KR102083777B1 - Cured product, laminate, printed circuit board, and semiconductor device - Google Patents

Abstract

[PROBLEMS] The high content of the inorganic filler, and also provides a cured product showing an excellent peel strength to the conductor layer.
[MEANS FOR SOLVING PROBLEMS] As the inorganic filler content of the cured product obtained by curing the resin composition at least 50% by mass, in the cured product surface on the vertical cross-section, the area of the resin in the region in the depth 1㎛ from the cured product surface and A _0-1, Hardened | cured material in which resin area A _1-2 in the area | region from 1 micrometer in depth to 2 micrometers in depth satisfies _A0-1 / A _1-2 > 1.1.

Description

Cured product, laminated body, printed wiring board and semiconductor device {CURED PRODUCT, LAMINATE, PRINTED CIRCUIT BOARD, AND SEMICONDUCTOR DEVICE}

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

As a manufacturing technique of a printed wiring board, the manufacturing method by the buildup system which alternately laminates an insulating layer and a conductor layer is known. In the manufacturing method by a buildup system, generally, an insulating layer is formed by thermosetting a resin composition. For example, Patent Literature 1 discloses a technique of roughening a cured product obtained by thermosetting a resin composition containing silica particles to form an insulating layer.

While the wiring density is required to be further improved, the number of stacked layers due to build-up of a printed wiring board tends to increase, but as the number of stacked layers increases, cracks and circuit deformations are generated due to differences in thermal expansion between the insulating layer and the conductor layer. It is a problem. As a technique for suppressing the problem of such cracks and circuit deformation, for example, Patent Document 2, by increasing the content of inorganic fillers such as silica particles in the resin composition, to lower the thermal expansion coefficient of the insulating layer formed Techniques are disclosed.

International Publication No. 2010/35451 Japanese Unexamined Patent Publication No. 2010-202865

In the technique of patent document 1, the insulating layer which shows sufficient peeling strength with respect to a conductor layer is implement | achieved by the silica particle of the hardening surface detaching in a roughening process. However, when a resin composition having a high content of an inorganic filler such as silica particles is used in order to form an insulating layer having a low thermal expansion rate, a decrease in the peel strength of the insulating layer and the conductor layer formed also in such a technique cannot be avoided. There was.

An object of this invention is to provide the hardened | cured material which shows the outstanding peeling strength with respect to a conductor layer after a roughening process, maintaining the bulk characteristic that content of an inorganic filler is high.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the said subject, in the area | region near a surface, the gradient in the quantity ratio (inorganic filler / resin component) of an inorganic filler and a resin component (namely, the quantity more than a fixed value toward the depth direction from the hardened surface) It was found that the cured product having a gradient of (positive) exhibits excellent peeling strength to the conductor layer after the roughening treatment, while maintaining the bulk characteristic that the content of the inorganic filler is high.

That is, this invention includes the following content.

[1] A cured product obtained by curing the resin composition having an inorganic filler content of 50% by mass or more,

In the cross section perpendicular to the surface of the cured body, the resin area A _0-1 in the region from the surface of the cured body to 1 μm deep and the resin area A _1-2 in the region from 1 μm deep to 2 μm deep, A cured product that satisfies A _0-1 / A _1-2 > 1.1.

[2] A cured product obtained by curing the resin composition having an inorganic filler content of 50% by mass or more,

In the cross section perpendicular to the surface of the cured body, the resin area A _0-0.5 in the region from the surface of the cured body to 0.5 μm deep and the resin area A _0.5-1 in the region from the depth 0.5 μm to 1 μm deep, A cured product that satisfies A _0-0.5 / A _0.5-1 > 1.1.

[3] In the cross section perpendicular to the surface of the cured product, the resin area A _0.5-d in the region from 0.5 μm to the depth d μm and the resin area A in the region from the depth d μm to the depth of _{0.5 D} μm. _d-0.5D is 0.9≤kA _0.5-d / A _d- 0.5D≤1.1 (where k is a coefficient that satisfies k = │d-0.5D│ / │0.5-d│, and d is 0.5 < The hardening body as described in [1] or [2] which satisfy | fills d <0.5D, and D is thickness of hardening body.

[4] [1] to [3], wherein [(the number of metal elements derived from the inorganic filler) / (the number of power stations on the surface of the hardened body)] on the surface of the cured product measured by X-ray photoelectron spectroscopy is less than 0.01. The hardened | cured material in any one of Claims.

[5] A cured product obtained by curing the resin composition having an inorganic filler content of 50% by mass or more,

Regarding the surface of the cured product, when (1) sputtering treatment by Ar under the following conditions, and 2) surface composition analysis by X-ray photoelectron spectroscopy after the sputtering treatment are repeated, [(Number of atoms of metal elements derived from inorganic filler)) The hardened | cured material which is the number of times of the sputtering process required until the value of / (the number of atoms of the power source of the hardened body surface after sputtering process)] becomes 0.01 or more for the first time.

[Conditions: Ar ⁺ ions, acceleration voltage; 5 kV, irradiation range; 2 mm x 2 mm, sputtering time per turn; For 30 seconds]

[6] A roughened cured product having a root mean square roughness (Rq) of the surface obtained by roughening the cured product according to any one of [1] to [5], which is 350 nm or less.

[7] A laminate comprising the roughened cured product according to [6] and a metal layer formed on the surface of the roughened cured product.

[8] The laminate according to [7], in which the peel strength of the roughened cured product and the metal layer is 0.5 kgf / cm or more.

[9] A printed wiring board on which an insulating layer is formed by the cured product according to any one of [1] to [5].

[10] A semiconductor device comprising the printed wiring board described in [9].

According to this invention, the hardened | cured material which shows 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.

Moreover, the hardened | cured material of this invention shows the peeling strength outstanding with respect to the conductor layer (metal layer), although the surface roughness after a roughening process is small.

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

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on the suitable embodiment.

[Hardening body]

The hardened | cured material of this invention is obtained by hardening | curing the resin composition with high inorganic filler content, and it gradients to the ratio (inorganic filler / resin component) of an inorganic filler and a resin component in the area | region near a surface (namely, a depth direction from a hardened body surface). Towards a certain value of the gradient).

Regarding the cured product which becomes an insulating layer of a printed wiring board, research and development are made in order to realize a uniform composition throughout hardening from a viewpoint of strength, heat resistance, etc. On the other hand, the hardened | cured material of this invention has a rapid composition gradient in the area | region near the surface, maintaining a uniform composition as a bulk characteristic.

1, the cross-sectional SEM photograph of the hardened | cured material which has a "uniform" composition produced based on the conventional design idea is shown. In such a hardened | cured material, the particle | grains of an inorganic filler are disperse | distributed uniformly in the resin component, and the particle | grains of an inorganic filler exist in the same ratio as another area also on the surface of a hardened | cured material. As 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 cured body surface.

2, the cross-sectional SEM photograph of the hardened body produced based on the design idea of this invention is shown. In the hardening body of this invention, it has a steep gradient in the ratio (inorganic filler / resin component) of an inorganic filler and a resin component in the area | region near a surface. In detail, although the particle | grains of an inorganic filler exist substantially on the surface of hardened | cured material, but the phase which consists of a resin component exists substantially, the ratio of the particle | grains of an inorganic filler raises rapidly at a fixed depth position from the hardened | cured body surface. . Preferably it is in the position of 0.05-2 micrometers in depth from the surface of hardening body, More preferably, it is the position of 0.05-1.5 micrometers in depth from hardening surface, More preferably, in the position of 0.05-1 micrometer in depth from hardening body surface, Especially preferably, in the position of 0.05-0.5 micrometer in depth from the hardened | cured material surface, the ratio of the particle | grains of an inorganic filler raises rapidly.

When it progresses further in a depth direction, a gradient will disappear in the ratio of the quantity of an inorganic filler and a resin component, and it will become an image which has a uniform composition. In the cured product of the present invention having a sharp compositional gradient only in a limited region near the surface, since the uniform composition is maintained as a bulk property, the composition is excellent in strength, heat resistance, and the like, and on the cured surface, after the roughening treatment, The remarkable effect of showing excellent peel strength is shown. Although the detail is mentioned later, although the hardening body of this invention shows the outstanding peeling strength with respect to a conductor layer (metal layer), although the surface roughness after a roughening process is small, the hardening body of this invention is remarkable for the fine wiring of a printed wiring board. To contribute.

In addition, in this invention, when showing the gradient of the ratio of the inorganic filler and resin component in the area | region near the hardening surface, a predetermined depth from predetermined depth d1 (micrometer) in the cross section perpendicular | vertical to the hardening surface. Ratio of resin area A _d1-d2 of the area | region to d2 (micrometer), and resin area A _d2-d3 of the area | region from predetermined depth d2 (micrometer) to predetermined depth d3 (micrometer) (kA _d1-d2 / A _d2-d3 ). Here, d1, d2, and d3 are numbers satisfying 0≤d1 <d2 <d3, and k is a coefficient satisfying k = │d2-d3 | / │d1-d2 |.

SEM observation of the cross section perpendicular | vertical to the surface of hardened | cured material is carried out SEM observation, and resin area A _{d1-d2 in the} area | region from depth d1 (micrometer) to depth d2 (micrometer), and depth d3 (micrometer) from depth d2 (micrometer). Resin area A _d2-d3 in the area | region up to (micrometer) can be measured, and it can calculate from the obtained A _d1-d2 value and A _d2-d3 value. In the measurement of the A _d1-d2 value and the A _d2-d3 value, the width (measurement distance in the direction parallel to the surface of the hardened body) of the measurement area is set equally.

In addition, in this invention, "resin area" means the area which a resin component occupies. "Resin component" said about the resin area means the component except an inorganic filler among the components which comprise a resin composition.

