JP2014127644A - Roughened and hardened body, laminate, printed circuit board, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a roughened and hardened body that has low surface roughness and presents excellent peel strength to a conductor layer, while holding characteristics in which an inorganic filler content is high.SOLUTION: A roughened and hardened body is obtained by roughening a thermally hardened body of a thermosetting resin composition with an inorganic filler content of 50 mass% or more. In the roughened and hardened body, an Si amount of a surface, which is measured by X-ray photoelectron spectroscopy, is 25 atom% or less, and an O amount of the surface is 25 atom% or more.

Description

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

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

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

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

  In the technique described in Patent Document 1, an insulating layer exhibiting sufficient peel strength with respect to the conductor layer is realized by desorbing silica particles on the surface of the cured body in the roughening treatment. However, when a resin composition having a high content of inorganic fillers such as silica particles is used to form an insulating layer having a low coefficient of thermal expansion, the surface of the cured body after the roughening treatment becomes highly rough. Furthermore, the present inventors have found that the peel strength with respect to the conductor layer may also decrease.

  This invention makes it a subject to provide the roughening hardening body which has the characteristic that the content of an inorganic filler is high, the surface roughness is low, and the peeling strength which was excellent with respect to the conductor layer is exhibited.

  As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by making the amounts of silicon atoms (Si) and oxygen atoms (O) in the surface of the roughened cured body a specific range, The present invention has been completed.

That is, the present invention includes the following contents.
[1] A roughened cured body obtained by roughening a thermoset of a thermosetting resin composition having an inorganic filler content of 50% by mass or more,
A roughened cured body having a surface Si amount of 25 atom% or less and a surface O amount of 25 atom% or more measured by X-ray photoelectron spectroscopy.
[2] The roughened cured body according to [1], wherein a ratio of O amount to Si amount on the surface (O / Si) is 2.1 or more.
[3] The roughened cured body according to [1] or [2], wherein the surface of the thermoset has a scratch hardness (JIS K5600-5-4) of H or higher.
[4] The roughened cured body according to any one of [1] to [3], wherein the amount of Si on the surface of the thermoset is less than 2 atom% as measured by X-ray photoelectron spectroscopy.
[5] The roughened cured body according to any one of [1] to [4], wherein an etching amount per unit surface area in the roughening treatment is 2 g / m ² or less.
[6] The roughened cured body according to any one of [1] to [5], wherein the arithmetic average roughness Ra of the surface is 300 nm or less.
[7] A laminate comprising the roughened cured body according to any one of [1] to [6] and a conductor layer formed on the surface of the roughened cured body.
[8] The laminate according to [7], wherein the peel strength between the roughened cured body and the conductor layer is 0.3 kgf / cm or more.
[9] A printed wiring board in which an insulating layer is formed of the roughened cured body according to any one of [1] to [6].
[10] A semiconductor device including the printed wiring board according to [9].

  ADVANTAGE OF THE INVENTION According to this invention, the roughening hardening body which has the characteristic that the content of an inorganic filler is high, the surface roughness is low, and the peeling strength excellent with respect to the conductor layer can be provided.

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

[Roughened hardened body]
The roughened cured body of the present invention is obtained by roughening a thermoset of a thermosetting resin composition having an inorganic filler content of 50% by mass or more, and is obtained by X-ray photoelectron spectroscopy. The measured surface Si amount is 25 atom% or less, and the surface O amount is 25 atom% or more.

The amount of Si on the surface of the roughened cured body of the present invention measured by X-ray photoelectron spectroscopy from the viewpoint of obtaining a roughened cured body exhibiting excellent peel strength with respect to the conductor layer even when the surface has a low roughness. Is preferably 24 atom% or less, more preferably 22 atom% or less, still more preferably 20 atom% or less, even more preferably 18 atom% or less, particularly preferably 16 atom% or less, 14 atom% or less, 12 atom% or less, 10 atom% or less, or 8 atom% or less. The lower limit of such Si amount is not particularly limited, and is usually 0 atom% or more, preferably 0.01 atom% or more, more preferably 0.5 atom% or more, and further preferably 1 atom% or more.
In addition, Si atoms on the surface of the roughened cured body are derived from an inorganic filler and a surface treatment agent described later. Since Si atoms are nonpolar atoms that do not contribute to adhesion to the conductor layer (metal layer), from the viewpoint of obtaining a roughened cured body exhibiting excellent peel strength with respect to the conductor layer, The smaller the amount of Si on the surface of the chemical cured body, the better.

