JP6477941B2 - Hardened body, laminate, printed wiring board, and semiconductor device - Google Patents

Description

  The present invention relates to a cured body, a laminate, a printed wiring board, and a semiconductor device.

  As a technique for manufacturing a printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the manufacturing method by the build-up method, the insulating layer is generally formed by thermosetting a resin composition. For example, Patent Document 1 discloses a technique for forming an insulating layer by roughening a cured body obtained by thermally curing a resin composition containing silica particles.

  While further improvement in wiring density is demanded, the number of layers due to build-up of printed wiring boards tends to increase, but as the number of layers increases, cracks due to differences in thermal expansion between insulating layers and conductor layers Generation of circuit distortion becomes a problem. As a technique for suppressing the problem of such cracks and circuit distortion, for example, Patent Document 2 discloses a coefficient of thermal expansion of an insulating layer formed by increasing the content of an inorganic filler such as silica particles in a resin composition. A technique for keeping the value low is disclosed.

International Publication No. 2010/35451 JP 2010-202865 A

  In the technique described in Patent Document 1, an insulating layer exhibiting sufficient peel strength with respect to the conductor layer is realized by desorbing silica particles on the surface of the cured body in the roughening treatment. However, if a resin composition having a high content of inorganic fillers such as silica particles is used to form an insulating layer having a low coefficient of thermal expansion, even in such a technique, the formed insulating layer and the conductor layer are separated. In some cases, a decrease in strength was inevitable.

  This invention makes it a subject to provide the hardening body which exhibits the outstanding peeling strength with respect to a conductor layer after a roughening process, hold | maintaining the bulk characteristic that content of an inorganic filler is high.

  As a result of intensive studies on the above problems, the present inventors have found that the amount ratio (inorganic filler / resin component) between the inorganic filler and the resin component in the region in the vicinity of the surface is gradient (that is, depth direction from the surface of the cured body). The cured product having a positive gradient of a certain value or more toward the surface exhibits excellent peel strength to the conductor layer after the roughening treatment while maintaining the bulk property that the content of the inorganic filler is high. I found.

That is, the present invention includes the following contents.
[1] A cured product obtained by curing a resin composition having an inorganic filler content of 50% by mass or more,
In a cross section perpendicular to the surface of the cured body, a resin area A _0-1 in a region from the cured body surface to a depth of 1 μm and a resin area A _1-2 in a region from a depth of 1 μm to a depth of 2 μm are A _{0. −1} / A _1-2 > 1.1, a cured product.
[2] A cured product obtained by curing a resin composition having an inorganic filler content of 50% by mass or more,
In a cross section perpendicular to the surface of the cured body, a resin area A _0-0.5 in a region from the cured body surface to a depth of 0.5 μm, and a resin area A _0.5-1 in a region from a depth of 0.5 μm to a depth of 1 μm Is a cured product satisfying A _0-0.5 / A _0.5-1 > 1.1.
[3] In a cross section perpendicular to the surface of the cured body, the resin area A _0.5-d in a region from a depth of 0.5 μm to a depth _d μm, and the resin area A _d in a region from a depth _d μm to a depth of _0.5 Dμm. _-0.5D is 0.9 ≦ kA _0.5-d / A _d-0.5D ≦ 1.1 (where k is a coefficient satisfying k = | d−0.5D | / | 0.5−d |) D is a number satisfying 0.5 <d <0.5D, and D is the thickness of the cured body.) The cured body according to [1] or [2].
[4] [(number of metal elements derived from inorganic filler) / (number of all elements on the surface of the cured body)] on the surface of the cured body, measured by X-ray photoelectron spectroscopy, is less than 0.01. The cured product according to any one of [1] to [3].
[5] A cured product obtained by curing a resin composition having an inorganic filler content of 50% by mass or more,
When the surface composition analysis by repeating 1) sputter treatment with Ar under the following conditions and 2) surface composition analysis by X-ray photoelectron spectroscopy after the sputter treatment is repeated on the surface of the cured product [[number of atoms of metal element derived from inorganic filler] ) / (Number of atoms of all elements on the surface of the cured body after the sputtering process)] is a cured body in which the number of sputtering processes required until the value of 0.01 or more for the first time is 4 or more.
[Conditions: Ar ⁺ ion, acceleration voltage: 5 kV, irradiation range: 2 mm × 2 mm, sputtering time per one time: 30 seconds]
[6] A roughened cured body having a surface root mean square roughness Rq of 350 nm or less, obtained by roughening the cured body according to any one of [1] to [5].
[7] A laminate comprising the roughened cured body according to [6] and a metal layer formed on the surface of the roughened cured body.
[8] The laminate according to [7], wherein the peel strength between the roughened cured body and the metal layer is 0.5 kgf / cm or more.
[9] A printed wiring board having an insulating layer formed of the cured body according to any one of [1] to [5].
[10] A semiconductor device including the printed wiring board according to [9].

  ADVANTAGE OF THE INVENTION According to this invention, the hardening body which exhibits the outstanding peeling strength with respect to a conductor layer after a roughening process can be provided, maintaining the bulk characteristic that content of an inorganic filler is high.

  Furthermore, the cured body of the present invention exhibits excellent peel strength with respect to the conductor layer (metal layer) despite the small surface roughness after the roughening treatment.

FIG. 1 shows a cross-sectional SEM photograph of a prior art cured body. FIG. 2 shows a cross-sectional SEM photograph of a cured body according to an embodiment of the present invention.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

[Hardened body]
The cured body of the present invention is obtained by curing a resin composition having a high inorganic filler content, and the ratio of the inorganic filler to the resin component in the region near the surface (inorganic filler / resin component). ) Has a gradient (that is, a positive gradient of a certain value or more from the surface of the cured body in the depth direction).

  Research and development has been conducted on a cured body that becomes an insulating layer of a printed wiring board in order to achieve a uniform composition over the entire cured body from the viewpoint of strength, heat resistance, and the like. On the other hand, the cured body of the present invention is characterized by having a steep composition gradient in a region near the surface while maintaining a uniform composition as a bulk property.

  FIG. 1 shows a cross-sectional SEM photograph of a cured body having a “uniform” composition produced based on a conventional design concept. In such a cured body, the particles of the inorganic filler are uniformly dispersed in the resin component, and the particles of the inorganic filler are also present on the surface of the cured body in the same proportion as other regions. As can be understood from the cross-sectional SEM photograph, in the cured body having such a “uniform” composition, some of the particles of the inorganic filler are exposed to the external environment on the surface of the cured body.

In FIG. 2, the cross-sectional SEM photograph of the hardening body produced based on the design concept of this invention is shown. In the hardened | cured material of this invention, in the area | region of the surface vicinity, it has a steep gradient in the quantity ratio (inorganic filler / resin component) of an inorganic filler and a resin component. Specifically, there are almost no inorganic filler particles on the surface of the cured body, and a phase consisting essentially of a resin component is present. However, the inorganic filler particles suddenly appear at a certain depth from the surface of the cured body. The proportion of increases. Preferably, at a position 0.05 μm to 2 μm deep from the surface of the cured body, more preferably at a position 0.05 μm to 1.5 μm deep from the surface of the cured body, and even more preferably from a depth of 0.05 μm to the surface of the cured body. At the position of 1 μm, particularly preferably, at the position of depth of 0.05 μm to 0.5 μm from the surface of the cured body, the proportion of the inorganic filler particles rapidly increases.
Further, in the depth direction, there is no gradient in the quantity ratio between the inorganic filler and the resin component, and the phase has a uniform composition. In the cured product of the present invention having a steep composition gradient only in a limited region near the surface, it retains a uniform composition as a bulk property, so that it has excellent strength, heat resistance, etc. Has a remarkable effect of exhibiting excellent peel strength to the conductor layer after the roughening treatment. Although details will be described later, the cured body of the present invention has been confirmed to exhibit excellent peel strength with respect to the conductor layer (metal layer) despite the small surface roughness after the roughening treatment, The cured body of the present invention significantly contributes to the fine wiring of the printed wiring board.

In the present invention, in expressing the gradient of the quantitative ratio between the inorganic filler and the resin component in the region in the vicinity of the cured body surface, the predetermined depth d1 (μm) in the cross section perpendicular to the cured body surface is a predetermined depth. The ratio (kA _d1 ) between the resin area A _d1-d2 of the region up to d2 (μm) and the resin area A _d2-d3 of the region from the predetermined depth d2 (μm) to the predetermined depth d3 (μm) _-D2 / _Ad2-d3 ). Here, d1, d2, and d3 are numbers that satisfy 0 ≦ d1 <d2 <d3, and k is a coefficient that satisfies k = | d2-d3 | / | d1-d2 |.
The resin area ratio is obtained by SEM observation of a cross section perpendicular to the surface of the cured body, and from the resin area A _{d1 -d2} and the depth d2 (μm) in the region from the depth d1 (μm) to the depth d2 (μm). The resin area A _d2-d3 in the region up to the depth d3 (μm) is measured, and can be calculated from the obtained A _d1-d2 value and A _d2-d3 value. In measuring the A _d1-d2 value and the A _d2-d3 value, the width of the measurement region (measurement distance in a direction parallel to the surface of the cured body) is set equal.
In the present invention, “resin area” means an area occupied by a resin component. The “resin component” for the resin area refers to a component excluding the inorganic filler among the components constituting the resin composition.