Regarding the cured product having a "uniform" composition produced based on the conventional design idea, the ratio kA _d1-d2 / A _d2-d3 is theoretically 1, regardless of the values of d1, d2, and d3, and actually measured. It is also in the range of 0.9 to 1.1.

On the other hand, the cured product of the present invention has a steep gradient in the amount ratio of the inorganic filler and the resin component, the kA _d1 in the region near the surface _{- d2} / A _{d2 - d3} ratio is larger by the value of d1, d2 and d3 change do.

That is, the cured product of the present invention has a resin area A _0-1 in a region from the cured surface to a depth of 1 µm and a region from a depth of 1 µm to a depth of 2 µm in a cross section perpendicular to the surface of the cured body. The resin area A _1-2 satisfies A _0-1 / A _1-2 > 1.1. From the viewpoint of improving the peel strength to the conductor layer after the roughening treatment, while maintaining the bulk properties of the high content of the inorganic filler, the cured product of the present invention is preferably A _0-1 / A _1-2 ≧ 1.15, Preferably satisfies A _0-1 / A _1-2 ≧ 1.2.

Although the upper limit of the A _0-1 / A _1-2 ratio is not specifically limited, Usually, it is 20 or less, Preferably it is 15 or less, More preferably, it is 10 or less, More preferably, it is 5 or less.

From the viewpoint of improving the peel strength to the conductor layer after the roughening treatment while maintaining the bulk properties such as the uniform composition and the high inorganic filler content, in the cured body of the present invention, in the cross section perpendicular to the cured body surface, the depth from the cured body surface is increased. Resin area A _{0-0.5 in} an area up to 0.5 μm and resin area A _0.5-1 in an area from 0.5 μm to 1 μm deep satisfy A _0-0.5 / A _0.5-1 > 1.1 It is preferable to make it. From the standpoint of realizing the surface of the cured body exhibiting 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, still more preferably A _{0- 0.5} / A _0.5-1 ≥1.4, still more preferably _0-0.5 A / A ≥1.6 _0.5-1, more preferably _0-0.5 A / A ≥1.8 _{0.5-1, 0-0.5} A / 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.

Although the upper limit of A- _0-0.5 / A _0.5-1 ratio is not specifically limited, Usually, it is 20 or less, Preferably it is 15 or less, More preferably, it is 10 or less, More preferably, it is 5 or less.

As mentioned above, the hardened | cured material of this invention has a composition gradient only in the limited area | region near the surface, and maintains a uniform composition as a bulk characteristic.

In a preferred embodiment, the cured product 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 in a cross section perpendicular to the surface of the cured body, and from a depth of _d μm to a depth of 0.5 D μm. The resin area A _d-0.5D in the region of is 0.9 ≦ kA _2-d / A _d-0.5D ≦ 1.1 (where k satisfies k = │d-0.5D│ / │2-d│ And d is a number satisfying 2 < d < 0.5 D, and D is the thickness of the cured product. This means that the cured product of the present invention has a uniform composition in a region of 2 µm or more in depth from the surface of the cured product.

In more suitable embodiment, the hardened | cured material of this invention is resin area A _{1.5-d in the} area | region from depth 1.5 micrometer to depth dmicrometer in the cross section perpendicular | vertical to the hardened body surface, and depth 0.5D from depth dmicrometer. The resin area A _d-0.5D in the region up to μm is 0.9 ≦ kA _1.5-d / A _d-0.5D ≦ 1.1 (where k is k = │d-0.5D│ / │1.5-d│ Is a number satisfying 1.5 <d <0.5D, and D is the thickness of the cured product. This means that the cured product of the present invention has a uniform composition in a region of 1.5 µm or more in depth from the surface of the cured product.

In a more suitable embodiment, the cured product 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 in a cross section perpendicular to the surface of the cured body, and a depth of 0.5 D from a depth of _d μm. The resin area A _d-0.5D in the region up to μm is 0.9 ≦ kA _1-d / A _d-0.5D ≦ 1.1 (where k is k = │d-0.5D│ / │1-d│ Is a number satisfying 1 < d < 0.5D, and D is the thickness of the cured product. This means that the cured product of the present invention has a uniform composition in a region of 1 µm or more in depth from the surface of the cured product.

In a particularly suitable embodiment, the cured product of the present invention has a resin area A of _0.5-d in a region from a depth of 0.5 μm to a depth of d μm in a cross section perpendicular to the surface of the cured body, and a depth of 0.5 D from a depth of _d μm. The resin area A _d-0.5D in the region up to μm is 0.9 ≦ kA _0.5-d / A _d-0.5D ≦ 1.1 (where k is k = │d-0.5D│ / │0.5-d│ It is a coefficient which satisfies, d is a number which satisfy | fills 0.5 <d <0.5D, and D is the thickness of hardened | cured material. This means that the cured product of the present invention has a uniform composition in a region of 0.5 µm or more in depth from the surface of the cured product.

Preferably the thickness of the hardened | cured material of this invention is 3 micrometers or more, More preferably, it is 5 micrometers or more, More preferably, it is 10 micrometers or more, More preferably, it is 15 micrometers or more, Especially preferably, it is 20 micrometers 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, particularly preferably 60 µm or less.

Hereinafter, the resin composition used when forming the hardened | cured material of this invention is demonstrated.

<Resin composition>

The hardening body of this invention is obtained by hardening | curing the resin composition whose inorganic filler content is 50 mass% or more. From the viewpoint of sufficiently lowering the thermal expansion coefficient of the resulting cured product (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, and even more preferably It is 65 mass% or more.

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 components in a resin composition is 100 mass%.

In the cross section perpendicular to the surface of the cured body, the ratio of the resin area A _0-1 in the region from the surface of the cured body to 1 μm deep and the resin area A _1-2 in the region from 1 μm deep to 2 μm deep. In the cured product of the present invention in which (A _0-1 / A _1-2 ) is in a specific range, the content of the inorganic filler can be further increased without lowering the peel strength to the metal layer (conductor layer). For example, content of the inorganic filler in a resin composition raises to 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. Also good.

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, even more preferably 85% by mass from the viewpoint of the mechanical strength of the cured product obtained by thermosetting of the resin composition. % Or less

As the inorganic filler, for example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, and titanate Calcium, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, etc. are mentioned. Among these, silica, such as amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica, is especially suitable. Moreover, spherical silica is preferable as 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 Adomatex.

The range of 0.01-2 micrometers is preferable, as for the average particle diameter of an inorganic filler, the range of 0.05-1.5 micrometers is more preferable, The range of 0.07-1 micrometer is still more preferable, 0.1-0.8 micrometer is still more preferable. The average particle diameter of an inorganic filler can be measured by the laser diffraction scattering method based on the Mie scattering theory. Specifically, it can measure by making a particle size distribution of an inorganic filler by volume basis with a laser diffraction scattering type particle size distribution measuring device, and making the median diameter into an average particle diameter. The measurement sample can use preferably what disperse | distributed the inorganic filler in water according to the ultrasonic wave. As a laser diffraction scattering particle size distribution measuring apparatus, LA-500 manufactured by Horiba Sesaku Sho, etc. can be used.

Inorganic fillers include one or two kinds of aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents and the like for improving moisture resistance. It is preferable to be processed with the above-mentioned surface treating agent. As a commercial item of a surface treating agent, "KBM403" (3-glycidoxy propyl trimethoxysilane) by Shin-Etsu Chemical Co., Ltd., "KBM803" by Shin-Etsu Chemical Co., Ltd. (3- Mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) by Shin-Etsu Chemical Co., Ltd., "KBM573" by Shin-Etsu Chemical Co., Ltd. (N-phenyl-3 -Aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane) by Shin-Etsu Chemical Co., Ltd., etc. are mentioned.

In addition, the inorganic filler surface-treated with the surface treating agent can measure the amount of carbon per unit surface area of the inorganic filler after the washing treatment 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 treating agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After the supernatant is removed and the solids are dried, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba Sesaku Sho, etc. can be used.

From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and even more preferably 0.2 mg / m 2 or more. 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 a viewpoint of preventing the melt viscosity of a resin varnish and the raise of the melt viscosity in a film form. Thus, by controlling the surface treatment amount of an inorganic filler, the melt viscosity of a resin composition falls, a resin component is easy to move to the hardened | cured body surface, and there exists a tendency to form the rapid composition gradient of the hardened body surface.

The resin composition used in order to form the hardened | cured material of this invention contains a thermosetting resin as 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, Among these, an epoxy resin is preferable. The resin composition may contain the hardening | curing agent further as needed. 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 thermoplastic resins, curing accelerators, flame retardants, and rubber particles.

Hereinafter, the epoxy resin, hardening | curing agent, and additive which can be used as a material of a resin composition are demonstrated.

(Epoxy resin)

Examples of the epoxy resin include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol epoxy resins, and naphthol novolac epoxy resins. , Phenol novolak 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, cresolno Volac 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 resin, cyclohexanedimethanol type epoxy resin, naphthylene ether Type epoxy resin, trimethylol type epoxy resin, etc. are mentioned. An epoxy resin may be used individually by 1 type, or may use 2 or more types together.

It is preferable that an epoxy resin contains the epoxy resin which has two or more epoxy groups in 1 molecule. When the nonvolatile component of an epoxy resin is 100 mass%, it is preferable that at least 50 mass% or more is an epoxy resin which has two or more epoxy groups in 1 molecule. Among these, one molecule has two or more epoxy groups 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 phase at a temperature of 20 ° C. It is preferable to contain the epoxy resin (henceforth "solid epoxy resin."). As an epoxy resin, the resin composition which has the outstanding flexibility is obtained by using together a liquid epoxy resin and a solid epoxy resin. In addition, the breaking strength of the cured product formed by curing the resin composition is also improved. In particular, by containing a liquid epoxy resin, a resin component tends to move to the hardened | cured body surface, and it becomes a tendency to form the rapid composition gradient of the hardened body surface.