The amount of O on the surface of the roughened cured product of the present invention, measured by X-ray photoelectron spectroscopy, is preferably 26 atom% or more, more preferably 27 atom% or more, still more preferably 28 atom% or more, and even more preferably 29 atom. % Or more, particularly preferably 30 atom% or more. The upper limit of such O amount is usually 65 atom% or less, preferably 60 atom% or less, more preferably 55 atom% or less, further preferably 50 atom% or less, even more preferably 45 atom% or less, particularly preferably 40 atom% or less. , 38 atom% or less, 36 atom% or less, 34 atom% or less, or 32 atom% or less.
The O atoms on the surface of the roughened cured body are derived from O atom-containing components such as an inorganic filler, a surface treatment agent, a thermosetting resin, and a curing agent described later. Since the O atom is a polar atom that contributes to adhesion to the conductor layer (metal layer), the roughening hardening of the present invention is performed from the viewpoint of obtaining a roughened cured body exhibiting excellent peel strength with respect to the conductor layer. The amount of O on the surface of the body preferably satisfies the above lower limit condition.

  The surface composition analysis of the roughened cured body by X-ray photoelectron spectroscopy can be carried out, for example, under the following measurement conditions using the following measurement apparatus.

〔measuring device〕
Device type: QUANTERA SXM (Fully automatic scanning X-ray photoelectron spectrometer manufactured by ULVAC-PHI)
Ultimate vacuum: 7.0 × 10 ⁻¹⁰ Torr
X-ray source: monochromatic Al Kα (1486.6 eV)
Spectrometer: electrostatic concentric hemispherical analyzer Detector: Multi-channel type (32 Multi-Channel Detector)
Neutralizing gun setting Electron: 1.0 V (20 μA), ion: 10.0 V (7 mA)

〔Measurement condition〕
[Survey spectrum (wide scan)]
X-ray beam diameter: 100 μmΦ (HP mode, 100.6 W, 20 kV)
Measurement area: 1400 μm × 100 μm
Signal capture angle: 45.0 °
Pass energy: 280.0eV

  From the viewpoint of obtaining a roughened cured body exhibiting excellent peel strength with respect to the conductor layer even if the surface has a low roughness, the ratio of O amount to Si amount (O / Si) on the surface of the roughened cured body is 2 1 or more, preferably 2.2 or more, more preferably 2.4 or more, still more preferably 2.6 or more, and 2.8 or more. It is particularly preferably 0 or more, 3.2 or more, 3.4 or more, 3.6 or more, or 3.7 or more.

By setting the ratio of Si atoms and O atoms on the surface to the above range, the roughened cured product of the present invention can exhibit excellent peel strength with respect to the conductor layer even if the surface has a low roughness. In one embodiment, the arithmetic average roughness Ra of the surface of the roughened cured body of the present invention is preferably less than 350 nm, more preferably 300 nm or less, still more preferably 250 nm or less, and even more, from the viewpoint of improving the fine wiring forming ability. It is preferably 200 nm or less, particularly preferably 180 nm or less, 160 nm or less, 140 nm or less, 120 nm or less, 100 nm or less, or 80 nm or less. The lower limit value of the arithmetic average roughness Ra is not particularly limited, and is 20 nm, 40 nm, or the like. The peel strength between the roughened cured body and the conductor layer of the present invention will be described later.
In addition, arithmetic mean roughness Ra of the surface of a roughening hardening body can be measured using a non-contact-type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by Bee Coins Instruments can be cited.

  The roughened cured body of the present invention is obtained by roughening a thermoset of a thermosetting resin composition having an inorganic filler content of 50% by mass or more.

  From the viewpoint of obtaining a roughened cured body in which the ratio of Si atoms and O atoms on the surface is in a desired range, the thermoset used for forming the roughened cured body of the present invention is JIS K5600-5-4 ( The surface scratch hardness measured in accordance with ISO 15184) is preferably H or more, more preferably 2H or more, further preferably 3H or more, and particularly preferably 4H or more. . The upper limit of such scratch hardness is 8H, preferably 5H or less.

  The thermosetting body also preferably has a surface Si amount of less than 2 atom%, more preferably 1.5 atom% or less, and 1.0 atom% or less as measured by X-ray photoelectron spectroscopy. Is more preferably 0.8 atom% or less, 0.6 atom% or less, 0.4 atom% or less, or 0.2 atom% or less. The lower limit of such Si amount is not particularly limited, and may be 0 atom%.