For a cured product having a “uniform” composition produced based on a conventional design concept, the kA _{d1 -d2} / A _{d2 -d3} ratio is theoretically 1 regardless of the values of d1, d2 and d3. Yes, even if it is actually measured, it falls within the range of 0.9 to 1.1.

On the other hand, the cured body of the present invention has a steep gradient in the amount ratio between the inorganic filler and the resin component in the region near the surface, and the kA _d1-d2 / A _d2-d3 ratio is d1, d2, and d3. It varies greatly depending on the value.

That is, the cured body of the present invention has a resin area A _0-1 in a region from the cured body surface to a depth of 1 μm and a resin area in a region from a depth of 1 μm to a depth of 2 μm in a cross section perpendicular to the cured body surface. A _1-2 satisfies A _0-1 / A _1-2 > 1.1. From the viewpoint of increasing the peel strength with respect to the conductor layer after the roughening treatment while maintaining the bulk property that the content of the inorganic filler is high, the cured product of the present invention is preferably A _0-1 / A _1-2 ≧ 1.15, more preferably, A _0-1 / A _1-2 ≧ 1.2 is satisfied.
The upper limit of the A _0-1 / A _1-2 ratio is not particularly limited, but is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less.

From the viewpoint of increasing the peel strength to the conductor layer after the roughening treatment while maintaining the bulk characteristics such as a uniform composition and high inorganic filler content, the cured body of the present invention is cured in a cross section perpendicular to the surface of the cured body. the resin area a _0-0.5 in the region from the body surface to a depth of 0.5 [mu] m, the resin area a _0.5-1 in the region to a depth of 1μm in depth from 0.5 [mu] m is, a _0-0.5 / a _0.5- It is preferable to satisfy ₁ > 1.1. From the viewpoint of realizing a cured body surface that exhibits higher peel strength to the conductor layer after the roughening treatment, the cured body of the present invention is more preferably A _0-0.5 / A _0.5-1 ≧ 1.2, and more preferably Is A _0-0.5 / A _0.5-1 ≧ 1.4, even more preferably A _0-0.5 / A _0.5-1 ≧ 1.6, particularly preferably A _0-0.5 / A _0.5-1 ≧ 1.8, A _0-0.5 / A _0.5-1 ≧ 1.9, A _0-0.5 / A _0.5-1 ≧ 2.0, A _0-0.5 / A _0.5-1 ≧ 2.1, or A _0-0.5 / A _{0.5 -1} ≥ 2.2.
The upper limit of the ratio A _0-0.5 / A _0.5-1 is not particularly limited, but is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less.

As described above, the cured body of the present invention has a composition gradient only in a limited region near the surface, and maintains a uniform composition as a bulk property.
In a preferred embodiment, the cured body of the present invention has a resin area A _2-d in a region from a depth of 2 μm to a depth of _d μm and a depth of _d μm to a depth of 0.5 Dμm in a cross section perpendicular to the surface of the cured body. The resin area A _d−0.5D in the region up to 0.9 ≦ kA _2−d / A _d−0.5D ≦ 1.1 (where k is k = | d−0.5D | / | 2 -D |, where d is a number that satisfies 2 <d <0.5D, and D is the thickness of the cured body. This indicates that the cured body of the present invention has a uniform composition in a region having a depth of 2 μm or more from the surface of the cured body.
In a more preferred embodiment, the cured body of the present invention has a resin area A _1.5-d in a region from a depth of 1.5 μm to a depth of _d μm and a depth of from d μm to a depth in a cross section perpendicular to the surface of the cured body. The resin area A _d- 0.5D in the region up to _{0.5 D} μm is 0.9 ≦ kA _1.5-d / A _d-0.5D ≦ 1.1 (where k is k = | d−0.5D | / | 1.5−d |, where d is a number that satisfies 1.5 <d <0.5D, and D is the thickness of the cured body. This means that the cured body of the present invention has a uniform composition in a region having a depth of 1.5 μm or more from the surface of the cured body.
In a more preferred embodiment, the cured body of the present invention has a resin area A _1-d in a region from a depth of 1 μm to a depth of _d μm, and a depth of from 0 μm to a depth of 0. The resin area A _d- 0.5D in the region up to 5D μm is 0.9 ≦ kA _1-d / A _d-0.5D ≦ 1.1 (where k is k = | d−0.5D | / | 1−d |, d is a number satisfying 1 <d <0.5D, and D is the thickness of the cured body). This means that the cured body of the present invention has a uniform composition in a region having a depth of 1 μm or more from the surface of the cured body.
In a particularly preferred embodiment, the cured body of the present invention has a resin area A _0.5-d in a region from a depth of 0.5 μm to a depth _d μm and a depth from the depth _d μm to a depth in a cross section perpendicular to the surface of the cured body. The resin area A _d- 0.5D in the region up to _{0.5 D} μm is 0.9 ≦ kA _0.5-d / A _d-0.5D ≦ 1.1 (where k is k = | d−0.5D | / | 0.5−d |, where d is a number that satisfies 0.5 <d <0.5D, and D is the thickness of the cured body. This indicates that the cured body of the present invention has a uniform composition in a region having a depth of 0.5 μm or more from the surface of the cured body.

  The thickness of the cured product of the present invention is preferably 3 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more, still more preferably 15 μm or more, and particularly preferably 20 μm or more. The thickness of the cured product of the present invention is preferably 100 μm or less, more preferably 90 μm or less, still more preferably 80 μm or less, still more preferably 70 μm or less, and particularly preferably 60 μm or less.

  Hereinafter, the resin composition used when forming the cured body of the present invention will be described.

<Resin composition>
The cured product of the present invention is obtained by curing a resin composition having an inorganic filler content of 50% by mass or more. From the viewpoint of sufficiently reducing the thermal expansion coefficient of the obtained cured body (insulating layer), the content of the inorganic filler in the resin composition is preferably 55% by mass or more, more preferably 60% by mass or more. Preferably, it is 65 mass% or more more preferably.
In addition, in this invention, content of each component which comprises a resin composition is a value when the sum total of the non-volatile component in a resin composition is 100 mass%.

In a cross section perpendicular to the surface of the cured body, the ratio of the resin area A _0-1 in the region from the cured body surface to the depth of 1 μm and the resin area A _1-2 in the region from the depth of 1 μm to the depth of 2 μm (A _In the cured body of the present invention in which _0-1 / A _1-2 ) is in a specific range, the content of the inorganic filler can be further increased without reducing the peel strength with respect to the metal layer (conductor layer). For example, the content of the inorganic filler in the resin composition is 66 mass% or more, 68 mass% or more, 70 mass% or more, 72 mass% or more, 74 mass% or more, 76 mass% or more, or 78 mass% or more. It may be increased to.

  The upper limit of the content of the inorganic filler in the resin composition is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably from the viewpoint of the mechanical strength of a cured product obtained by thermosetting the resin composition. Is 85 mass% or less.

  Examples of the inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, Examples include strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica is particularly suitable. Moreover, spherical silica is preferable as the silica. An inorganic filler may be used individually by 1 type, or may use 2 or more types together. Examples of commercially available spherical fused silica include “SOC2” and “SOC1” manufactured by Admatechs.

  The average particle size of the inorganic filler is preferably in the range of 0.01 μm to 2 μm, more preferably in the range of 0.05 μm to 1.5 μm, still more preferably in the range of 0.07 μm to 1 μm, and 0.1 μm to 0.8 μm. Even more preferred. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-500 manufactured by Horiba, Ltd. can be used.

  Inorganic filler is one kind of aminosilane coupling agent, epoxysilane coupling agent, mercaptosilane coupling agent, silane coupling agent, organosilazane compound, titanate coupling agent, etc. for improving moisture resistance. Or it is preferable to process with 2 or more types of surface treating agents. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical "SZ-31" (Hexamethyldisilazane) manufactured by Co., Ltd.

  In addition, the inorganic filler surface-treated with the surface treatment agent can measure the amount of carbon per unit surface area of the inorganic filler after being washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.

Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is more preferable from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the film form. preferable. Thus, by controlling the surface treatment amount of the inorganic filler, the melt viscosity of the resin composition decreases, the resin component tends to move to the surface of the cured body, and a tendency to form a sharp composition gradient on the surface of the cured body It becomes.

The resin composition used for forming the cured body of the present invention contains a thermosetting resin as a resin. As a thermosetting resin, the conventionally well-known thermosetting resin used when forming the insulating layer of a printed wiring board can be used, and an epoxy resin is especially preferable. The resin composition may also contain a curing agent as necessary. In one Embodiment, the hardening body of this invention can be formed using the resin composition containing an inorganic filler, an epoxy resin, and a hardening | curing agent. The resin composition used for forming the cured product of the present invention may further contain additives such as a thermoplastic resin, a curing accelerator, a flame retardant, and rubber particles.
Hereinafter, an epoxy resin, a curing agent, and an additive that can be used as a material for the resin composition will be described.