As a liquid epoxy resin, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, or a naphthalene type epoxy resin is preferable, and a bisphenol A type epoxy resin or a 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, "jER828EL" manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol A type) Epoxy resin), "jER807" (bisphenol F-type epoxy resin), "jER152" (phenol novolak-type epoxy resin), etc. are mentioned. These may be used individually by 1 type, or may use 2 or more types together.

As a solid epoxy resin, a tetrafunctional naphthalene type epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol epoxy resin, a naphthol novolak epoxy resin, a biphenyl type epoxy resin, or a naphthylene ether type epoxy Resin is preferable and 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" (4-functional naphthalene type epoxy resin), "N-690" (cresol novolac type epoxy resin), and "N-" manufactured by DIC Corporation. 695 "(cresol novolak-type epoxy resin)," HP-7200 "(dicyclopentadiene type epoxy resin)," EXA7311 "," EXA7311-G3 "," HP6000 "(naphthylene ether type epoxy resin), Nihon Kaya "EPPN-502H" (trisphenol epoxy resin), `` NC7000L '' (naphthol novolac epoxy resin), `` NC3000H '', `` NC3000 '', `` NC3000L '', `` NC3100 '' (Biphenyl type epoxy resin) ), "ESN475" (naphthol novolak-type epoxy resin) of Shin-Nitetsu Chemical Co., Ltd., "ESN485" (naphthol novolak-type epoxy resin), "YX4000H" of Mitsubishi Chemical Co., Ltd., "YX4000HK" "YL6121" (biphenyl type epoxy resin), etc. are mentioned.

As an epoxy resin, when using a liquid epoxy resin and a solid epoxy resin together, these quantity ratio (liquid epoxy resin: solid epoxy resin) has a mass ratio of the preferable range of 1: 0.1-1: 3, 1: 0.1 The range of 1: 2.5 is more preferable, and the range of 1: 0.1-1: 2 is still more preferable. By setting the ratio between the liquid epoxy resin and the solid epoxy resin in such a range, i) suitable adhesiveness is caused when i) is used in the form of an adhesive sheet to be described later, ii) sufficient flexibility when used in the form of an adhesive sheet. It is obtained, and the handleability is improved, and iii) the effect of being able to obtain sufficient breaking strength in the hardened | cured material of a resin composition is acquired. From the viewpoint of the effects of i) to iii), the ratio of the liquid epoxy resin and the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1: 0.3 to 1: 1.8 by mass ratio. , 1: 0.6 to 1: 1.5 is particularly preferred.

3-50 mass% is preferable, as for content of the epoxy resin in a resin composition, 5-45 mass% is more preferable, 5-40 mass% is more preferable, 7-35 mass% is especially preferable.

The epoxy equivalent of an epoxy resin becomes like this. Preferably it is 50-3000, More preferably, it is 80-2000, More preferably, it is 110-1000. By setting it as this range, the crosslinking density of hardened | cured material becomes enough and it brings about the insulating layer with low surface roughness. In addition, epoxy equivalent can be measured according to JISK7236, and is the mass of resin containing 1 equivalent of epoxy groups.

(Hardener)

The curing agent is not particularly limited as long as it has a function of curing an epoxy resin. Examples of the curing agent include a phenol curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, and a cyanate ester curing agent. In particular, a phenolic hardening | curing agent is more preferable. When a phenolic hardening | curing agent is used, since fluidity with a epoxy resin is comparatively favorable, fluidity will become high, a resin component will move easily to the hardened | cured body surface, and it will become the tendency to form the rapid composition gradient of the hardened body surface. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

As a phenol type hardening | curing agent and a naphthol type hardening | curing agent, the phenol type hardening | curing agent which has a novolak structure, or the naphthol hardening | curing agent which has a novolak structure is preferable from a heat resistance and a water resistance viewpoint. Moreover, from a viewpoint of adhesiveness (peel strength) with a conductor layer, a nitrogen containing phenol type hardening | curing agent is preferable and a triazine skeleton containing phenol type hardening | curing agent is more preferable. Among these, it is preferable to use a triazine skeleton containing phenol novolak resin as a hardening | curing agent from a viewpoint of satisfying heat resistance, water resistance, and adhesiveness (peel strength) with a conductor layer highly.

As a specific example of a phenol type hardening | curing agent and a naphthol type hardening | curing agent, for example, "MEH-7700", "MEH-7810", "MEH-7851" by Meiwa Kasei Co., Ltd., Nippon Kayaku Co., Ltd. manufacture "NHN", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395" of Totosei Co., Ltd. make) And "LA7052", "LA7054", "LA3018" by DIC Corporation, etc. are mentioned.

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-hydroxy amine ester, ester of a heterocyclic hydroxy compound, have 2 in 1 molecule. Compounds having two or more are preferably used. It is preferable that the said active ester type hardening | curing agent is obtained by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound, 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, 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, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, and m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxy benzophenone, tetrahydroxy benzophenone, fluoroglucin, benzene triol, dicyclopentadienyl diphenol compound, phenol novolac and the like. Here, a "dicyclopentadienyl diphenol compound" means the diphenol compound obtained by condensing 2 molecules of phenol to 1 molecule of dicyclopentadiene.

Specifically, an active ester compound containing a dicyclopentadienyldiphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylate of phenol novolac, and an benzoylate of phenol novolak An ester compound is preferable, and the active ester compound containing a naphthalene structure and the active ester compound containing a dicyclopentadienyl diphenol structure are more preferable among these. Specific examples of the active ester curing agent include, for example, "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" (DIC (Note) as an active ester compound containing a dicyclopentadienyldiphenol structure. `` EXB9416-70BK '' (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, and `` DC808 '' (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing an acetylide of phenol novolac. And "YLH1026" (made by Mitsubishi Chemical Co., Ltd.) etc. are mentioned as an active ester compound containing the benzoylidene of a phenol novolak.

As a specific example of a benzoxazine type hardening | curing agent, "HFB2006M" by the Showa Co., Ltd. product, "P-d" and the "F-a" by the Shikoku Chemical Co., Ltd. product are mentioned.

As a cyanate ester type hardening | curing agent, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylene bis (2,6-, for example) Dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4- Cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-sia Bifunctional cyanate resins such as natephenyl) thioether and bis (4-cyanatephenyl) ether, polyfunctional cyanate resins derived from phenol novolac and cresol novolak, and these cyanate resins are partially triazine Prepolymer etc. As a specific example of a cyanate ester type hardening | curing agent, "PT30" and "PT6" of Lonja Japan Co., Ltd. product are mentioned. 0 "(all phenol novolak-type polyfunctional cyanate ester resin)," BA230 "(a prepolymer in which one part or all part of bisphenol A dicyanate was triazine-ized and became a trimer), etc. are mentioned.

The ratio of the quantity of an epoxy resin and a hardening | curing agent is a ratio of [the total number of epoxy groups of an epoxy resin]: [the total number of reactors of a hardening | curing agent], The range of 1: 0.2-1: 2 is preferable, 1: 0.3-1: 1 1.5 is more preferable, and 1: 0.4-1: 1 are more preferable. Here, the reactor of a hardening | curing agent is an active hydroxyl group, an active ester group, etc., and changes with kinds of hardening | curing agent. In addition, the total number of epoxy groups of an epoxy resin is the value which divided the solid content mass of each epoxy resin by the epoxy equivalent, and it totals it about all the epoxy resins, and the total number of the reactor of a hardening | curing agent divided the solid content mass of each hardening | curing agent by the reactor equivalent. It is the value which totaled the value about all the hardening | curing agents. By setting the ratio between 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 hardened | cured material of this invention contains said inorganic filler, an epoxy resin, and a hardening | curing agent. From the viewpoint of obtaining a cured product exhibiting excellent peel strength to the metal layer (conductor layer) after the roughening treatment, the resin composition is a mixture of a liquid epoxy resin and a solid epoxy resin (liquid epoxy resin: solid epoxy resin) as silica as an inorganic filler and an epoxy resin. The mass ratio of 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, still more preferably in the range of 1: 0.1 to 1: 2, and 1: 0.3 to 1: The range of 1.8 is still more preferable, and the range of 1: 0.6-1: 1.5 is especially preferable), The phenol type hardening | curing agent which has a novolak structure as a hardening | curing agent, the phenol type hardening | curing agent containing nitrogen (preferably triazine skeleton containing phenol) It is preferable to contain 1 or more types chosen from the group which consists of a system hardening | curing agent) and an active ester type hardening | curing agent, respectively. Regarding the resin composition layer containing a combination of such specific components, suitable contents of the inorganic filler, the epoxy resin, and the curing agent are as described above. Among these, the content of the inorganic filler is 50 to 95% by mass and the content of the epoxy resin is It is preferable that it is 3-50 mass%, and it is more preferable that content of an inorganic filler is 50-90 mass% and content of 5-45 mass%. About content of a hardening | curing agent, ratio of the total number of the epoxy groups of an epoxy resin and the total number of the reactor of a hardening | curing agent becomes like this. Preferably it is the range of 1: 0.2-1: 2, More preferably, it is 1: 0.3-1: 1.5 In a range, 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 hardening accelerator, a flame retardant, and rubber particle as needed.

(Thermoplastic)

Examples of the thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyimide resins, polyamideimide resins, polyethersulfone resins, and polysulfone resins. By containing a thermoplastic resin, even during a thermosetting process, a resin component becomes easy to move to the hardened | cured body surface, and it becomes a tendency to form the rapid composition gradient of the hardened body surface. A thermoplastic resin may be used individually by 1 type, or may use 2 or more types together.