When obtaining a roughened cured body by roughening the thermoset, the etching amount per unit surface area of the thermoset in the roughening process is roughened and hardened so that the ratio of Si atoms and O atoms on the surface is in the desired range. from the viewpoint of obtaining a body, preferably at 2 g / ^{m 2} or less, more preferably more preferably 1.8 g / ^{m 2} or less, 1.6 g / ^{m 2} or less, 1.4 g / m Particularly preferred is ² or less. The lower limit of the etching amount is not particularly limited, but is preferably 0.01 g / m ² or more, more preferably 0.5 g / m ² or more.

  The thickness of the roughened cured body of the present invention is preferably 3 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, even more preferably 15 μm or more, and particularly preferably 20 μm or more, from the viewpoint of improving insulation. . The thickness of the roughened cured body of the present invention is preferably 100 μm or less, more preferably 90 μm or less, further preferably 80 μm or less, even more preferably 70 μm or less, and particularly preferably 60 μm or less from the viewpoint of thinning. .

  The roughened cured body of the present invention may have a multilayer structure composed of two or more layers. In the case of a roughened cured body having a multilayer structure, the overall thickness is preferably in the above range.

  Hereafter, the thermosetting resin composition used in order to form the roughening hardening body of this invention is demonstrated.

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

  In the roughened cured body of the present invention in which the ratio of Si atoms and O atoms on the surface is in a specific range, the content of the inorganic filler can be further increased without reducing the peel strength with respect to the conductor layer. For example, the content of the inorganic filler in the thermosetting resin composition is 66 mass% or more, 68 mass% or more, 70 mass% or more, 72 mass% or more, 74 mass% or more, 76 mass% or more, or 78 You may raise even to the mass% or more.

  The upper limit of the content of the inorganic filler in the thermosetting resin composition is preferably 95% by mass or less, more preferably 90% by mass, from the viewpoint of preventing a decrease in mechanical strength of the thermosetting body of the thermosetting resin composition. % Or less, more preferably 85% by mass or less.

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

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

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

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

Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is more preferable from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the film form. preferable.

In one embodiment, the thermosetting resin composition includes the inorganic filler and a thermosetting resin. As a thermosetting resin, the conventionally well-known thermosetting resin used when forming the insulating layer of a printed wiring board can be used, and an epoxy resin is especially preferable. The thermosetting resin composition may also contain a curing agent. In one embodiment, the thermosetting resin composition includes an inorganic filler, an epoxy resin, and a curing agent. The thermosetting resin composition may further contain additives such as a thermoplastic resin, a curing accelerator, a flame retardant, and rubber particles as necessary.
Hereinafter, an epoxy resin, a curing agent, and an additive that can be used as a material for the resin composition will be described.

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

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

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

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

  When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 4 in terms of mass ratio. preferable. By setting the amount ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) moderate tackiness is obtained when used in the form of an adhesive film described later, and ii) used in the form of an adhesive film. In this case, sufficient flexibility can be obtained, handling properties can be improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii) above, the quantitative ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is from 1: 0.3 to 1: 3.5 in mass ratio. Is more preferable, the range of 1: 0.6 to 1: 3 is more preferable, and the range of 1: 0.8 to 1: 2.6 is particularly preferable.

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

(Curing agent)
The curing agent is not particularly limited as long as it has a function of curing the epoxy resin. For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, and a cyanate ester curing agent may be used. Can be mentioned. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

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

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN375”, “SN395” manufactured by Toto Kasei Co., Ltd. And “LA7052”, “LA7054”, “LA3018” manufactured by DIC Corporation, “GDP-6140” manufactured by Gunei Chemical Industry Co., Ltd., and the like.

  From the viewpoint of adhesion (peel strength) to the conductor layer, an active ester curing agent is also preferable. Although details will be described later, by using an active ester curing agent, even if the temperature condition when thermosetting the thermosetting resin composition is “non-step” condition or “step” condition, it is desirable. Thus, it is possible to easily obtain a thermosetting body having a scratch hardness, and it is possible to easily realize a roughened hardening body in which the ratio of Si atoms to O atoms on the surface is in a desired range.