(Epoxy resin)
Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, phenol novolac. Type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin , Linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy Resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins and trimethylol type epoxy resins. An epoxy resin may be used individually by 1 type, or may use 2 or more types together.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, it has two or more epoxy groups in one molecule and has a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and three or more epoxy groups in one molecule. And a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). By using a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the cured body formed by curing the resin composition is also improved. In particular, by including a liquid epoxy resin, the resin component easily moves to the surface of the cured body, and tends to form an abrupt composition gradient on the surface of the cured body.

  As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, or naphthalene type epoxy resin is preferable, and bisphenol A type epoxy resin or naphthalene type epoxy resin is more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “EXA4032SS”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, and “jER828EL” (bisphenol A) manufactured by Mitsubishi Chemical Corporation. Type epoxy resin), “jER807” (bisphenol F type epoxy resin), “jER152” (phenol novolac type epoxy resin) and the like. These may be used individually by 1 type, or may use 2 or more types together.

  Examples of solid epoxy resins include tetrafunctional naphthalene type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, biphenyl type epoxy resins, and naphthylene ether type epoxy resins. A tetrafunctional naphthalene type epoxy resin, a biphenyl type epoxy resin, or a naphthylene ether type epoxy resin is more preferable. Specific examples of the solid epoxy resin include “HP-4700”, “HP-4710” (tetrafunctional naphthalene type epoxy resin), “N-690” (cresol novolac type epoxy resin) manufactured by DIC Corporation, “ N-695 ”(cresol novolac type epoxy resin),“ HP-7200 ”(dicyclopentadiene type epoxy resin),“ EXA7311 ”,“ EXA7311-G3 ”,“ HP6000 ”(naphthylene ether type epoxy resin), Nippon Kayaku “EPPN-502H” (trisphenol epoxy resin), “NC7000L” (naphthol novolac epoxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), manufactured by Yakuhin Co., Ltd. “ESN475” manufactured by Nippon Steel Chemical Co., Ltd. Tall novolak epoxy resin), "ESN485" (naphthol novolak type epoxy resin), "YX4000H" manufactured by Mitsubishi Chemical Corporation, "YX4000HK", "YL6121" (biphenyl type epoxy resin) and the like.

  When the liquid epoxy resin and the solid epoxy resin are used in combination as the epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 3 by mass ratio. The range of 1: 0.1 to 1: 2.5 is more preferable, and the range of 1: 0.1 to 1: 2 is even more preferable. By setting the quantity ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) moderate adhesiveness is obtained when used in the form of an adhesive sheet described later, and ii) used in the form of an adhesive sheet. In this case, sufficient flexibility can be obtained, handling properties can be improved, and iii) sufficient breaking strength can be obtained in the cured product of the resin composition. From the viewpoint of the effects i) to iii), the quantitative ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is 1: 0.3 to 1: 1.8 in terms of mass ratio. Is even more preferable, and a range of 1: 0.6 to 1: 1.5 is particularly preferable.

  The content of the epoxy resin in the resin composition is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 45% by mass, still more preferably 5% by mass to 40% by mass, and 7% by mass to 35% by mass. % Is particularly preferred.

  The epoxy equivalent of the epoxy resin is preferably 50 to 3000, more preferably 80 to 2000, and still more preferably 110 to 1000. By being in this range, the crosslink density of the cured product is sufficient and an insulating layer having a low surface roughness is obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

(Curing agent)
The curing agent is not particularly limited as long as it has a function of curing the epoxy resin. For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, and a cyanate ester curing agent may be used. In particular, phenolic curing agents are more preferable. When a phenolic curing agent is used, the compatibility with the epoxy resin is relatively good, so the fluidity is high, the resin component easily moves to the surface of the cured body, and a steep composition gradient on the surface of the cured body. Tend to form. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion (peel strength) to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Among these, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesiveness (peel strength) to the conductor layer, it is preferable to use a triazine skeleton-containing phenol novolac resin as a curing agent.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN375”, “SN395” manufactured by Toto Kasei Co., Ltd. "LA7052", "LA7054", "LA3018", etc. manufactured by DIC Corporation.

  From the viewpoint of adhesion (peel strength) to the conductor layer, an active ester curing agent is also preferable. Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Examples thereof include benzenetriol, dicyclopentadienyl diphenol compound, phenol novolac and the like. Here, the “dicyclopentadienyl diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  Specifically, an active ester compound containing a dicyclopentadienyl diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of a phenol novolak, and an active ester compound containing a benzoylated product of a phenol novolak are preferred. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadienyl diphenol structure are more preferred. Specific examples of the active ester curing agent include, for example, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T” (DIC ()) as an active ester compound containing a dicyclopentadienyl diphenol structure. Manufactured by Co., Ltd.), “EXB9416-70BK” (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac “YLH1026” (manufactured by Mitsubishi Chemical Corporation) and the like are mentioned as active ester compounds containing a benzoylated product of novolak.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Examples of cyanate ester-based curing agents include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Novolac and K Examples include polyfunctional cyanate resins derived from sol novolac, prepolymers in which these cyanate resins are partly triazines, etc. Specific examples of cyanate ester curing agents include “PT30” manufactured by Lonza Japan Co., Ltd. “PT60” (both phenol novolac-type polyfunctional cyanate ester resins), “BA230” (prepolymer in which a part or all of bisphenol A dicyanate is triazine-modified), and the like.

  The amount ratio of the epoxy resin and the curing agent is preferably a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the curing agent] in the range of 1: 0.2 to 1: 2. 1: 0.3-1: 1.5 are more preferable, and 1: 0.4-1: 1 are still more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent. Moreover, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the value obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is: The value obtained by dividing the solid mass of each curing agent by the reactive group equivalent is the total value for all curing agents. By setting the amount ratio of the epoxy resin and the curing agent in such a range, the heat resistance of the cured product of the resin composition is further improved.

  In one Embodiment, the resin composition used in order to form the hardening body of this invention contains the above-mentioned inorganic filler, an epoxy resin, and a hardening | curing agent. From the viewpoint of obtaining a cured product exhibiting excellent peel strength with respect to the metal layer (conductor layer) after the roughening treatment, the resin composition comprises silica as an inorganic filler, liquid epoxy resin as an epoxy resin, and solid epoxy resin. (Mass ratio of liquid epoxy resin: solid epoxy resin is preferably in the range of 1: 0.1 to 1: 3, more preferably in the range of 1: 0.1 to 1: 2.5, and 1: 0. A range of 1-1: 2 is more preferred, a range of 1: 0.3-1: 1.8 is even more preferred, and a range of 1: 0.6-1: 1.5 is particularly preferred). It preferably contains at least one selected from the group consisting of a phenolic curing agent having a novolak structure, a nitrogen-containing phenolic curing agent (preferably a triazine skeleton-containing phenolic curing agent) and an active ester curing agent. . Regarding the resin composition layer containing a combination of such specific components, the preferred content of the inorganic filler, the epoxy resin, and the curing agent is as described above, and among them, the content of the inorganic filler is 50 mass. The content of the epoxy resin is preferably 3% by mass to 50% by mass, the content of the inorganic filler is 50% by mass to 90% by mass, and the content of the epoxy resin is 5% by mass to More preferably, it is 45 mass%. Regarding the content of the curing agent, the ratio of the total number of epoxy groups of the epoxy resin to the total number of reactive groups of the curing agent is preferably in the range of 1: 0.2 to 1: 2, more preferably 1: It is contained so as to be in the range of 0.3 to 1: 1.5, more preferably in the range of 1: 0.4 to 1: 1.

  The resin composition may further contain additives such as a thermoplastic resin, a curing accelerator, a flame retardant, and rubber particles as necessary.

(Thermoplastic resin)
Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyethersulfone resin, and polysulfone resin. By including the thermoplastic resin, the resin component easily moves to the surface of the cured body even during the thermosetting process, and tends to form an abrupt composition gradient on the surface of the cured body. A thermoplastic resin may be used individually by 1 type, or may use 2 or more types together.

  The weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, or may use 2 or more types together. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition, “FX280” and “FX293” manufactured by Toto Kasei Co., Ltd., “YL7553”, “YL6794”, “YL7213” manufactured by Mitsubishi Chemical Corporation, YL7290 "," YL7482 ", etc. are mentioned.

  Specific examples of the polyvinyl acetal resin include: Electric Butyral 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., S-Lec BH Series, BX Series manufactured by Sekisui Chemical Co., Ltd. KS series, BL series, BM series, etc. are mentioned.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (described in JP-A No. 2002-12667 and JP-A No. 2000-319386).

  Specific examples of the polyamide-imide resin include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.

  The content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 20% by mass. By setting the content of the thermoplastic resin within such a range, the viscosity of the resin composition becomes appropriate, and a uniform resin composition having a thickness and a bulk property can be formed. The content of the thermoplastic resin in the resin composition is more preferably 0.5% by mass to 10% by mass.

