedded in hardened | cured material, and the maximum of the space | interval in the whole of the said several metal layer part embedded in the said laminated body were obtained. In addition, the maximum of the space | interval in the whole of the said some metal layer part embedded in the hardened | cured material in the obtained laminated body A existed in the reflection electron image of five obtained visual fields.

(2) In the laminated body A, the minimum and maximum of S / D in the whole of the some metal layer part embedded in hardened | cured material (evaluation of S / D)

In the five electron images obtained in the above evaluation (1), the average D μm of the two depths and the interval S μm were evaluated to obtain S / D. The obtained S / D was determined based on the following criteria. In addition, in the whole of the said some metal layer part embedded in the hardened | cured material in the obtained laminated body A, the minimum and maximum of S / D existed in the reflection electron image of five obtained visual fields.

[Minimum and maximum judgment criteria of S / D] A: 0.15 ≤ S / D ≤ 5.0 B: 0.15 ≤ S / D ≤ 5.0

(3) Average linear expansion rate of hardened | cured material

The obtained hardened | cured material A was cut | judged to the magnitude | size of 3 mm x 25 mm. Average line at 0-50 degreeC of the hardened | cured material A cut | disconnected on condition of tensile load 3.3x10 <^-2> N, the temperature increase rate of 5 degree-C / min using the linear expansion rate meter ("TMA / SS120C" by Seiko Instruments) The expansion rate was measured.

(4) Break strength and elongation at break of the cured product

The obtained hardened | cured material A was cut | judged to the magnitude | size of 10 mm x 80 mm. Two cut cured products A were laminated to obtain a test sample having a thickness of 80 μm. Using a tensile tester (&quot; Tensilon &quot; manufactured by Orient, Inc.), a tensile test was conducted under conditions of 60 mm between checks and 5 mm / min cross head speed, and the breaking strength (MPa) and breaking elongation (%) of the test sample. Was measured.

(5) Glass transition temperature of hardened | cured material

The obtained hardened | cured material A was cut | judged to the magnitude | size of 10 mm x 80 mm. The glass transition temperature of the obtained hardened | cured material A was measured on the conditions of the temperature increase rate of 5 degree-C / min, and the frequency of 10 Hz using DMA (Dynamic Mechanical Analysis) apparatus (manufactured by SII Nano Technology Co., Ltd.).

(6) lowest melt viscosity of epoxy resin material

50-150 degreeC of the unhardened | cured material (B stage film) of the obtained resin sheet using the rheometer apparatus (AR-2000 by the TA instrument company) on the conditions of 21.6% of distortion and 1 Hz of frequency. The viscosity in the temperature range was measured, and the value at which the viscosity was the lowest was regarded as the minimum melt viscosity.

(7) Surface roughness (arithmetic mean roughness Ra and ten point mean roughness Rz)

Arithmetic mean roughness Ra and ten point average roughness Rz are measured on the surface of the obtained prehardened | cured material B in the measurement area | region of 94 micrometers x 123 micrometers using a non-contact three-dimensional surface shape measuring apparatus (part number "WYKO NT1100", the Veeco company make). did.

(8) plating adhesive strength

The groove | channel was inserted in the surface of the copper plating layer of the obtained laminated body A by 10 mm width. Then, the adhesive strength of hardened | cured material and a copper plating layer was measured on the conditions of 5 mm / min of crosshead speed | rate using the tensile tester ("Autograph" by Shimadzu Corporation). The obtained measured value was made into plating adhesive strength.

(9) flash etching evaluation

The flash etching process was performed about the precured material B to which electroless copper plating was performed. "SAC" made from Ebara Eudylite Co. was used for the etching solution. Treatment temperature 30 ℃, SAC formulation (35wt% -H ₂ O: 5vol%, 98wt% -H ₂ SO ₄ : 5vol%, Cu: 20g / L), treatment time at 1 minute intervals from 1 to 3 minutes Carried out.

Thereafter, the cross-sectional observation of the pre-cured product B by FE-SEM ("JSM-6700F" manufactured by JEOL Corporation, M x 3000) evaluated the electroless copper plating removability, and determined the flash etching property based on the following criteria. did.

[Criteria for Determining Flash Etchability]

○: Electroless copper plating removed within 1 minute

(Triangle | delta): Electroless copper plating is removed in more than 1 minute and within 3 minutes.