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

  The active ester curing agent includes an active ester compound containing a dicyclopentadienyl diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing a phenol novolac acetylated product, and an active ester containing a phenol novolak benzoylated product. Compounds are preferred, and active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadienyl diphenol structure are more preferred.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (DIC Corporation) as active ester compounds containing a dicyclopentadienyl diphenol structure. Manufactured product), "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac, Examples of the active ester compound containing a benzoylated compound include “YLH1026” (manufactured by Mitsubishi Chemical Corporation).

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

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

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

  In one Embodiment, the thermosetting resin composition used in order to form the roughening hardening body of this invention contains the above-mentioned inorganic filler, an epoxy resin, and a hardening | curing agent. The thermosetting resin composition comprises silica as an inorganic filler and a mixture of a liquid epoxy resin and a solid epoxy resin as an epoxy resin (the mass ratio of liquid epoxy resin: solid epoxy resin is 1: 0.1 to 1: The range of 4 is preferable, the range of 1: 0.3 to 1: 3.5 is more preferable, the range of 1: 0.6 to 1: 3 is more preferable, and the range of 1: 0.8 to 1: 2.6 is preferable. It is preferable that each of the curing range includes at least one selected from the group consisting of a phenolic curing agent, a naphthol curing agent, and an active ester curing agent. Regarding the thermosetting resin composition layer containing a combination of such specific components, the preferred content of the inorganic filler, the epoxy resin, and the curing agent is as described above, and among them, the content of the inorganic filler Is preferably 50% by mass to 95% by mass, the epoxy resin content is preferably 3% by mass to 50% by mass, the inorganic filler content is 50% by mass to 90% by mass, and the epoxy resin content is 5%. It is more preferable that it is mass%-45 mass%. Regarding the content of the curing agent, the ratio of the total number of epoxy groups of the epoxy resin to the total number of reactive groups of the curing agent is preferably in the range of 1: 0.2 to 1: 2, more preferably 1: It is contained so as to be in the range of 0.3 to 1: 1.5, more preferably in the range of 1: 0.4 to 1: 1.

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

(Thermoplastic resin)
From the viewpoint of easily realizing a roughened cured body in which the ratio of Si atoms and O atoms on the surface is in a desired range, the thermosetting resin composition preferably includes a thermoplastic resin. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyethersulfone resin, and polysulfone resin. Among these, phenoxy resin and polyvinyl acetal resin are preferable. A thermoplastic resin may be used individually by 1 type, or may use 2 or more types together.

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

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

  As the polyvinyl acetal resin, polyvinyl butyral resin is preferable, and specific examples thereof include electrified butyral 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., Sekisui Chemical Co., Ltd. Examples include S-LEC BH series, BX series, KS series, BL series, and BM series.

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

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

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

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

  The content of the thermoplastic resin in the thermosetting resin composition is 0.1% by mass to 20% from the viewpoint of easily realizing a roughened cured body in which the ratio of Si atoms and O atoms on the surface is in a desired range. It is preferable that it is mass%, and it is more preferable that it is 0.5 mass%-10 mass%.

  Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and guanidine-based curing accelerators. From the viewpoint of easily realizing a roughened cured body in which the ratio of Si atoms and O atoms on the surface is in a desired range, amine-based curing accelerators and imidazole-based curing accelerators are more preferable.

  Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like.

  Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo. (5,4,0) -undecene and the like are mentioned, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- -Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl] -(1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino -6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl -4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl Examples include imidazole compounds such as -3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2- Phenylimidazole is preferred.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like.

  A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type. In a preferred embodiment, the curing accelerator contained in the heat-effective resin composition is at least one selected from the group consisting of amine-based curing accelerators and imidazole-based curing accelerators. The content of the curing accelerator in the thermosetting resin composition may be used in the range of 0.05% by mass to 3% by mass when the total amount of nonvolatile components of the epoxy resin and the curing agent is 100% by mass. preferable.

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

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

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

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

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

  The roughening hardening body of this invention can be used as a roughening hardening body (roughening hardening body for insulating layers of a printed wiring board) for forming the insulating layer of a printed wiring board. Above all, in the production of printed wiring boards by the build-up method, it can be suitably used as a roughened and hardened body for forming insulating layers (roughened and hardened body for buildup insulating layers of printed wiring boards). It can be more suitably used as a cured body for forming a conductor layer (a roughened cured body for a build-up insulating layer of a printed wiring board on which a conductor layer is formed by plating).