  Examples of the curing accelerator include organic phosphine compounds, imidazole compounds, amine adduct compounds, and tertiary amine compounds. The content of the curing accelerator is preferably used in the range of 0.05% by mass to 3% by mass when the total amount of nonvolatile components of the epoxy resin and the curing agent is 100% by mass. A hardening accelerator may be used individually by 1 type, or may use 2 or more types together.

  Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may use 2 or more types together. The content of the flame retardant in the resin composition layer is not particularly limited, but is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 9% by mass, and 1.5% by mass to 8% by mass. Is more preferable.

  As the rubber particles, for example, those that do not dissolve in an organic solvent described later and are incompatible with the above-described epoxy resin, curing agent, thermoplastic resin, and the like are used. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which it does not dissolve in an organic solvent or resin and making it into particles.

  Examples of the rubber particles include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, a two-layer structure in which an outer shell layer is made of a glassy polymer and an inner core layer is made of a rubbery polymer, or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glassy polymer layer is made of, for example, methyl methacrylate polymer, and the rubbery polymer layer is made of, for example, butyl acrylate polymer (butyl rubber). A rubber particle may be used individually by 1 type, or may use 2 or more types together.

  The average particle size of the rubber particles is preferably in the range of 0.005 μm to 1 μm, more preferably in the range of 0.2 μm to 0.6 μm. The average particle diameter of the rubber particles can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and a particle size distribution of rubber particles is created on a mass basis using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). And it can measure by making the median diameter into an average particle diameter. The content of the rubber particles in the resin composition is preferably 1% by mass to 10% by mass, and more preferably 2% by mass to 5% by mass.

  The resin composition used to form the cured product of the present invention may contain other additives as necessary. Examples of such other additives include organic copper compounds and organic zinc. Examples include organic metal compounds such as compounds and organic cobalt compounds, and resin fillers such as organic fillers, thickeners, antifoaming agents, leveling agents, adhesion-imparting agents, colorants, and curable resins.

  The cured body of the present invention includes a cured body for forming an insulating layer of a metal-clad laminate (cured body for an insulating layer of a metal-clad laminate), and a cured body for forming an insulating layer of a printed wiring board (printed wiring) It can be used as a cured body for an insulating layer of a plate). In particular, in the production of printed wiring boards by the build-up method, it can be suitably used as a cured body for forming an insulating layer (cured body for build-up insulating layers of printed wiring boards), and a conductor layer is formed by plating It can be more suitably used as a cured body (a cured body for a build-up insulating layer of a printed wiring board on which a conductor layer is formed by plating).

  When the cured product of the present invention is used, the resin composition used for forming the cured product of the present invention is obtained from the resin composition from the viewpoint that stacking of the cured product (insulating layer) can be performed easily and efficiently. It is preferable to use it in the form of an adhesive sheet including a layer.

  In one embodiment, the adhesive sheet includes a support and a resin composition layer (adhesive layer) bonded to the support, and the resin composition layer (adhesive layer) is formed from the resin composition. Is done.

  A film made of a plastic material is preferably used as the support. Examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”), polycarbonate (hereinafter referred to as “PET”). PC ”), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable. In a preferred embodiment, the support is a polyethylene terephthalate film.

  The support may be subjected to a mat treatment or a corona treatment on the surface to be joined to the resin composition layer. Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used.

  Although the thickness of a support body is not specifically limited, The range of 5 micrometers-75 micrometers is preferable, and the range of 10 micrometers-60 micrometers is more preferable. In addition, when a support body is a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  The adhesive sheet is prepared by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish on a support using a die coater, and further heating or blowing hot air to the organic solvent. It can manufacture by drying and forming a resin composition layer.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol. And aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, or may use 2 or more types together.

  The drying conditions are not particularly limited, but the organic solvent content (residual solvent amount) in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Moreover, from a viewpoint of preventing the raise of the melt viscosity in the handleability of a resin composition layer and a film form, 0.5 mass% or more is preferable and 1 mass% or more is more preferable. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition is dried at 50 ° C. to 150 ° C. for 3 to 10 minutes. A layer can be formed. Thus, by controlling the residual solvent amount, the melt viscosity of the resin composition decreases, the resin component easily moves to the surface of the cured body, and a rapid composition gradient on the surface of the cured body tends to be formed.

  In the adhesive sheet, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive sheet can be wound and stored in a roll shape, and can be used by removing the protective film when forming the cured body of the present invention.

The cured body of the present invention is obtained by curing the above resin composition having an inorganic filler content of 50% by mass or more. In one embodiment, the cured body of the present invention is subjected to a heating step of holding a resin composition having an inorganic filler content of 50% by mass or more at a temperature T _{1 for a} certain time, and then the temperature is higher than the temperature T _1. obtained is subjected to a heat curing step for a predetermined holding time at a higher temperature T _2. In a preferred embodiment, the cured product of the present invention comprises a resin composition having an inorganic filler content of 50% by mass or more at a temperature T ₁ (where 50 ° C. ≦ T ₁ <150 ° C.) for 10 minutes or more. After being subjected to the heating step for holding, it is obtained by being subjected to a thermosetting step for holding at temperature T ₂ (150 ° C. ≦ T ₂ ≦ 240 ° C.) for 5 minutes or more.

In the heating step, the temperature T ₁ depends on the composition of the resin composition, but is preferably 60 ° C. ≦ T ₁ ≦ 130 ° C., more preferably 70 ° C. ≦ T ₁ ≦ 120 ° C., and further preferably 80 ° C. ≦ T _1. ≦ 110 ° C., particularly preferably 80 ° C. ≦ T ₁ ≦ 100 ° C.

In the heating step, the time of holding at temperatures _{T 1} depends on the value of the temperatures _{T 1,} preferably 10 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, more preferably 20 to 120 minutes is there.

  The heating step may be carried out under normal pressure or under reduced pressure, but from the viewpoint of realizing a desired resin area ratio, it is preferably in the range of 0.075 mmHg to 3751 mmHg (0.1 hPa to 5000 hPa). It is preferable to carry out at an air pressure in the range of 1 mmHg to 1875 mmHg (1.3 hPa to 2500 hPa).

In the thermosetting step, the temperature T ₂ depends on the composition of the resin composition, but is preferably 155 ° C. ≦ T ₂ ≦ 230 ° C., more preferably 160 ° C. ≦ T ₂ ≦ 220 ° C., and more preferably 170 ° C. ≦ T. ₂ ≦ 210 ° C., particularly preferably 180 ° C. ≦ T ₂ ≦ 200 ° C.

The temperature T ₁ and the temperature T ₂ are preferably 20 ° C. ≦ T ₂ −T ₁ ≦ 150 ° C., more preferably 30 ° C. ≦ T ₂ −T ₁ ≦ 140 ° C., and further preferably 40 ° C. ≦ T ₂ −T. ₁ ≦ 130 ° C., particularly preferably 50 ° C. ≦ T ₂ −T ₁ ≦ 120 ° C.

In the thermosetting process, the time of heat curing at temperature _{T 2} depends on the value of temperature _{T 2,} preferably 5 minutes to 100 minutes, more preferably 10 minutes to 80 minutes, more preferably 10 minutes to 50 For minutes.

  The thermosetting step may be performed under normal pressure or under reduced pressure. Preferably, the air pressure is the same as in the heating step.

After the heating step at a temperature T _1, the resin composition once cooled, may be subjected to a heat curing step at a temperature T _2. Alternatively, after the heating step at a temperature T _1, without cool down resin composition may be subjected to a heat curing step at a temperature T _2. In a preferred embodiment, the cured product of the present invention, between the heating step and the heat curing step, the resulting further subjected to the step of raising the temperature from temperatures T ₁ to a temperature T _2. In such a temperature raising step, the rate of temperature rise from the temperature T ₁ to the temperature T ₂ is preferably 1.5 ° C./min to 30 ° C./min, more preferably 2 ° C./min to 30 ° C./min, and even more preferably. Is 4 ° C./min to 20 ° C./min, even more preferably 4 ° C./min to 10 ° C./min.
In addition, thermosetting of the resin composition may be started in the middle of such a temperature raising step.

  As described above, the cured product of the present invention thus obtained has a steep composition gradient in a region near the surface while maintaining bulk properties such as a uniform composition and a high inorganic filler content.