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

Examples of the phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetphenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton and naphthalene skeleton. And phenoxy resins having at least one skeleton selected from the group consisting of anthracene skeletons, adamantane skeletons, terpene skeletons, and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group. A phenoxy resin may be used individually by 1 type, or may use 2 or more types together. As a specific example of a phenoxy resin, Mitsubishi Chemical Co., Ltd. product "1256" and "4250" (both bisphenol A skeleton containing phenoxy resin), "YX8100" (bisphenol S skeleton containing phenoxy resin), and "YX6954" (Bisphenol acetenone skeleton-containing phenoxy resin), In addition, "FX280" and "FX293" by Totogsei Co., Ltd., "YL7553", "YL6794" by Mitsubishi Chemical Co., Ltd., "YL7213", "YL7290", "YL7482", etc. are mentioned.

As a concrete example of a polyvinyl acetal resin, the Denkabutyral 4000-2, 5000-A, 6000-C, 6000-EP, Sekisui Chemical Co., Ltd. product Esrek BH series manufactured by Denki Chemical Co., Ltd. make , BX series, KS series, BL series, BM series and the like.

As a specific example of a polyimide resin, "Rika coat SN20" and "Rika coat PN20" by Shin-Nihon Rica Co., Ltd. are mentioned. Specific examples of the polyimide resin may also include linear polyimides (described in JP 2006-37083) and polysiloxane skeletons obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic anhydride. Modified polyimide, such as containing polyimide (thing of Unexamined-Japanese-Patent No. 2002-12667, Unexamined-Japanese-Patent No. 2000-319386, etc.) is mentioned.

As a specific example of polyamide-imide resin, "Biromix HR11NN" and "Biromix HR16NN" by Toyo Boseki Co., Ltd. are mentioned. Specific examples of the polyamideimide resin include modified polyamideimides such as polysiloxane skeleton-containing polyamideimide "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd.

As a specific example of polyether sulfone resin, "PES5003P" by Sumitomo Chemical Co., Ltd. etc. is mentioned.

As a specific example of polysulfone resin, the polysulfone "P1700", "P3500", etc. by Solvay Advanced Polymers Co., Ltd. are mentioned.

It is preferable that content of the thermoplastic resin in a resin composition is 0.1-20 mass%. By making content of a thermoplastic resin into this range, the viscosity of a resin composition becomes moderate and can form a resin composition with a uniform thickness and bulk property. As for content of the thermoplastic resin in a resin composition, it is more preferable that it is 0.5-10 mass%.

As a hardening accelerator, an organic phosphine compound, an imidazole compound, an amine adduct compound, a tertiary amine compound, etc. are mentioned, for example. When content of a hardening accelerator makes the total amount of non volatile components of an epoxy resin and a hardening agent 100 mass%, it is preferable to use in 0.05-3 mass%. A hardening accelerator may be used individually by 1 type, or may use 2 or more types together.

As a flame retardant, an organophosphorus flame retardant, an organic nitrogen containing phosphorus compound, a nitrogen compound, a silicone flame retardant, a metal hydroxide, etc. are mentioned, for example. A flame retardant may be used individually by 1 type, or may use 2 or more types together. Although content of the flame retardant in a resin composition layer is not specifically limited, 0.5-10 mass% is preferable, 1-9 mass% is more preferable, 1.5-8 mass% is further more preferable.

As a rubber particle, what is not melt | dissolved in the organic solvent mentioned later, and is not compatible with said epoxy resin, a hardening | curing agent, a thermoplastic resin, etc. is used, for example. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level which does not dissolve in an organic solvent or a resin and making it particulate.

Examples of the rubber particles include core shell rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, and the like. The core-shell rubber particles are rubber particles having a core layer and a shell layer. For example, the shell layer of the outer layer is made of a glassy polymer, and the inner layer core layer is made of a rubbery polymer, or the shell layer of the outer layer is glass. The three layer structure etc. which consist of a polymer, an intermediate | middle layer consist of a rubbery polymer, and a core layer consist of a glassy polymer are mentioned. The glassy polymer layer is composed of, for example, a methyl methacrylate polymer or the like, and the rubbery polymer layer is composed of, for example, a butylacrylate polymer (butyl rubber) or the like. A rubber particle may be used individually by 1 type, or may use 2 or more types together.

The average particle diameter of the rubber particles is preferably in the range of 0.005 to 1 µm, more preferably in the range of 0.2 to 0.6 µm. The average particle diameter of a rubber particle can be measured using a dynamic light scattering method. For example, the rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, and the particle size distribution of the rubber particles is determined based on mass by using a thick particle diameter analyzer (FPAR-1000; manufactured by Otsuka Denshi Co., Ltd.). It can create and measure by making the median diameter into an average particle diameter. Content of the rubber particle in a resin composition becomes like this. Preferably it is 1-10 mass%, More preferably, it is 2-5 mass%.

The resin composition used in order to form the hardened | cured material of this invention may contain other additives as needed, As these other additives, For example, organic metals, such as an organic copper compound, an organic zinc compound, and an organic cobalt compound, etc. The compound and resin additives, such as an organic filler, a thickener, an antifoamer, a leveling agent, adhesiveness giving agent, a coloring agent, and curable resin, etc. are mentioned.

The hardening body of this invention can be used as a hardening body (hardening body for insulating layers of a metal-clad laminate), and a hardening body (hardening body for insulating layers of a printed wiring board) for forming the insulating layer of a printed wiring board. Among these, in manufacture of a printed wiring board by a buildup system, it can be used suitably as a hardening body (hardening body for buildup insulating layers of a printed wiring board) for forming an insulating layer, and the hardening body for forming a conductor layer by plating ( Hardened | cured material for buildup insulation layers of printed wiring boards which form a conductor layer by plating) can be used more suitably.

When using the hardening body of this invention, the resin composition used in order to form the hardening body of this invention contains the layer which consists of said resin composition from a viewpoint which can carry out lamination | stacking of hardened body (insulating layer) easily and efficiently. It is suitable to use in the form of an adhesive sheet.

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

As the support, a film made of a plastic material is suitably used. Examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), and polycarbonates. (Hereinafter, it may be abbreviated as "PC".), Acryl, cyclic polyolefin, such as polymethyl methacrylate (PMMA), triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide Etc. can be mentioned. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable. In one suitable embodiment, the support is a polyethylene terephthalate film.

The support body may apply the mat process and the corona treatment to the surface of the side joined with a resin composition layer. In addition, you may use the support body with a release layer which has a mold release layer on the surface of the side joined with a resin composition layer as a support body.

Although the thickness of a support body is not specifically limited, The range of 5-75 micrometers is preferable, and the range of 10-60 micrometers is more preferable. Moreover, 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 onto a support using a die coater, or the like, drying the organic solvent by heating or hot air spraying, or the like. It can manufacture by forming a composition layer.

As an organic solvent, For example, ketones, such as acetone, methyl ethyl ketone, and cyclohexanone, an acetate ester, such as ethyl acetate, butyl acetate, a cellosolve acetate, a propylene glycol monomethyl ether acetate, and a carbitol acetate, a cellosolve, Carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, and 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.

Although drying conditions are not specifically limited, It drys so that content (amount of residual solvent) of the organic solvent in a resin composition layer may be 10 mass% or less, Preferably it is 5 mass% or less. Moreover, from a viewpoint of preventing the handleability of a resin composition layer and the raise of the melt viscosity in a film form, 0.5 mass% or more is preferable, and 1 mass% or more is more preferable. Although it changes also with the boiling point of the organic solvent in a resin varnish, when using the resin varnish containing 30-60 mass% organic solvent, for example, a resin composition layer is dried by drying at 50-150 degreeC for 3 to 10 minutes. Can be formed. Thus, by controlling the amount of residual solvent, the melt viscosity of the resin composition is lowered, and the resin component tends to move to the surface of the cured body, which tends to form an abrupt composition gradient on the surface of the cured body.

In an adhesive sheet, the protective film based on a support body can further be laminated | stacked on the surface (that is, the surface on the opposite side to a support body) which is not joined to the support body of a resin composition layer. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating | stacking a protective film, adhesion | attachment and a scratch of dust etc. to the surface of a resin composition layer can be prevented. An adhesive sheet can be wound and preserve | saved in roll shape, and when forming the hardened body of this invention, it can be used by peeling a protective film.

The hardening body of this invention is obtained by hardening | curing the said resin composition whose inorganic filler content is 50 mass% or more. In one embodiment, the cured product of the present invention, the inorganic filler content is a certain amount of time the resin composition is at least 50% by mass, as after treatment with the heating process to maintain a certain amount of time to a temperature T _1, the temperature T ₁ higher than the temperature T ₂ It is obtained by processing by the thermosetting process to hold | maintain. In one suitable embodiment, the cured product of the present invention is treated with a heating step in which a resin composition having an inorganic filler content of 50% by mass or more is held at a temperature T ₁ (50 ° C. ≦ T ₁ <150 ° C.) for 10 minutes or more. After that, it is obtained by treating with a thermosetting step held at a temperature T ₂ (150 ° C. ≦ T ₂ ≦ 240 ° C.) for 5 minutes or more.

In the heating step, the temperature T ₁ is different depending on the composition of the resin composition, but preferably 60 ℃ ≤T ₁ ≤130 ℃, more preferably from 70 ℃ ≤T ₁ ≤120 ℃, and more preferably from 80 ℃ ≤T ₁ ≤110 ℃, thereby particularly preferably satisfies 80 ℃ ≤T ₁ ≤100 ℃.