  When the roughened cured body of the present invention is used for a printed wiring board, the thermosetting resin composition used to form the roughened cured body of the present invention can be easily and efficiently laminated on a circuit board. From the viewpoint, it is suitable to use in the form of an adhesive film including a layer made of the thermosetting resin composition.

  In one embodiment, the adhesive film comprises a support and a thermosetting resin composition layer (adhesive layer) bonded to the support.

  In addition, in order to form the roughening hardening body of a multilayer structure, you may use the thermosetting resin composition layer of a multilayer structure. In this case, inorganic filler content should just be 50 mass% or more as the whole thermosetting resin composition layer.

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

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

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

  The adhesive film is prepared, for example, by preparing a resin varnish in which a thermosetting resin composition is dissolved in an organic solvent, and applying the resin varnish onto a support using a die coater or the like, and further heating or blowing hot air, etc. Thus, the organic solvent can be dried to form a thermosetting resin composition layer.

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

  The drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the thermosetting resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of the organic solvent is used, it is thermosetting by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes. A resin composition layer can be formed.

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

The roughened cured body of the present invention is obtained by roughening a thermoset of the above thermosetting resin composition having an inorganic filler content of 50% by mass or more. For example, the roughened cured body of the present invention is produced by a method including the following steps (A) and (B).
(A) Step of thermosetting a thermosetting resin composition having an inorganic filler content of 50% by mass or more to form a thermosetting body (B) Roughening the thermosetting body to obtain a roughened hardening body Forming process

  The structure of the thermosetting resin composition used in the step (A) is as described above. From the viewpoint of easily realizing a roughened cured body in which the ratio of Si atoms and O atoms on the surface is in a desired range, thermosetting including an inorganic filler (preferably silica), an epoxy resin, a curing agent, and a thermoplastic resin. It is preferable to use a resin composition, and it is more preferable to use a thermosetting resin composition containing an inorganic filler (preferably silica), an epoxy resin, a curing agent, a thermoplastic resin, and a curing accelerator. From the viewpoint of easily realizing a roughened cured body in which the ratio of Si atoms and O atoms on the surface is in a desired range, the curing agent is selected from the group consisting of phenolic curing agents, naphthol curing agents and active ester curing agents. One or more selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin as the thermoplastic resin, and a group consisting of an amine curing accelerator and an imidazole curing accelerator as the curing accelerator It is preferable to use at least one selected from

The thermosetting of the thermosetting resin composition in the step (A) may be carried out under conditions (hereinafter referred to as “non-step conditions”) in which the thermosetting resin composition is heated at a predetermined temperature for a predetermined time. well, or after heating the predetermined time at a temperature T _1, it may be carried out under the conditions (hereinafter referred to as "step condition".) for heating a predetermined time at a higher temperature T ₂ than the temperature T _1. In addition, when thermosetting the thermosetting resin composition under step conditions, it is not limited to two stages of heating (T ₁ → T ₂ ), but three stages (T ₁ → T ₂ → T ₃ ) or more stages. Heating may be used.

  From the viewpoint of more easily realizing a roughened cured body in which the ratio of Si atoms and O atoms on the surface is in a desired range, it is preferable to thermoset the thermosetting resin composition under step conditions. When an active ester type curing agent is used as the curing agent, the ratio of Si atoms and O atoms on the surface is in a desired range even when the thermosetting resin composition is thermally cured under non-step conditions or step conditions. A roughened cured body can be easily realized.

  When thermosetting the thermosetting resin composition under non-step conditions, the curing temperature is preferably in the range of 150 ° C to 240 ° C, more preferably 150 ° C to 210 ° C, although it varies depending on the composition of the thermosetting resin composition. The curing time is preferably in the range of 5 minutes to 90 minutes, more preferably in the range of 10 minutes to 75 minutes, and even more preferably in the range of 15 minutes to 60 minutes. Range. The rate of temperature increase from room temperature to the curing temperature is not particularly limited, but is preferably 1.5 ° C / min to 30 ° C / min, more preferably 2 ° C / min to 30 ° C / min.

When thermosetting the thermosetting resin composition under step conditions, for example, after heating for 10 minutes or more at a temperature T ₁ (where 50 ° C. ≦ T ₁ <150 ° C.), a temperature T ₂ (where 150 ° C. ≦ T ₍₂ ≦ 240 ° C.) for 5 minutes or more.