With respect to the cured product of the present invention, it is preferable that almost no inorganic filler is exposed on the surface to the external environment. In one embodiment, [(number of atoms of metal element derived from inorganic filler) / (number of atoms of all elements on the surface of the cured body)] on the surface of the cured body, measured by X-ray photoelectron spectroscopy, is less than 0.01. It is preferable that For example, when silica is used as the inorganic filler, [(number of silicon atoms) / (number of atoms of all elements on the cured body surface)] on the surface of the cured body, measured by X-ray photoelectron spectroscopy, is 0.01. It is preferable that it is less than. When a mixture of silica and alumina is used as the inorganic filler, [(number of atoms of silicon and aluminum) / (number of atoms of all elements on the surface of the cured body)] measured by X-ray photoelectron spectroscopy on the surface of the cured body Is preferably less than 0.01.
The surface composition analysis of the cured body by X-ray photoelectron spectroscopy can be performed, for example, under the following conditions.
Measuring device: “PHI Quantera SXM” manufactured by ULVAC-PHI
X-ray source: AlKα
X-ray beam diameter: 100 μm
Electric power value: 25W
Voltage: 15kV
Extraction angle: 45 °
Measurement range: 500 × 500 (μm ² )
Charging correction: Neutralizer and Ar ⁺ ion irradiation

  In the cured body of the present invention, as described above, there are almost no inorganic filler particles on the surface of the cured body and a phase consisting essentially of a resin component exists, but at a certain depth position from the cured body surface. The proportion of the inorganic filler particles increases rapidly. Such structural characteristics of the cured product of the present invention can also be confirmed by performing composition analysis in the depth direction of the cured product after surface composition analysis by X-ray photoelectron spectroscopy. The composition analysis in the depth direction can be performed, for example, by the following procedure. 1) Sputtering treatment with Ar and 2) Surface composition analysis after the sputtering treatment are repeated. 2) The surface composition analysis after the sputter treatment can be performed under the same conditions as the surface composition analysis by the X-ray photoelectron spectroscopy. Then, the number of sputter treatments required until the value of [(number of atoms of metal element derived from inorganic filler) / (number of atoms of all elements on the surface of the cured body after sputter treatment)] reaches a predetermined level is obtained. . At this time, the sputter treatment with Ar is performed under the same conditions for all the cured body samples, so that the number of times of the obtained sputter treatment is [(number of atoms of the metal element derived from the inorganic filler) / (after the sputter treatment]. The value of the number of atoms of all elements on the surface of the cured body)] is an index of the depth from the surface of the cured body, which is a predetermined level or more.

The sputtering process using Ar can be performed, for example, under the following conditions.
・ Ar ⁺ ion ・ Acceleration voltage: 5 kV
・ Irradiation range: 2mm x 2mm
-Sputtering time per time: 30 seconds

  When performing the sputtering process with Ar under the above conditions, the cured body of the present invention is [(number of atoms of the metal element derived from the inorganic filler) / (number of atoms of all elements on the surface of the cured body after the sputtering process)]. The number of sputter treatments required for the value to be 0.01 or more for the first time is 4 or more. From the viewpoint of realizing a cured body surface exhibiting higher peel strength with respect to the conductor layer after the roughening treatment, when performing the sputtering treatment with Ar under the above conditions, [(number of atoms of the metal element derived from the inorganic filler) / The number of sputter treatments required for the value of (number of atoms of all elements on the surface of the cured body after the sputter treatment) to be 0.01 or more for the first time is preferably 5 times or more, more preferably 10 times or more, and still more preferably. Is 15 times or more, particularly preferably 20 times or more. In addition, from the viewpoint of maintaining bulk properties such as a uniform composition and high inorganic filler content, [(number of atoms of metal element derived from inorganic filler) / (number of atoms of all elements on the surface of the cured body after sputtering treatment) )] Is preferably 100 times or less, more preferably 50 times or less, and even more preferably 30 times or less until the value of)] reaches 0.01 or more for the first time.

[Roughened hardened body]
In a hardened body having a “uniform” composition based on the conventional design concept, the inorganic filler present on the surface is detached in the roughening treatment, and irregularities are formed on the surface. Such unevenness is considered to exhibit an anchor effect between the metal layer (conductor layer) and contribute to an improvement in peel strength between the roughened cured body and the metal layer. However, when the content of the inorganic filler in the cured body is high, even if it has an anchor effect due to such unevenness, a decrease in peel strength between the roughened cured body and the metal layer may be unavoidable, Moreover, the surface roughness of the roughened cured body may increase.

  As described above, the cured body of the present invention has almost no inorganic filler exposed to the external environment on the surface of the cured body. Regarding the cured product of the present invention, although it contains an inorganic filler in a high content, the detachment of the inorganic filler due to the roughening treatment is compared with a cured product having a “uniform” composition based on the conventional design concept. It is hard to happen. The cured product of the present invention exhibits excellent peel strength to the metal layer after the roughening treatment. This is due to the balance between the content of the inorganic filler and the detachment of the inorganic filler. This is probably due to the reproduction of the surface that contributes to

  The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed. For example, the surface of the cured body can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include Swelling Dip Securigans P and Swelling Dip Securigans SBU manufactured by Atotech Japan. Although the swelling process by a swelling liquid is not specifically limited, For example, it can carry out by immersing a hardening body for 1 minute-20 minutes in 30-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin of the cured body to an appropriate level, it is preferable to immerse the cured body in a swelling liquid at 40 to 80 ° C. for 5 seconds to 15 minutes. Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the cured product in an oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as Concentrate Compact P and Dosing Solution Securigans P manufactured by Atotech Japan Co., Ltd. As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, for example, Reduction Sholysin Securigant P manufactured by Atotech Japan Co., Ltd. may be mentioned. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidant solution in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidant solution in a neutralizing solution at 40 to 70 ° C. for 5 to 20 minutes is preferable.

In a preferred embodiment, the roughened cured product of the present invention has a surface root mean square roughness Rq of 350 nm or less. The surface roughness Rq of the roughened cured product of the present invention is preferably 300 nm or less, more preferably 250 nm or less, still more preferably 220 nm or less, and particularly preferably 200 nm or less. In the roughened cured body of the present invention, even when the surface roughness Rq is as small as 180 nm or less, 160 nm or less, 140 nm or less, or 120 nm or less, excellent peel strength against the metal layer (conductor layer) Presents. On the other hand, the lower limit value of the surface roughness Rq is not particularly limited, but is 10 nm or more, 30 nm or more, 50 nm or more, etc. in order to stabilize the peel strength.
The root mean square roughness Rq of the roughened cured body can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by Bee Coins Instruments can be cited.

[Laminate]
The laminated body of this invention is equipped with the roughening hardening body of this invention, and the metal layer formed in the surface of this roughening hardening body.

  Although the metal used for the metal layer is not particularly limited, in a preferred embodiment, the metal layer is made of gold, platinum, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. One or more metals selected from the group consisting of: The metal layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of metal layer formation, cost, ease of removal by etching, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, silver or copper, or nickel-chromium alloy, copper Nickel alloy, copper / titanium alloy alloy layer is preferable, chromium, nickel, titanium, aluminum, zinc, gold, silver or copper single metal layer, or nickel / chromium alloy alloy layer is more preferable, copper single metal layer Is more preferable.

  The metal layer may have a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the metal layer has a multilayer structure, the layer in contact with the roughened cured body is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel / chromium alloy.

  The metal layer can be formed by dry plating or wet plating. Examples of the dry plating include known methods such as vapor deposition, sputtering, and ion plating. In the case of wet plating, for example, a metal layer is formed by combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the metal layer (conductor layer) can be formed, and the metal layer can be formed only by electroless plating. As a method for forming the wiring pattern, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.

  The thickness of the metal layer is preferably 40 μm or less, more preferably 1 to 35 μm, and still more preferably 3 to 20 μm, from the viewpoint of miniaturization of the printed wiring board. Even when the metal layer has a multilayer structure, the thickness of the entire metal layer is preferably within the above range.

In the laminate of the present invention, the peel strength between the roughened cured body and the metal layer is preferably 0.5 kgf / cm or more, more preferably 0.55 kgf / cm or more, still more preferably 0.60 kgf / cm or more, particularly Preferably it is 0.65 kgf / cm or more. On the other hand, the upper limit value of the peel strength is not particularly limited, but is 1.2 kgf / cm or less, 0.9 kgf / cm or less, and the like.
Although the laminate of the present invention exhibits such a high peel strength even though the surface roughness Rq of the roughened cured body is as small as 350 nm or less, it greatly contributes to the fine wiring of the printed wiring board. is there.
In the present invention, the peel strength between the roughened cured body and the metal layer means the peel strength when the metal layer is peeled in the direction perpendicular to the roughened cured body (90-degree direction) (90-degree peel strength). The peel strength when the metal layer is peeled in the direction perpendicular to the roughened cured body (90-degree direction) can be determined by measuring with a tensile tester. Examples of the tensile tester include “AC-50C-SL” manufactured by TSE Corporation.

[Printed wiring board]
The printed wiring board of the present invention is characterized in that an insulating layer is formed by the cured body of the present invention.

  In one embodiment, the printed wiring board of the present invention can be manufactured using the above-described adhesive sheet. In such an embodiment, after the laminating process is performed so that the resin composition layer of the adhesive sheet is bonded to the circuit board, the above-described “heating step” and “thermosetting step” are performed, and the cured body of the present invention is circuitized. It can be formed on a substrate. In addition, when an adhesive sheet has a protective film, it can use for manufacture after removing a protective film.