In the heating step, the time to be maintained at the temperature T ₁ also varies depending on the value of the temperature T ₁ , but preferably 10 to 150 minutes, more preferably 15 to 120 minutes, still more preferably 20 to 120 minutes. .

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

In the thermosetting step, the temperature T ₂ also varies depending 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.

Further, the temperature T ₁ and temperature T ₂ is preferably _{20 ℃ ≤T 2 -T 1 ≤150 ℃} , more preferably from _{30 ℃ ≤T 2 -T 1 ≤140 ℃} , more preferably from 40 ℃ ≤T ₂ -T ₁ ≤130 ℃, thereby particularly preferably satisfies the relationship of _{50 ℃ ≤T 2 -T 1 ≤120 ℃} .

In the thermosetting process, the time for heat curing at a temperature T ₂ is the temperature differs depending on the value of T _2, but preferably 5 to 100 minutes, more preferably from 10 to 80 minutes, more preferably from 10 to 50 Minutes.

The thermosetting step may be performed under normal pressure or under reduced pressure. Preferably, it is preferable to carry out by air pressure similar to a heating process.

After the heating step at the temperature T _1, the resin composition is cooled once, or may be treated with a thermosetting step in the temperature T _2. Or, after the heating step at a temperature T _1, does not cool the resin composition, it may be treated with a thermosetting step in the temperature T _2. In a suitable embodiment, the cured product of the present invention is obtained by treating, in addition to the step of between the heating step and the heat curing step, the temperature was raised to the temperature T ₂ by the temperature T _1. In this temperature raising step, the rate of temperature increase from the temperature T ₁ to the temperature T ₂ is preferably 1.5 to 30 ° C./min, more preferably 2 to 30 ° C./min, still more preferably 4 to 20 ° C./min, further More preferably, it is 4-10 degreeC / min.

In addition, the thermosetting of a resin composition may be started in the middle of such a temperature rising process.

Thus, the hardened | cured material of this invention obtained as described above has a rapid composition gradient in the area | region near the surface, maintaining a bulk composition like a uniform composition and high inorganic filler content.

As for the cured product of the present invention, it is preferable that there are almost no inorganic fillers exposed to the external environment on the surface. In one embodiment, it is preferable that [(the number of atoms of the metal element derived from the inorganic filler) / (the number of atoms of the power station on the surface of the hardened body)] in the surface of the hardened body measured by X-ray photoelectron spectroscopy is less than 0.01. . For example, in the case of using silica as an inorganic filler, the fact that [(atomic number of silicon) / (atomic number of power stations 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. desirable. When using a mixture of silica and alumina as the inorganic filler, [(Number of atoms of silicon and aluminum) / (Number of atoms of power station on the surface of the cured body) on the surface of the cured body measured by X-ray photoelectron spectroscopy is 0.01. It is preferable that it is less than.

In addition, the surface composition analysis of the hardened | cured material by X-ray photoelectron spectroscopy can be performed, for example on the following conditions.

Measuring device: PHI Quantera SXM manufactured by Albagpai

X-ray source: AlKα

X-ray beam diameter: 100 μm

Power value: 25 W

Voltage: 15kV

Blowout angle: 45 °

Measuring range: 500 × 500 (㎛ ² )

Charge Compensation: Neutralizer and Ar ⁺ Ion Irradiation

In the cured body of the present invention, as described above, the particles of the inorganic filler are virtually absent on the surface of the cured body, and a phase substantially composed of the resin component is present, but the particle ratio of the inorganic filler is rapidly increased at a constant depth position from the surface of the cured body. It rises. The structural characteristic of the hardened | cured body of this invention can also be confirmed by performing a compositional analysis about the depth direction of a hardened body after surface composition analysis by X-ray photoelectron spectroscopy. Compositional analysis in the depth direction can be performed, for example, in the following order. The surface composition analysis after 1) sputtering process by Ar and 2) sputtering process is repeated. 2) Surface composition analysis after sputtering process can be performed on the conditions similar to surface composition analysis by said X-ray photoelectron spectroscopy. Then, the number of sputtering processes required until the value of [(atomic number of metal elements derived from inorganic filler) / (atomic number of power stations on the surface of the cured body after sputtering)) becomes a predetermined level is determined. At this time, by setting the sputtering treatment by Ar to the same condition for all the cured samples, the number of sputtering treatments obtained was calculated as follows: ((atomic number of metal elements derived from inorganic filler) / (atomic number of power stations on the surface of the cured body after sputtering) )] Is an index of the depth from the surface of the cured product, which becomes a predetermined level or more.

The sputtering process by Ar can be performed, for example on the following conditions.

Ar ⁺ ions

Acceleration voltage: 5 kV

Irradiation range: 2mm × 2mm

Sputtering time per once: 30 seconds

When the sputtering process using Ar under the above conditions, the cured product of the present invention has a value of [(atomic number of metal elements derived from inorganic filler) / (atomic number of power stations on the surface of the cured body after sputtering)] for the first time. The number of sputtering processes required until it becomes 0.01 or more is four or more times. From the viewpoint of realizing a hardened surface showing a higher peeling strength to the conductor layer after the roughening treatment, when performing the sputtering treatment with Ar under the above conditions, [(atomic number of metal elements derived from inorganic filler) / (sputtering treatment) The number of sputtering treatments required until the value of the number of atoms of a power source on the surface of the cured body after the first time becomes 0.01 or more is preferably 5 or more times, more preferably 10 or more times, still more preferably 15 Times or more, particularly preferably 20 times or more. In addition, from the standpoint of maintaining bulk properties such as uniform composition and high inorganic filler content, the value of [(atomic number of metal elements derived from inorganic filler) / (atomic number of power stations on the surface of the cured body after sputtering)] is the first value. The number of sputtering processes required until it becomes 0.01 or more is preferably 100 times or less, more preferably 50 times or less, and still more preferably 30 times or less.

[Harmony hardened body]

In the hardening body which has a "uniform" composition based on the conventional design idea, the inorganic filler which exists in the surface detach | desorbs in a roughening process, and an unevenness | corrugation is formed in the surface. Such unevenness exerts an anchor effect between a metal layer (conductor layer), and is considered to contribute to the improvement of peeling strength between a roughening hardening body and a metal layer. However, when the content of the inorganic filler in the cured product is high, even if it has an anchor effect due to such unevenness, a decrease in peel strength between the roughened cured product and the metal layer may be unavoidable, and the surface roughness of the roughened cured product becomes high. There was a case.

As described above, the cured product of the present invention has almost no inorganic filler exposed to the external environment on the surface of the cured product. Regarding the cured product of the present invention, the inorganic filler is contained in a high content, but desorption of the inorganic filler by the roughening treatment is less likely to occur than a cured product having a "uniform" composition based on the conventional design idea. The hardened | cured material of this invention shows the peeling strength outstanding with respect to the metal layer after a roughening process, and it is inferred that the surface which contributes to peeling strength with a metal layer was reproduced in the balance of content of an inorganic filler and desorption of an inorganic filler. .

The order and conditions of a roughening process are not specifically limited, The well-known procedure and conditions normally used when forming the insulating layer of a printed wiring board can be employ | adopted. For example, the swelling process with a swelling liquid, the roughening process with an oxidizing agent, and the neutralization process with a neutralizing liquid can be performed in this order, and the hardened body surface can be roughened. Although it does not specifically limit as a swelling liquid, Alkali solution, surfactant solution, etc. are mentioned, Preferably it is an alkali solution, As said alkaline solution, sodium hydroxide solution and potassium hydroxide solution are more preferable. As a commercially available swelling liquid, the swelling dip security P, the swelling dip security SBU etc. by Atotech Japan Co., Ltd. are mentioned, for example. Although the swelling process by a swelling liquid is not specifically limited, For example, it can be performed by immersing a hardened | cured material for 1 to 20 minutes in 30-90 degreeC swelling liquid. From a viewpoint of suppressing swelling of resin of a hardened | cured material to a suitable level, it is preferable to immerse a hardened | cured material for 5 second-15 minutes in 40-80 degreeC swelling liquid. 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. It is preferable to perform roughening processing by oxidizing agents, such as an alkaline permanganic acid solution, by immersing a hardened | cured material in 10 to 30 minutes in the oxidizing agent solution heated at 60-80 degreeC. Moreover, as for the density | concentration of the permanganate in alkaline permanganate solution, 5-10 mass% is preferable. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Atotech Japan Co., Ltd. manufactured condensate compact P and dosing solution secure P. Moreover, as a neutralization liquid, an acidic aqueous solution is preferable, As a commercial item, the reduction solution security P of the Atotech Japan Co., Ltd. product is mentioned, for example. The treatment with the neutralizing liquid can be performed by immersing the treated surface on which the roughening treatment with the oxidizing agent solution is applied in the neutralizing liquid at 30 to 80 ° C for 5 to 30 minutes. In view of workability, a method of immersing the object subjected to the roughening treatment by the oxidizing agent solution in a neutralizing liquid at 40 to 70 ° C for 5 to 20 minutes is preferable.

In one suitable embodiment, the roughening hardening body of this invention has a root mean square roughness (Rq) of a surface 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 roughening cured product of the present invention, even when the surface roughness Rq is very small, 180 nm or less, 160 nm or less, 140 nm or less, or 120 nm or less, excellent peeling strength is exhibited with respect to the metal layer (conductor layer). On the other hand, although the lower limit of surface roughness Rq is not specifically limited, In order to stabilize peeling strength, it becomes 10 nm or more, 30 nm or more, 50 nm or more.

The root mean square roughness Rq of the roughened cured product can be measured using a non-contact surface roughness machine. As a specific example of the non-contact type surface roughening machine, "WYKO NT3300" by non-coinstrument manufacture is mentioned.

[Laminated body]

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 the said roughening hardening body.