X: electroless copper plating not removed even more than 3 minutes

The compositions and results are shown in Table 1 below.

1 laminate
2 cured products
2A resin part
2B inorganic filler part
3 metal layers
(3a) to (3d) metal layer parts
11 multilayer boards
12 circuit board
12a top
13 to 16 cured product
17 metal layer (wiring)

Claims (13)

Hardened | cured material which hardened the epoxy resin material containing an epoxy resin, a hardening | curing agent, and an inorganic filler,
A metal layer laminated on the surface of the cured product,
A part of said metal layer is buried in said hardened | cured material in several places,
The maximum of the depth in the whole of the said some metal layer part embedded in the said hardened | cured material is 0.5 micrometer or more, and the maximum of the space | interval in the whole of the said several metal layer parts embedded in the said hardened | cured material is 0.5 micrometer or more,
When the average of the depths of two of two adjacent metal layer parts is made into D micrometer among the some metal layer parts buried in the said hardened | cured material, and the space | interval of the two metal layer parts is set to S micrometer,
The laminated body of the whole of the some said metal layer part embedded in the said hardened | cured material whose minimum of S / D is 0.15 or more and the maximum of S / D is 5.0 or less. The method of claim 1,
The laminated body whose maximum of the depth in the whole of the some metal layer part embedded in the said hardened | cured material is 5.0 micrometers or less. The method of claim 2,
The laminated body whose maximum of the depth in the whole of the some said metal layer part embedded in the said hardened | cured material is 4.1 micrometers or less. The method according to any one of claims 1 to 3,
The laminated body whose content of the said inorganic filler is 60 weight% or more and 80 weight% or less in 100 weight% of solid content in the said epoxy resin material. The method according to any one of claims 1 to 3,
The laminated body whose average particle diameter of the said inorganic filler contained in the said epoxy resin material is 0.1 micrometer or more and 5 micrometers or less. The method of claim 4, wherein
The laminated body whose average particle diameter of the said inorganic filler contained in the said epoxy resin material is 0.1 micrometer or more and 5 micrometers or less. Using a cured product obtained by curing an epoxy resin material containing an epoxy resin, a curing agent, and an inorganic filler, by removing the inorganic filler by a roughening treatment, forming a plurality of voids in the cured product;
And forming a metal layer so as to be laminated on the surface of the cured product so as to bury a part of the plurality of voids, thereby obtaining a laminate.
With the said laminated body, one part of the said metal layer is buried in the said hardened | cured material in several places, the maximum of the depth in the whole of the some of said metal layer parts buried in the said hardened | cured material is 0.5 micrometer or more, and in the said hardened | cured material The maximum of the space | interval in the whole of the some embedded said metal layer part is 0.5 micrometer or more, and the average of the depth of the two of two adjacent metal layer parts is made into D micrometer among the said several metal layer parts embedded in the said hardened | cured material When the distance between the two metal layer portions is set to S µm, in the entirety of the plurality of metal layer portions embedded in the cured product, the minimum of S / D is 0.15 or more, and the maximum of S / D is 5.0 or less. The manufacturing method of a laminated body which obtains a laminated body. The method of claim 7, wherein
The said roughening process is a wet roughening process, The manufacturing method of the laminated body. The method according to claim 7 or 8,
And curing the epoxy resin to obtain a cured product.
The manufacturing method of the laminated body using the epoxy resin material whose minimum melt viscosity of 50-150 degreeC is 5 Pa * s or more and 300 Pa * s or less as said epoxy resin material. Circuit board,
The laminate according to any one of claims 1 to 3,
The multilayer substrate with which the said laminated body is arrange | positioned on the surface of the said circuit board from the said hardened | cured material side. Circuit board,
The laminated body of Claim 4 is provided,
The multilayer substrate with which the said laminated body is arrange | positioned on the surface of the said circuit board from the said hardened | cured material side. Circuit board,
The laminated body of Claim 5 is provided,
The multilayer substrate with which the said laminated body is arrange | positioned on the surface of the said circuit board from the said hardened | cured material side. Circuit board,
The laminated body of Claim 6 is provided,
The multilayer substrate with which the said laminated body is arrange | positioned on the surface of the said circuit board from the said hardened | cured material side.

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