The conditions for the laminating treatment are not particularly limited, and known conditions used for forming an insulating layer of a printed wiring board using an adhesive sheet can be employed. For example, it can be performed by pressing a heated metal plate such as a SUS mirror plate from the support side of the adhesive sheet. In this case, it is preferable not to press the metal plate directly, but to press through an elastic material such as heat-resistant rubber so that the adhesive sheet sufficiently follows the circuit irregularities of the circuit board. The pressing temperature is preferably in the range of 70 ° C. to 140 ° C., and the pressing pressure is preferably 1 kgf / cm ^{2 to} 11 kgf / cm ² (9.8 × 10 ⁴ N / m ^{2 to} 107.9 × 10 ⁴ N / m ² ), and the pressing time is preferably in the range of 5 seconds to 3 minutes. The laminating process is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. Lamination treatment can be performed using a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like.

  In the present invention, the “circuit board” is mainly patterned on one or both sides of a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. This means that a conductor layer (circuit) is formed. Further, when the printed wiring board is manufactured, an inner layer circuit board of an intermediate product on which an insulating layer and / or a conductor layer is to be formed is also included in the “circuit board” in the present invention.

  In other embodiment, the printed wiring board of this invention can be manufactured using the above-mentioned resin varnish. In such an embodiment, after the resin varnish is uniformly applied on the circuit board by a die coater or the like, and the resin composition layer is formed on the circuit board by heating and drying, the above-mentioned “heating step” and “ The cured body of the present invention can be formed on a circuit board by performing a “thermosetting step”. The organic solvent used for the resin varnish and the heating and drying conditions may be the same as those described for the production of the adhesive sheet.

  Next, after the above-mentioned “roughening treatment” is performed on the cured body formed on the circuit board to form the roughened cured body, a metal layer (conductor layer) is formed on the surface of the roughened cured body. Form. Note that the manufacturing of the printed wiring board may further include a drilling step for drilling the insulating layer. These steps can be performed according to various methods used for manufacturing a printed wiring board, which are known to those skilled in the art.

[Semiconductor device]
A semiconductor device can be manufactured using the printed wiring board.

  Examples of such semiconductor devices include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts). .

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, “parts” means “parts by mass” unless otherwise specified.

  First, various measurement methods and evaluation methods will be described.

<Measurement of resin area ratio>
The resin area ratio of the cured bodies produced in the examples and comparative examples was observed by SEM for the cross section perpendicular to the cured body surface, and the resin area A _d1− in the region from the depth d1 (μm) to the depth d2 (μm). _d2 and the resin area A _d2-d3 in the region from the depth d2 (μm) to the depth d3 (μm) were measured, and calculated from the obtained A _d1-d2 value and A _d2-d3 value.
Specifically, the resin area is stored as an SEM observation image as an image, and using image analysis software, the resin part is black and the inorganic filler part other than resin is white and is binarized, and the number of bits of the black part Was the area of the resin part.
The resin area ratio (A _0-1 / A _1-2 ) is determined by SEM observation of a cross section perpendicular to the surface of the cured body. The resin area A _0-1 in the region from the cured body surface to a depth of 1 μm and the depth of 1 μm The resin area A _1-2 in the region from 1 to 2 μm in depth was measured and calculated from the obtained A _0-1 value and A _1-2 value.
The resin area ratio (A _0-0.5 / A _0.5-1 ) was determined by SEM observation of a cross section perpendicular to the surface of the cured body, and the resin area A _0-0.5 in the region from the cured body surface to a depth of 0.5 μm, The resin area A _0.5-1 in a region from a depth of 0.5 μm to a depth of 1 μm was measured and calculated from the obtained A _0-0.5 value and A _0.5-1 value.
The resin area ratio (kA _0.5-d / A _d-0.5D ) is determined by SEM observation of a cross section perpendicular to the surface of the cured body, and the resin area A _0.5- in the region from depth 0.5 μm to depth d (μm). _d and the resin area A _d-0.5D in the region from the depth d (μm) to the depth 0.5 D (μm), and from the obtained A _0.5-d value and A _d-0.5D value Calculated. Here, in the present embodiment, d = 1 (μm), D = 35 (μm), k = | d−0.5D | / | 0.5−d | = 16.5 / 0. .5 = 33.
The SEM observation of the cross-section of the cured product was performed using a focused ion beam / scanning ion microscope “SMI3050SE” manufactured by SII Nanotechnology, and the width of the measurement region was 7.5 μm.

<Composition analysis of cured body by X-ray photoelectron spectroscopy>
The surface composition of the cured bodies produced in Examples and Comparative Examples, that is, [(number of atoms of metal element derived from inorganic filler) / (number of atoms of all elements on the surface of the cured body)] is X-ray photoelectron spectrometer ( The measurement was performed under the following conditions using “PHI Quantera SXM” manufactured by ULVAC-PHI.
X-ray source: AlKα
X-ray beam diameter: 100 μm
Electric power value: 25W
Voltage: 15kV
Extraction angle: 45 °
Measurement range: 500 × 500 (μm ² )
Charging correction: Neutralizer and Ar ⁺ ion irradiation After surface composition analysis, composition analysis was performed in the depth direction of the cured product. The composition analysis in the depth direction was performed by repeating 1) sputtering with Ar and 2) surface composition analysis after the sputtering. The number of sputtering processes required until the value of [(number of atoms of the metal element derived from the inorganic filler) / (number of atoms of all elements on the surface of the cured body after the sputtering process)] becomes 0.01 or more for the first time. Asked. In addition, the conditions of the sputter | spatter process by Ar are as follows, It was set as the same conditions about all the hardening body samples.
Ar ⁺ ion Acceleration voltage: 5 kV
Irradiation range: 2mm x 2mm
Sputtering time per time: 30 seconds

<Measurement of root mean square roughness (Rq) of surface of roughened cured body>
The root mean square roughness (Rq) of the surfaces of the roughened cured bodies obtained in the examples and comparative examples was measured using a non-contact type surface roughness meter ("WYKO NT3300" manufactured by BEIKO INSTRUMENTS Co., Ltd.) in the VSI mode. The value (nm) of the root mean square roughness (Rq) was obtained from the numerical value obtained by setting the measurement range to 121 μm × 92 μm with a 50 × lens. Moreover, it measured by calculating | requiring the average value of 10 points | pieces.

<Measurement of peel strength>
The metal layer (conductor layer) of the laminate manufactured in the examples and comparative examples was cut into a portion having a width of 10 mm and a length of 100 mm, this one end was peeled off and grasped with a gripper, and at room temperature, 50 mm / min. The load (kgf / cm) when peeling 35 mm in the vertical direction at a speed of was measured to determine the peel strength. For the measurement, a tensile tester (manufactured by TSE, “AC-50C-SL”) was used.

  Adhesive sheets having the resin composition layers 1, 2, 3, or 4 used in Examples and Comparative Examples were prepared according to the following method.

(Preparation of adhesive sheet having resin composition layer 1)
(1) Preparation of resin varnish 1 20 parts of biphenyl type epoxy resin (epoxy equivalent of about 290, “NC3000H” manufactured by Nippon Kayaku Co., Ltd.), naphthalene type tetrafunctional epoxy resin (epoxy equivalent of 162, “HP” manufactured by DIC Corporation) -4700 ") 5 parts, 20 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180," jER828EL "manufactured by Mitsubishi Chemical Corporation), and phenoxy resin (weight average molecular weight 35000," YL7553BH30 "manufactured by Mitsubishi Chemical Corporation), 12 parts of a methyl ethyl ketone (MEK) solution having a solid content of 30% by mass was dissolved by heating in a mixed solvent of 8 parts of MEK and 8 parts of cyclohexanone with stirring. There, 15 parts of phenol novolac-based curing agent (phenolic hydroxyl group equivalent of about 124, “LA-7054” manufactured by DIC Corporation, MEK solution of 60% by mass of nonvolatile component), active ester-based curing agent (active ester equivalent of about 223) , "HPC8000-65T" manufactured by DIC Corporation, toluene part of 65% by mass nonvolatile component), tetrabutylphosphonium decanoate which is a quaternary phosphonium-based curing accelerator ("TBP-" manufactured by Hokuko Chemical Co., Ltd.) DA ") 0.2 parts, spherical silica (" SOC2 "manufactured by Admatechs Co., Ltd.) surface-treated with an aminosilane-based coupling agent (" KBM573 "manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.5 [mu] m, carbon per unit area 75 parts by weight of 0.39 mg / m ² ), polyvinyl butyral resin solution (glass transition temperature 105 ° C., manufactured by Sekisui Chemical Co., Ltd.) Resin varnish 1 was prepared by mixing 2.5 parts of “KS-1”, a mixed solution of 15% by mass of a non-volatile component of 15% by mass of ethanol and toluene in a mass ratio of 1: 1) and uniformly dispersing with a high-speed rotary mixer.
When the total of the non-volatile components in the resin varnish 1 was 100% by mass, the content of the inorganic filler (spherical silica) was 54.1% by mass.
(2) Preparation of Adhesive Sheet A polyethylene terephthalate film (thickness 38 μm, hereinafter abbreviated as “PET film”) was prepared as a support. The resin varnish 1 obtained above was uniformly applied on the support with a die coater and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes to form a resin composition layer 1. The resin composition layer 1 had a thickness of 40 μm and a residual solvent amount of about 2% by mass.
Next, a polypropylene film (thickness: 15 μm) as a protective film was wound around the surface of the resin composition layer 1 in a roll shape. The obtained roll-shaped adhesive sheet was slit to a width of 507 mm to obtain an adhesive sheet having dimensions of 507 mm × 336 mm.