The metal used for the metal layer is not particularly limited, but in one suitable embodiment, the metal layer is selected from the group consisting of gold, platinum, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. It includes one or more metals. The metal layer may be a short metal layer or an alloy layer, and as the alloy layer, for example, an alloy of two or more metals selected from the above-described group (for example, nickel chromium alloy, copper nickel alloy and copper Titanium alloy). Among these, from the viewpoints of versatility, cost, and ease of removal by etching, such as metal layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, silver or copper, or a nickel-chromium alloy or a copper-nickel alloy , An alloy layer of a copper-titanium alloy is preferable, a monometal layer of chromium, nickel, titanium, aluminum, zinc, gold, silver or copper, or an alloy layer of nickel-chromium alloy is more preferable, and a monometal layer of copper is further preferred. desirable.

The metal layer may be a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. In the case where 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. As dry plating, well-known methods, such as vapor deposition, sputtering, ion plating, are mentioned, for example. In the case of wet plating, for example, a metal layer is formed by combining electroless plating and electrolytic plating. Alternatively, the plating resist of the reverse pattern can be formed with the metal layer (conductor layer), and the metal layer can be formed only by electroless plating. As a method of wiring pattern formation, the subtractive method, the semiadditive method, etc. which are known to a person skilled in the art can be used, for example.

40 micrometers or less are preferable from a viewpoint of the fine wiring of a printed wiring board, as for the thickness of a metal layer, 1-35 micrometers is more preferable, and its 3-20 micrometers are more preferable. Also in the case where the metal layer has a multilayer structure, the thickness of the entire metal layer is preferably in the above range.

In the laminate of the present invention, the peel strength of 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 0.65 kgf / cm or more. On the other hand, the upper limit of the peel strength is not particularly limited, but it is 1.2 kgf / cm or less, 0.9 kgf / cm or less.

Although the laminated body of this invention shows such high peeling strength, even though the surface roughness Rq of a roughening hardening body is 350 nm or less, it contributes remarkably to the fine wiring of a printed wiring board.

In addition, in this invention, the peeling strength of a roughening hardening body and a metal layer means the peeling strength (90 degree peeling strength) when peeling a metal layer in the perpendicular direction (90 degree direction) with respect to a roughening hardening body, and a metal layer is perpendicular to a roughening hardening body It can obtain | require by measuring the peeling strength at the time of peeling to a direction (90 degree direction) with a tensile tester. As a tensile tester, "AC-50C-SL" by TSE Corporation, etc. are mentioned, for example.

[Printed wiring board]

The printed wiring board of the present invention is characterized in that an insulating layer is formed by the cured product of the present invention.

In one embodiment, the printed wiring board of this invention can be manufactured using said adhesive sheet. In such embodiment, after laminating so that the resin composition layer of an adhesive sheet may bond with a circuit board, said "heating process" and a "thermal curing process" may be performed, and the hardening body of this invention can be formed on a circuit board. . On the other hand, when an adhesive sheet has a protective film, it can provide for manufacture after removing a protective film.

The conditions of lamination processing are not specifically limited, The well-known conditions used when forming the insulating layer of a printed wiring board using an adhesive sheet can be employ | adopted. For example, it can carry out by pressing metal plates, such as a heated SUS hard board, from the support body side of an adhesive sheet. In this case, it is preferable not to press a metal plate directly, but to press it through elastic materials, such as heat resistant rubber, so that an adhesive sheet can fully follow the circuit unevenness | corrugation of a circuit board. The press temperature is preferably in the range of 70 to 140 ° C., and the press pressure is preferably in the range of 1 to 11 kgf / cm 2 (9.8 × 10 ⁴ N / m 2 to 107.9 × 10 ⁴ N / m 2), and the press time Is preferably in the range of 5 seconds to 3 minutes. The lamination treatment is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. Lamination processing can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressurized laminators manufactured by Meiki Sesaku Co., Ltd. and vacuum applicators manufactured by Nichigo Morton Co., Ltd., and the like.

In addition, in this invention, a "circuit board" mainly means a pattern on one side or both sides of board | substrates, such as a glass epoxy board | substrate, a metal board | substrate, a polyester board | substrate, a polyimide board | substrate, a BT resin board | substrate, and a thermosetting polyphenylene ether board | substrate. It means that the processed conductor layer (circuit) was formed. In addition, when manufacturing a printed wiring board, the inner circuit board of the intermediate | middle manufacture to which the insulation layer and / or conductor layer should be formed is also included in the "circuit board" which is used in this invention.

In other embodiment, the printed wiring board of this invention can be manufactured using said resin varnish. In such embodiment, after apply | coating a resin varnish uniformly on a circuit board with a die coater etc., and heating and drying, after forming a resin composition layer on a circuit board, said "heating process" and a "heat curing process" are performed. Thus, the cured product of the present invention can be formed on a circuit board. It can be said that the conditions of the organic solvent used for a resin varnish, and heating and drying are the same as what was demonstrated about manufacture of an adhesive sheet.

Subsequently, after performing said "harmonic treatment" about the hardening body formed on the circuit board and forming a roughening hardening body, a metal layer (conductor layer) is formed in the surface of the said roughening hardening body. In addition, in manufacture of a printed wiring board, you may further include the punching process etc. which make a hole in an insulating layer. This process can be performed according to the various methods used for manufacture of a printed wiring board known to a person skilled in the art.

[Semiconductor Device]

A semiconductor device can be manufactured using said printed wiring board.

Examples of such semiconductor devices include various semiconductor devices provided in electrical appliances (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trams, ships, aircrafts, etc.). Can be.

EXAMPLES

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In addition, in the following description, "part" means a "mass part" unless there is particular notice.

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

<Measurement of resin area ratio>

The resin area ratio of the hardened | cured material manufactured by the Example and the comparative example is SEM observed about the cross section perpendicular | vertical to the hardened body surface, and the resin area A _{d1-d2 in the} area | region from depth d1 (micrometer) to depth d2 (micrometer) and And resin area A _d2-d3 in the area | region from depth d2 (micrometer) to depth d3 (micrometer) was measured, and it computed from the obtained A _d1-d2 value and A _d2-d3 value.

Specifically, the resin area preserves the SEM observation image as an image, and uses image analysis software to make the resin portion black and binary digitize the inorganic filler portion other than the resin as white, and the number of bits of the black portion is resin. The area of the part was taken.

The resin area ratio (A _0-1 / A _0-2 ) was observed by SEM with respect to the cross section perpendicular to the surface of the cured product, and from the resin area A _0-1 and the depth of 1 µm in the region from the surface of the cured product to a depth of 1 µm. The resin area A _1-2 in the area | region up to 2 micrometers in depth was measured, and it calculated from the obtained A _0-1 value and A _1-2 value.

In addition, the resin area ratio (A _0-0.5 / A _0.5-1 ) was SEM observed with respect to the cross section perpendicular to the surface of the cured product, and the resin area A _0-0.5 and the depth of 0.5 µm in the area from the surface of the cured product to a depth of 0.5 µm. The resin area A _0.5-1 in the area | region up to 1 micrometer in depth was measured, and it 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 SEM observed with respect to the cross section perpendicular to the surface of the cured product, and the resin area A _{0.5-d in} the region from the depth of 0.5 μm to the depth d (μm); Resin area A _d-0.5D in the area | region from depth d (micrometer) to depth 0.5D (micrometer) was measured, and it calculated from the obtained A _0.5-d value and A _d-0.5D value. Here, in the present Example, it was d = 1 (micrometer), D = 35 (micrometer), and k = │d-0.5D | / | 0.5-d | = 16.5 / 0.5 = 33.

In addition, SEM observation of the cross section of hardened | cured material was performed using the focused ion beam / scanning ion microscope "SMI3050SE" made from SAI Nano Technology Co., Ltd., and the width | variety of the measurement area | region was 7.5 micrometers.

Composition Analysis of Cured Product by X-ray Photoelectron Spectroscopy

The surface composition of the cured product produced in the Examples and Comparative Examples, that is, [(Number of atoms of metal elements derived from inorganic filler) / (Number of atoms of power station on the surface of the cured body)] is an X-ray photoelectron spectroscopy apparatus (manufactured by Algipie Co. "PHI Quantera SXM") was used under the following conditions.

X-ray source: AlKα

X-ray beam diameter: 100 μm

Power value: 25 W

Voltage: 15kV

Blowout angle: 45 °

Measuring range: 500 × 500 (㎛ ² )

Charge Compensation: Neutralizer and Ar ⁺ Ion Irradiation

After surface composition analysis, composition analysis was performed about the depth direction of a hardened | cured material. The composition analysis in the depth direction was performed by repeating 1) the sputtering treatment with Ar and 2) the surface composition analysis after the sputtering treatment. And the number of times of sputtering process required until the value of [(the number of atoms of the metal element derived from an inorganic filler) / (the number of atoms of the power source on the surface of the hardened body after sputtering)) became 0.01 or more for the first time was calculated | required. In addition, the conditions of the sputtering process by Ar were as follows, and made the same conditions for all the hardened body samples.

Ar ⁺ ions

Acceleration voltage: 5 kV

Probe Range: 2mm × 2mm

Sputtering Time per Time: 30 seconds

<Measurement of root mean square roughness (Rq) of the surface of the hardened cured body>

The root mean square roughness (Rq) of the roughened cured product surface obtained in the examples and the comparative examples is measured by a VSI contact mode, a 50x lens, using a non-contact surface roughness machine (manufactured by Nonco Instruments, Inc., "WYKO NT3300"). The value (nm) of the root mean square roughness (Rq) was calculated | required by the numerical value set as 121 micrometers * 92 micrometers. Moreover, it measured by obtaining the average value of ten points.

<Measurement of peeling strength>

Into the metal layer (conductor layer) of the laminate produced in the examples and comparative examples, a partial notch having a width of 10 mm and a length of 100 mm was put in, and this end was peeled off and grasped with forceps, and at room temperature in a vertical direction at a rate of 50 mm / min. The load (kgf / cm) at the time of peeling 35 mm was measured, and peeling strength was calculated | required. A tensile tester (manufactured by TSE Corporation, "AC-50C-SL") was used for the measurement.

The adhesive sheet which has the resin composition layers 1, 2, 3, or 4 used by the Example and the comparative example was prepared according to the following method.

(Preparation of the adhesive sheet which has a resin composition layer 1)

(1) Preparation of Resin Varnish 1

Biphenyl type epoxy resin (epoxy equivalent approximately 290, Nihon Kayaku Co., Ltd. "NC3000H") 20 parts, naphthalene type tetrafunctional epoxy resin (epoxy equivalent 162, DIC Corp. make "HP-4700") 5 Part, 20 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, "jER828EL" of Mitsubishi Chemical Co., Ltd.), and phenoxy resin (weight average molecular weight 35000, "YL7553BH30" of Mitsubishi Chemical Co., Ltd.), 12 parts of methyl ethyl ketone (MEK) solutions of 30 mass% of solid content were melt | dissolved by stirring in the mixed solvent of 8 parts of MEK and 8 parts of cyclohexanone. There, 15 parts of phenol novolak-type hardening | curing agents (phenolic hydroxyl group equivalent approximately 124, "LA-7054" of DIC Corporation, MEK solution of 60 mass% of non volatile components), active ester type hardening | curing agent (active ester equivalent approximately) 223, `` HPC8000-65T '' manufactured by DIC Corporation, 5 parts of toluene solution of 65% by mass of nonvolatile components), tetrabutylphosphonium decanoate (manufactured by Hokogagaku Kogyo Co., Ltd.) Spherical silica ("SOC2" manufactured by Adomatex Co., Ltd.), surface particle treated with 0.2 part of "TBP-DA") and an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter of 0.5 µm, 75 parts of carbon amount per unit area 0.39 mg / m 2), polyvinyl butyral resin solution (glass transition temperature of 105 ° C., Sekisuga Chemical Co., Ltd. product "KS-1", non-volatile component 15% by mass of ethanol and 2.5 parts of a mixed solution having a mass ratio of toluene of 1: 1) was mixed and uniformly dispersed in a high speed rotary mixer to prepare a resin varnish 1. It was.

When the sum total of the non volatile components in the resin varnish 1 was 100 mass%, content of the inorganic filler (spherical silica) was 54.1 mass%.

(2) Preparation of Adhesive Sheet

As a support, a polyethylene terephthalate film (thickness: 38 µm, hereinafter abbreviated as "PET film") was prepared. The resin varnish 1 obtained above was apply | coated uniformly with the die coater on the said support body, and dried at 80-120 degreeC (average 100 degreeC) for 6 minutes, and the resin composition layer 1 was formed. Resin composition layer 1 was 40 micrometers in thickness, and the amount of residual solvent was about 2 mass%.

Next, it wound up in roll shape, bonding a polypropylene film (15 micrometers in thickness) as a protective film on the surface of the resin composition layer 1. The obtained rolled adhesive sheet was slit to a width of 507 mm to obtain an adhesive sheet having a size of 507 mm x 336 mm.

(Preparation of the adhesive sheet having the resin composition layer 2)

(1) Preparation of Resin Varnish 2

Biphenyl type epoxy resin (Epoxy equivalent approximately 290, "NC3000H" of Nippon Kayaku Co., Ltd.) 30 parts, naphthalene type tetrafunctional epoxy resin (Epoxy equivalent 162, "HP-4700" of DIC Corporation) 5 Part, 15 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, "jER828EL" of Mitsubishi Chemical Co., Ltd.), and phenoxy resin (weight average molecular weight 35000, "YL7553BH30" of Mitsubishi Chemical Co., Ltd.), 2 parts of methyl ethyl ketone (MEK) solutions of 30 mass% of solid content were melt | dissolved by stirring in the mixed solvent of 8 parts of MEK and 8 parts of cyclohexanone. There, 30 parts of phenol novolak-type hardening | curing agents (phenolic hydroxyl group equivalent approximately 124, "LA-7054" of DIC Corporation, MEK solution of 60 mass% of non volatile components), hardening accelerator (Koegagaku Kogyo ( SOC1 manufactured by Spherical Silica (Adomatex Co., Ltd.) surface-treated with 0.1 part of "4-dimethylaminopyridine (DMAP)" manufactured by Note) and an aminosilane coupling agent ("KBM573" by Shin-Etsu Chemical Co., Ltd.) ", Average particle diameter 0.24 micrometer, 160 parts of carbon amount per unit area) 160 parts, polyvinyl butyral resin solution (glass transition temperature of 105 degreeC," KS-1 "of Sekisui Chemical Co., Ltd. product, non-fluorescence) 2 parts of a mixed solution having a mass ratio of ethanol and toluene having a mass content of 15% by mass of 1: 1) was mixed and uniformly dispersed by a high speed rotary mixer to prepare a resin varnish 2.

When the sum total of the non volatile components in the resin varnish 2 was 100 mass%, content of the inorganic filler (spherical silica) was 69.4 mass%.

(2) Preparation of Adhesive Sheet

An adhesive sheet having a resin composition layer 2 (dimensions 507 mm x 336 mm) in the same manner as in the above "(Preparation of the adhesive sheet having the resin composition layer 1)" except that the resin varnish 2 obtained above was used instead of the resin varnish 1. Was prepared.

(Preparation of the adhesive sheet having the resin composition layer 3)

(1) Preparation of Resin Varnish 3

Biphenyl type epoxy resin (epoxy equivalent approximately 290, Nihon Kayaku Co., Ltd. "NC3000H") 35 parts, liquid bisphenol A type epoxy resin (epoxy equivalent 180, Mitsubishi Chemical Co., Ltd. "jER828EL") 15 Part and mixed solvent of phenoxy resin (weight average molecular weight 35000, Mitsubishi Chemical Co., Ltd. "YL7553BH30", 10 parts of methyl ethyl ketone (MEK) solution of 30 mass% of solid content) MEK of 8 parts, and cyclohexanone 8 parts It melt | dissolved under stirring, stirring. 10 parts of methoxypropanol solutions of 50 mass% of solid content of triazine containing cresol-type hardening | curing agent (hydroxyl equivalent 151, "LA-3018-50P" by DIC Corporation), and active ester type hardening | curing agent (active ester equivalent approximately) 223, "HPC8000-65T" by DIC Corporation, 40 parts by mass of a toluene solution of 65% by weight of nonvolatile components, a curing accelerator ("4-dimethylaminopyridine (DMAP)" manufactured by Koegaku Chemical Co., Ltd.) ) 0.5 part, hardening accelerator ("2-phenyl-4-methylimidazole (2P4MZ) by Shikoku Chemical Co., Ltd.)) 0.2 part, aminosilane type coupling agent (" KBM573 "by Shin-Etsu Chemical Co., Ltd.) 200 parts of spherical silica ("SOC1" manufactured by Ado-Matex, Inc., average particle diameter 0.24 µm, carbon amount per unit area 0.36 mg / m 2) were uniformly dispersed with a high-speed rotary mixer, and uniformly dispersed in a resin varnish. 3 was prepared.

When the sum total of the non volatile components in the resin varnish 3 was 100 mass%, content of the inorganic filler (spherical silica) was 70.2 mass%.

(2) Preparation of Adhesive Sheet

An adhesive sheet having a resin composition layer 3 (dimensions 507 mm x 336 mm) in the same manner as in the above "(Preparation of the adhesive sheet having the resin composition layer 1)" except that the resin varnish 3 obtained above was used instead of the resin varnish 1. Was prepared.

(Preparation of the adhesive sheet having the resin composition layer 4)

(1) Preparation of Resin Varnish 4

Biphenyl type epoxy resin (epoxy equivalent approximately 290, Nihon Kayaku Co., Ltd. "NC3000H") 35 parts, liquid bisphenol A type epoxy resin (epoxy equivalent 180, Mitsubishi Chemical Co., Ltd. "jER828EL") 15 Part and mixed solvent of phenoxy resin (weight average molecular weight 35000, Mitsubishi Chemical Co., Ltd. "YL7553BH30", 10 parts of methyl ethyl ketone (MEK) solution of 30 mass% of solid content) MEK of 8 parts, and cyclohexanone 8 parts It melt | dissolved under stirring, stirring. 10 parts of methoxypropanol solutions of 50 mass% of solid content of triazine containing cresol-type hardening | curing agent (hydroxyl equivalent 151, "LA-3018-50P" by DIC Corporation), and active ester type hardening | curing agent (active ester equivalent approximately) 223, "HPC8000-65T" by DIC Corporation, 40 parts of toluene solution of 65 mass% of non volatile components), hardening accelerator (made by Koe Chemical Co., Ltd., "4-dimethylaminopyridine (DMAP)" ) 0.3 parts, curing accelerator (manufactured by Shikoku Chemical Co., Ltd., "2-phenyl-4-methylimidazole (2P4MZ)") 0.1 part, aminosilane-based coupling agent ("KBM573" by Shin-Etsu Chemical Co., Ltd.) 300 parts of spherical silica ("SOC2" manufactured by Adomattex Co., Ltd., the average particle diameter of 0.5 µm, the amount of carbon per unit area of 0.39 mg / m 2) were surface-treated and uniformly dispersed in a high-speed rotary mixer to obtain a resin varnish. 4 was prepared.

When the sum total of the non volatile components in the resin varnish 4 was 100 mass%, content of the inorganic filler (spherical silica) was 78.0 mass%.