(Preparation of adhesive sheet having resin composition layer 2)
(1) Preparation of resin varnish 2 30 parts of biphenyl type epoxy resin (epoxy equivalent of about 290, “NC3000H” manufactured by Nippon Kayaku Co., Ltd.), naphthalene type tetrafunctional epoxy resin (epoxy equivalent of 162, “HP” manufactured by DIC Corporation) -4700 "), 5 parts, liquid bisphenol A type epoxy resin (epoxy equivalent 180," jER828EL "manufactured by Mitsubishi Chemical Corporation), and phenoxy resin (weight average molecular weight 35000," YL7553BH30 "manufactured by Mitsubishi Chemical Corporation), 2 parts of a methyl ethyl ketone (MEK) solution having a solid content of 30% by mass was dissolved by heating in a mixed solvent of 8 parts of MEK and 8 parts of cyclohexanone with stirring. There, 30 parts of a phenol novolac-based curing agent (phenolic hydroxyl group equivalent of about 124, “LA-7054” manufactured by DIC Corporation, MEK solution having a nonvolatile component of 60% by mass), a curing accelerator (manufactured by Guangei Chemical Industry Co., Ltd.) , “4-dimethylaminopyridine (DMAP)” 0.1 part, spherical silica surface treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SOC1” manufactured by Admatechs Co., Ltd.), average particle diameter 0.24 μm, 160 parts of carbon amount per unit area 0.36 mg / m ² , polyvinyl butyral resin solution (glass transition temperature 105 ° C., “KS-1” manufactured by Sekisui Chemical Co., Ltd.), 15% by mass of non-volatile components 2 parts of a mixed solution having a mass ratio of ethanol and toluene of 1: 1) was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 2.
When the total of the non-volatile components in the resin varnish 2 was 100% by mass, the content of the inorganic filler (spherical silica) was 69.4% by mass.
(2) Preparation of adhesive sheet Resin composition in the same manner as "(Preparation of adhesive sheet having resin composition layer 1)" except that resin varnish 2 obtained above was used instead of resin varnish 1. An adhesive sheet (size: 507 mm × 336 mm) having the physical layer 2 was prepared.

(Preparation of adhesive sheet having resin composition layer 3)
(1) Preparation of resin varnish 3 35 parts of biphenyl type epoxy resin (epoxy equivalent of about 290, “NC3000H” manufactured by Nippon Kayaku Co., Ltd.), liquid bisphenol A type epoxy resin (epoxy equivalent of 180, manufactured by Mitsubishi Chemical Corporation) jER828EL ") 15 parts, and phenoxy resin (weight average molecular weight 35000," YL7553BH30 "manufactured by Mitsubishi Chemical Corporation, methyl ethyl ketone (MEK) solution with a solid content of 30% by mass) in a mixed solvent of MEK 8 parts and cyclohexanone 8 parts The solution was heated and dissolved with stirring. Thereto, 10 parts of a methoxypropanol solution having a solid content of 50% by mass of a triazine-containing cresol-based curing agent (hydroxyl group equivalent 151, "LA-3018-50P" manufactured by DIC Corporation), an active ester-based curing agent (active ester equivalent of about 223, “HPC8000-65T” manufactured by DIC Corporation, 40 parts of a non-volatile component 65 mass% toluene solution, a curing accelerator (manufactured by Guangei Chemical Industry Co., Ltd., “4-dimethylaminopyridine (DMAP)”) 5 parts, 0.2 part of a curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., “2-phenyl-4-methylimidazole (2P4MZ)”), an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical) was surface treated. Spherical silica (“SOC1” manufactured by Admatechs Co., Ltd., average particle size 0.24 μm, carbon amount per unit area 0.36 mg / m ² ) 200 parts were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 3.
When the total of the non-volatile components in the resin varnish 3 was 100% by mass, the content of the inorganic filler (spherical silica) was 70.2% by mass.
(2) Preparation of Adhesive Sheet Resin composition in the same manner as “(Preparation of Adhesive Sheet Having Resin Composition Layer 1)”, except that instead of resin varnish 1, resin varnish 3 obtained above was used. An adhesive sheet (size: 507 mm × 336 mm) having the physical layer 3 was prepared.

(Preparation of adhesive sheet having resin composition layer 4)
(1) Preparation of resin varnish 4 35 parts of biphenyl type epoxy resin (epoxy equivalent of about 290, “NC3000H” manufactured by Nippon Kayaku Co., Ltd.), liquid bisphenol A type epoxy resin (epoxy equivalent of 180, manufactured by Mitsubishi Chemical Corporation) jER828EL ") 15 parts, and phenoxy resin (weight average molecular weight 35000," YL7553BH30 "manufactured by Mitsubishi Chemical Corporation, methyl ethyl ketone (MEK) solution with a solid content of 30% by mass) in a mixed solvent of MEK 8 parts and cyclohexanone 8 parts The solution was heated and dissolved with stirring. Thereto, 10 parts of a methoxypropanol solution having a solid content of 50% by mass of a triazine-containing cresol-based curing agent (hydroxyl group equivalent 151, "LA-3018-50P" manufactured by DIC Corporation), an active ester-based curing agent (active ester equivalent of about 223, “HPC8000-65T” manufactured by DIC Corporation, 40 parts of a non-volatile component 65 mass% toluene solution, a curing accelerator (manufactured by Guangei Chemical Industry Co., Ltd., “4-dimethylaminopyridine (DMAP)”) 3 parts, 0.1 part of a curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., “2-Phenyl-4-methylimidazole (2P4MZ)”), surface treatment with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical) Spherical silica (“SOC2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, carbon amount per unit area 0.39 mg / m ² ) 3 00 parts were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish 4.
When the total of the non-volatile components in the resin varnish 4 was 100% by mass, the content of inorganic filler (spherical silica) was 78.0% by mass.
(2) Preparation of adhesive sheet Resin composition in the same manner as "(Preparation of adhesive sheet having resin composition layer 1)" except that resin varnish 4 obtained above was used instead of resin varnish 1. An adhesive sheet (size: 507 mm × 336 mm) having the physical layer 4 was prepared.

<Example 1>
A cured product was produced according to the following method. About the obtained hardening body, the surface analysis by a X ray photoelectron spectroscopy and the measurement of the resin area ratio were performed. The results are shown in Table 2.

(Manufacture of cured product)
(1) Base treatment of inner layer circuit board Both surfaces of glass cloth base epoxy resin double-sided copper clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Works “R5715ES”) on which inner layer circuit is formed Was immersed in “CZ8100” manufactured by MEC Co., Ltd., and the copper surface was roughened.
(2) Adhesive sheet laminating process The adhesive sheet having the resin composition layer 1 is obtained by using a batch type vacuum pressure laminator (manufactured by Meiki Seisakusho Co., Ltd., “MVLP-500”). Lamination was performed on both sides of the inner layer circuit board so as to be bonded to the inner layer circuit board. The laminating process was performed by reducing the pressure for 30 seconds to reduce the air pressure to 13 hPa or less, and then pressing at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.
(3) Curing of resin composition The PET film was peeled from the laminated adhesive sheet, the resin composition was cured under curing conditions 1 listed in Table 1, and a cured body (on copper) on both surfaces of the inner circuit board. A thickness of 35 μm) was obtained.

  Next, the obtained cured body was roughened according to the following method to produce a roughened cured body. About the obtained roughening hardening body, the root mean square roughness Rq of the surface was measured. The results are shown in Table 2.

(Production of roughened cured body)
The cured product was immersed in a swelling solution (Atotech Japan Co., Ltd., “Swelling Dip / Seculigand P”, containing diethylene glycol monobutyl ether) at 60 ° C. for 5 minutes, and then a roughening solution (Atotech Japan Co., Ltd., “ Concentrate Compact P ”, an aqueous solution having a potassium permanganate concentration of about 6% by mass and a sodium hydroxide concentration of about 4% by mass) at 80 ° C. for 20 minutes. Finally, it was immersed for 5 minutes at 40 ° C. in a neutralizing solution (“Reduction Solutionin Securigant P” manufactured by Atotech Japan Co., Ltd.) to obtain a roughened cured body.

  Subsequently, according to the following method, a metal layer (conductor layer) was formed on the surface of the obtained roughened cured body, and a laminate was obtained on both surfaces of the inner layer circuit board. About the obtained laminated body, peel strength was measured. The results are shown in Table 2.

(Manufacture of laminates)
An inner layer circuit board having a roughened cured body on both sides is immersed in an electroless plating solution containing palladium chloride (PdCl ₂ ), and then immersed in an electroless copper plating solution, and a plating seed layer is formed on the surface of the roughened cured body. Formed. Then, after annealing for 30 minutes at 150 ° C., an etching resist was formed on the plating seed layer, and the plating seed layer was patterned by etching. Subsequently, copper sulfate electrolytic plating was performed to form a copper layer (conductor layer) having a thickness of 30 ± 5 μm, and then annealed at 180 ° C. for 60 minutes to obtain a laminate on both surfaces of the inner circuit board.