(2) Preparation of Adhesive Sheet

An adhesive sheet having a resin composition layer 4 (dimensions 507 mm x 336 mm) in the same manner as in the above "(Preparation of the adhesive sheet having the resin composition layer 1)" except that the resin varnish 4 obtained above was used instead of the resin varnish 1. Was prepared.

<Example 1>

The cured product was produced according to the following method. About the obtained hardened | cured material, the surface analysis by X-ray photoelectron spectroscopy and the resin area ratio were measured. The results are shown in Table 2.

(Manufacture of hardened body)

(1) base treatment of inner layer circuit board

Both sides of the glass cloth base material epoxy resin double-sided copper clad laminated board (copper foil thickness 18 micrometers, board | substrate thickness 0.3mm, "R5715ES" of Matsushita Denko Co., Ltd.) in which the inner layer circuit was formed are immersed in "CZ8100" of MEC Co. The roughening process of the copper surface was performed.

(2) Laminating Treatment of Adhesive Sheet

The inner layer circuit board is bonded so that the resin composition layer 1 is bonded to the inner layer circuit board by using a batch vacuum pressurized laminator ("MVLP-500" manufactured by Meiki Sekushoku Co., Ltd.) on the adhesive sheet having the resin composition layer 1. Both surfaces of the laminate were laminated. Lamination process was performed by depressurizing for 30 second, making air pressure 13 hPa or less, and pressing for 30 second at 100 degreeC and pressure 0.74 Mpa.

(3) curing of the resin composition

The PET film was peeled from the laminated adhesive sheet, the resin composition was cured under curing conditions 1 shown in Table 1, and a cured product (35 μm thick on copper) was obtained on both surfaces of the inner layer circuit board.

Next, the obtained hardened | cured body was roughened according to the following method, and the roughened hardened body was manufactured. 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 Harmonized Cured Product)

The hardened | cured material was immersed in 60 degreeC for 5 minutes in swelling liquid (Atotech Japan Co., Ltd. product, "swelling dip security P", diethylene glycol monobutyl ether containing), and then a roughening liquid (Atotech Japan ( (Manufacture), "concentrate compact P", an aqueous solution of potassium permanganate concentration of about 6% by mass and sodium hydroxide concentration of about 4% by mass) was immersed at 80 ° C for 20 minutes. Finally, it immersed in neutralization liquid (Atotech Japan Co., Ltd. product, "Reduction Solleucine Securitant P") at 40 degreeC for 5 minutes, and the roughening hardening body was obtained.

Then, according to the following method, the metal layer (conductor layer) was formed in the surface of the obtained roughening hardening body, and the laminated body was obtained on both surfaces of the inner layer circuit board. The peeling strength was measured about the obtained laminated body. The results are shown in Table 2.

(Manufacture of Laminate)

The inner circuit board having the roughened cured body on both sides was immersed in the solution for electroless plating containing palladium chloride (PdCl ₂ ), and then immersed in the electroless copper plating solution, and a plating seed layer was formed on the roughened cured body surface. Then, after performing an annealing process by heating at 150 degreeC for 30 minutes, the etching resist was formed on the plating seed layer, and the plating seed layer was pattern-formed by etching. Subsequently, copper sulfate electroplating was performed to form a copper layer (conductor layer) having a thickness of 30 ± 5 μm, followed by annealing at 180 ° C. for 60 minutes to obtain a laminate on both sides of the inner layer circuit board.

<Example 2>

Except having changed the hardening conditions of the resin composition into the hardening conditions 2 shown in Table 1, it carried out similarly to Example 1, the hardened | cured body, the roughening hardened body, and the laminated body were manufactured, and it evaluated. The results are shown in Table 2.

<Example 3>

Except having changed the hardening conditions of the resin composition into the hardening conditions 3 shown in Table 1, it carried out similarly to Example 1, the hardened | cured body, the roughening hardened body, and the laminated body were manufactured, and it evaluated. The results are shown in Table 2.

<Example 4>

Except having changed the hardening conditions of the resin composition into the hardening conditions 4 shown in Table 1, it carried out similarly to Example 1, the hardened | cured body, the roughening hardened body, and the laminated body were manufactured, and it evaluated. The results are shown in Table 2.

Example 5

Except having changed the hardening conditions of the resin composition into the hardening conditions 5 shown in Table 1, it carried out similarly to Example 1, the hardened | cured body, the roughening hardened body, and the laminated body were manufactured, and it evaluated. The results are shown in Table 2.

<Example 6>

Except having changed the hardening conditions of the resin composition into the hardening conditions 6 shown in Table 1, it carried out similarly to Example 1, the hardened | cured body, the roughening hardened | cured body, and the laminated body were manufactured and evaluated. The results are shown in Table 2.

<Example 7>

Except having changed the hardening conditions of the resin composition into the hardening conditions 7 shown in Table 1, it carried out similarly to Example 1, the hardened | cured body, the roughening hardened body, and the laminated body were manufactured, and it evaluated. The results are shown in Table 2.

<Example 8>

Except having changed the hardening conditions of the resin composition into the hardening conditions 8 shown in Table 1, it carried out similarly to Example 1, the hardened | cured body, the roughening hardened body, and the laminated body were manufactured, and it evaluated. The results are shown in Table 2.

Example 9

In the same manner as in Example 1, 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 curing conditions 4 shown in Table 1, A hardened | cured material, a roughening hardened body, and a laminated body were manufactured and evaluated. The results are shown in Table 2.

<Example 10>

In the same manner as in Example 1, except that the adhesive sheet having the resin composition layer 3 was used instead of the adhesive sheet having the resin composition layer 1, and the curing conditions of the resin composition were changed to curing conditions 4 shown in Table 1, A hardened | cured material, a roughening hardened body, and a laminated body were manufactured and evaluated. The results are shown in Table 2.

Example 11

In the same manner as in Example 1, 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 curing conditions 4 shown in Table 1, A hardened | cured material, a roughening hardened body, and a laminated body were manufactured and evaluated. The results are shown in Table 2.

Comparative Example 1

Except having changed the hardening conditions of the resin composition into the hardening conditions 9 shown in Table 1, it carried out similarly to Example 1, the hardened | cured body, the roughening hardened | cured body, and the laminated body were manufactured and evaluated. The results are shown in Table 2.

Comparative Example 2

Except having changed the hardening conditions of the resin composition into the hardening conditions 10 shown in Table 1, it carried out similarly to Example 1, the hardened | cured body, the roughening hardened body, and the laminated body were manufactured, and it evaluated. The results are shown in Table 2.

Comparative Example 3

Except having changed the hardening condition of the resin composition into the hardening condition 11 shown in Table 1, it carried out similarly to Example 1, the hardened | cured body, the roughening hardened body, and the laminated body were manufactured, and it evaluated. The results are shown in Table 2.

<Comparative Example 4>

Except having changed the hardening conditions of the resin composition into the hardening conditions 12 shown in Table 1, it carried out similarly to Example 1, the hardened | cured body, the roughening hardened body, and the laminated body were manufactured, and it evaluated. The results are shown in Table 2.

Claims (10)

As a hardening body obtained by hardening | curing the resin composition whose inorganic filler content is 50 mass% or more and 95 mass% or less,
In the cross section perpendicular to the surface of the cured body, the resin area A _0-1 in the region from the surface of the cured body to 1 μm deep and the resin area A _1-2 in the region from 1 μm deep to 2 μm deep, A cured product that satisfies A _0-1 / A _1-2 > 1.1. As a hardening body obtained by hardening | curing the resin composition whose inorganic filler content is 50 mass% or more and 95 mass% or less,
In the cross section perpendicular to the surface of the cured body, the resin area A _0-0.5 in the region from the surface of the cured body to 0.5 μm deep and the resin area A _0.5-1 in the region from the depth 0.5 μm to 1 μm deep, A cured product that satisfies A _0-0.5 / A _0.5-1 > 1.1. The cross-section perpendicular to the surface of the cured product according to claim 1, wherein the resin area A _0.5-d in a region from a depth of 0.5 mu m to a depth of d mu m, and a region from a depth of d mu m to a depth of _{0.5 d} mu m. Resin area A _d-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 that satisfies 0.5 <d <0.5D, and D is the thickness of the cured body.). The cured product according to claim 1, wherein [(atomic number of metal elements derived from an inorganic filler) / (atomic number of power stations on the surface of the cured body)] of the cured product measured by X-ray photoelectron spectroscopy is less than 0.01. As a hardening body obtained by hardening | curing the resin composition whose inorganic filler content is 50 mass% or more and 95 mass% or less,
Regarding the surface of the cured product, when (1) sputtering treatment by Ar under the following conditions and 2) surface composition analysis by X-ray photoelectron spectroscopy after the sputtering treatment are repeated, [(Number of atoms of metal elements derived from inorganic filler)) The hardened | cured material which is the number of times of the sputtering process required until the value of / (the number of atoms of the power source of the hardened body surface after sputtering process)] becomes 0.01 or more for the first time.
[Conditions: Ar ⁺ ions, acceleration voltage; 5 kV, irradiation range; 2 mm x 2 mm, sputtering time per turn; For 30 seconds] The roughening hardening body whose square root mean square roughness (Rq) of the surface obtained by roughening the hardening body in any one of Claims 1-5 is 350 nm or less. The laminated body provided with the roughening hardening body of Claim 6, and the metal layer formed in the surface of the said roughening hardening body. The laminated body of Claim 7 whose peeling strength of a roughening hardening body and a metal layer is 0.5 kgf / cm or more. The printed wiring board in which the insulating layer was formed with the hardening body in any one of Claims 1-5. The semiconductor device containing the printed wiring board of Claim 9.

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