<Example 2>
A cured product, a roughened cured product, and a laminate were produced and evaluated in the same manner as in Example 1 except that the curing condition of the resin composition was changed to the curing condition 2 described in Table 1. The results are shown in Table 2.

<Example 3>
A cured product, a roughened cured product, and a laminate were produced and evaluated in the same manner as in Example 1 except that the curing condition of the resin composition was changed to the curing condition 3 described in Table 1. The results are shown in Table 2.

<Example 4>
A cured product, a roughened cured product, and a laminate were produced and evaluated in the same manner as in Example 1 except that the curing condition of the resin composition was changed to the curing condition 4 described in Table 1. The results are shown in Table 2.

<Example 5>
A cured product, a roughened cured product, and a laminate were produced and evaluated in the same manner as in Example 1 except that the curing condition of the resin composition was changed to the curing condition 5 described in Table 1. The results are shown in Table 2.

<Example 6>
A cured product, a roughened cured product, and a laminate were produced and evaluated in the same manner as in Example 1 except that the curing condition of the resin composition was changed to the curing condition 6 described in Table 1. The results are shown in Table 2.

<Example 7>
A cured product, a roughened cured product, and a laminate were produced and evaluated in the same manner as in Example 1 except that the curing condition of the resin composition was changed to the curing condition 7 described in Table 1. The results are shown in Table 2.

<Example 8>
A cured product, a roughened cured product, and a laminate were produced and evaluated in the same manner as in Example 1 except that the curing condition of the resin composition was changed to the curing condition 8 described in Table 1. The results are shown in Table 2.

<Example 9>
Except that the adhesive sheet having the resin composition layer 2 was used instead of the adhesive sheet having the resin composition layer 1 and the curing conditions of the resin composition were changed to the curing conditions 4 described in Table 1, In the same manner as in Example 1, a cured product, a roughened cured product, and a laminate were produced and evaluated. The results are shown in Table 2.

<Example 10>
Except for using the adhesive sheet having the resin composition layer 3 instead of the adhesive sheet having the resin composition layer 1 and changing the curing conditions of the resin composition to the curing conditions 4 described in Table 1, In the same manner as in Example 1, a cured product, a roughened cured product, and a laminate were produced and evaluated. The results are shown in Table 2.

<Example 11>
Except that the adhesive sheet having the resin composition layer 4 was used instead of the adhesive sheet having the resin composition layer 1 and the curing conditions of the resin composition were changed to the curing conditions 4 described in Table 1, In the same manner as in Example 1, a cured product, a roughened cured product, and a laminate were produced and evaluated. The results are shown in Table 2.

<Comparative Example 1>
A cured product, a roughened cured product, and a laminate were produced and evaluated in the same manner as in Example 1 except that the curing condition of the resin composition was changed to the curing condition 9 described in Table 1. The results are shown in Table 2.

<Comparative example 2>
A cured product, a roughened cured product, and a laminate were produced and evaluated in the same manner as in Example 1 except that the curing condition of the resin composition was changed to the curing condition 10 described in Table 1. The results are shown in Table 2.

<Comparative Example 3>
A cured product, a roughened cured product, and a laminate were produced and evaluated in the same manner as in Example 1 except that the curing condition of the resin composition was changed to the curing condition 11 described in Table 1. The results are shown in Table 2.

<Comparative example 4>
A cured product, a roughened cured product, and a laminate were produced and evaluated in the same manner as in Example 1 except that the curing condition of the resin composition was changed to the curing condition 12 shown in Table 1. The results are shown in Table 2.

Claims (13)

A resin composition containing an epoxy resin and an inorganic filler and having an inorganic filler content of 50% by mass or more and 95% by mass or less (however, a resin composition containing a cyanate ester-based curing agent and a naphthylene ether type epoxy resin) A cured product obtained by curing
In a cross section perpendicular to the surface of the cured body, a resin area A _0-1 in a region from the cured body surface to a depth of 1 μm and a resin area A _1-2 in a region from a depth of 1 μm to a depth of 2 μm are A _{0. −1} / A _1-2 > 1.1, a cured product. A resin composition containing an epoxy resin and an inorganic filler and having an inorganic filler content of 50% by mass or more and 95% by mass or less (however, a resin composition containing a cyanate ester-based curing agent and a naphthylene ether type epoxy resin) A cured product obtained by curing
In a cross section perpendicular to the surface of the cured body, a resin area A _0-0.5 in a region from the cured body surface to a depth of 0.5 μm, and a resin area A _0.5-1 in a region from a depth of 0.5 μm to a depth of 1 μm Is a cured product satisfying A _0-0.5 / A _0.5-1 > 1.1. A resin composition containing a thermosetting resin and an inorganic filler and having an inorganic filler content of 50% by mass to 95% by mass (however, a resin composition containing a cyanate ester-based curing agent and a naphthylene ether type epoxy resin) A cured product obtained by curing
In a cross section perpendicular to the surface of the cured body, a resin area A _0-1 in a region from the cured body surface to a depth of 1 μm and a resin area A _1-2 in a region from a depth of 1 μm to a depth of 2 μm are A _{0. −1} / A _1-2 > 1.1, a cured body for an insulating layer of a printed wiring board. A resin composition containing a thermosetting resin and an inorganic filler and having an inorganic filler content of 50% by mass to 95% by mass (however, a resin composition containing a cyanate ester-based curing agent and a naphthylene ether type epoxy resin) A cured product obtained by curing
In a cross section perpendicular to the surface of the cured body, a resin area A _0-0.5 in a region from the cured body surface to a depth of 0.5 μm, and a resin area A _0.5-1 in a region from a depth of 0.5 μm to a depth of 1 μm Is a cured body for an insulating layer of a printed wiring board, satisfying A _0-0.5 / A _0.5-1 > 1.1. In the cross section perpendicular to the surface of the cured body, the resin area A _0.5-d in the region from the depth 0.5 μm to the depth _d μm and the resin area A _d- 0.5D in the region from the depth _d μm to the depth _0.5 Dμm. 0.9 ≦ kA _0.5-d / A _d-0.5D ≦ 1.1 (where k is a coefficient satisfying k = | d−0.5D | / | 0.5−d | The cured product according to any one of claims 1 to 4, wherein d is a number satisfying 0.5 <d <0.5D and D is a thickness of the cured product.   The [(number of atoms of metal element derived from inorganic filler) / (number of atoms of all elements on the surface of the cured body)] on the surface of the cured body, measured by X-ray photoelectron spectroscopy, is less than 0.01. Hardened | cured material as described in any one of 1-5. A resin composition containing an epoxy resin and an inorganic filler and having an inorganic filler content of 50% by mass or more and 95% by mass or less (however, a resin composition containing a cyanate ester-based curing agent and a naphthylene ether type epoxy resin) A cured product obtained by curing
When the surface composition analysis by repeating 1) sputter treatment with Ar under the following conditions and 2) surface composition analysis by X-ray photoelectron spectroscopy after the sputter treatment is repeated on the surface of the cured product [[number of atoms of metal element derived from inorganic filler] ) / (Number of atoms of all elements on the surface of the cured body after the sputtering process)] is a cured body in which the number of sputtering processes required until the value reaches 0.01 or more for the first time is 4 or more and 100 or less.
[Conditions: Ar ⁺ ion, acceleration voltage: 5 kV, irradiation range: 2 mm × 2 mm, sputtering time per one time: 30 seconds] A resin composition containing a thermosetting resin and an inorganic filler and having an inorganic filler content of 50% by mass to 95% by mass (however, a resin composition containing a cyanate ester-based curing agent and a naphthylene ether type epoxy resin) A cured product obtained by curing
When the surface composition analysis by repeating 1) sputter treatment with Ar under the following conditions and 2) surface composition analysis by X-ray photoelectron spectroscopy after the sputter treatment is repeated on the surface of the cured product [[number of atoms of metal element derived from inorganic filler] ) / (Number of atoms of all elements on the surface of the hardened body after the sputtering process)] The number of times of the sputtering process required until the value of 0.01 or more for the first time is 4 or more and 100 or less. Cured body for layer.
[Conditions: Ar ⁺ ion, acceleration voltage: 5 kV, irradiation range: 2 mm × 2 mm, sputtering time per one time: 30 seconds]   The roughening hardening body whose surface root mean square roughness Rq obtained by roughening the hardening body as described in any one of Claims 1-8 is 10 nm or more and 350 nm or less.   A laminate comprising the roughened cured body according to claim 9 and a metal layer formed on the surface of the roughened cured body.   The laminate according to claim 10, wherein the peeling strength between the roughened cured body and the metal layer is 0.5 kgf / cm or more and 1.2 kgf / cm or less.   The printed wiring board by which the insulating layer was formed with the hardening body as described in any one of Claims 1-8.   A semiconductor device comprising the printed wiring board according to claim 12.