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

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

In the step conditions, the temperature T ₂ is preferably 155 ° C. ≦ T ₂ ≦ 230 ° C., more preferably 160 ° C. ≦ T ₂ ≦ 220 ° C., more preferably 170 ° C., although it depends on the composition of the thermosetting resin composition. ≦ T ₂ ≦ 210 ° C. is satisfied.

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

In step condition, the time of heating at a temperature _{T 2} depends on the value of temperature _{T 2,} preferably 5 minutes to 100 minutes, more preferably 10 minutes to 80 minutes, more preferably 50 minutes to 10 minutes is there.

In step conditions are not particularly limited heating rate from room temperature to the temperature T _1, and preferably 1.5 ° C. / min to 30 ° C. / min, more preferably 2 ° C. / min to 30 ° C. / min. The rate of temperature increase from temperature T ₁ to temperature T ₂ is preferably 1.5 ° C./min to 30 ° C./min, more preferably 2 ° C./min to 30 ° C./min, and even more preferably 4 ° C./min. -20 ° C / min, even more preferably 4 ° C / min-10 ° C / min.

  The thermosetting of the thermosetting resin composition may be performed under normal pressure or under reduced pressure, but a roughened cured body in which the ratio of Si atoms and O atoms on the surface is in a desired range can be easily obtained. From the standpoint of realization, it is preferable to carry out at an air pressure of preferably 0.075 mmHg to 3751 mmHg (0.1 hPa to 5000 hPa), more preferably 1 mmHg to 1875 mmHg (1.3 hPa to 2500 hPa).

  As described above, the thermoset formed in this manner has a high surface scratch hardness measured according to JIS K5600-5-4 (ISO 15184), and is measured by X-ray photoelectron spectroscopy. The amount of Si tends to be low. Since the surface of such a thermosetting body is appropriately roughened in the roughening treatment in step (B) described later, it is possible to suppress an excessive increase in surface roughness. In addition, since the ratio of Si atoms and O atoms on the surface is in the desired range after the roughening treatment, a roughened cured body that exhibits high peel strength to the conductor layer even when the surface has low roughness is realized. be able to.

  The procedure and conditions of the roughening treatment in the step (B) are not particularly limited, and known procedures and conditions that are usually used when forming the insulating layer of the printed wiring board can be adopted.

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

  The roughened and cured product of the present invention thus obtained has a low inorganic surface content and exhibits excellent peel strength with respect to the conductor layer while maintaining the property that the inorganic filler content is high. This contributes significantly to the miniaturization of the board.

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

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

  The conductor layer may have a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor 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 thickness of the conductor layer is preferably 40 μm or less, more preferably 1 to 35 μm, and even more preferably 3 to 20 μm, from the viewpoint of fine wiring of the printed wiring board. Even when the metal layer has a multilayer structure, the thickness of the entire metal layer is preferably within the above range.

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

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

In the laminate of the present invention, the peel strength between the roughened cured body and the conductor layer is preferably 0.3 kgf / cm or more, more preferably 0.4 kgf / cm or more, still more preferably 0.5 kgf / cm or more, More preferably 0.55 kgf / cm or more, particularly preferably 0.6 kgf / cm or more. On the other hand, the upper limit of the peel strength is not particularly limited, but is 1.2 kgf / cm or less, 0.9 kgf / cm or less, and the like.
Although the laminate of the present invention exhibits such a high peel strength even though the arithmetic average roughness Ra of the surface of the roughened cured body is as small as less than 350 nm, it significantly contributes to the fine wiring of the printed wiring board. To do.
In the present invention, the peel strength between the roughened cured body and the conductor layer is the peel strength when the conductor layer is peeled in the direction perpendicular to the roughened cured body (90-degree direction) (90-degree peel strength). The peel strength when the conductor layer is peeled in the direction perpendicular to the roughened cured body (90-degree direction) can be obtained by measuring with a tensile tester. Examples of the tensile tester include “AC-50C-SL” manufactured by TSE Corporation.

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

  In one Embodiment, the printed wiring board of this invention can be manufactured using the above-mentioned adhesive film. In such an embodiment, after laminating so that the thermosetting resin composition layer of the adhesive film is bonded to the circuit board, the above-described “step (A)” and “step (B)” are performed. The roughened cured body of the invention can be formed on a circuit board. When an adhesive sheet has a protective film, it can use for manufacture after removing a protective film. The support may be peeled off between the laminating process and the step (A) or after the step (A), but the ratio of Si atoms to O atoms on the surface is in a desired range. It is preferable to carry out between the laminating process and the step (A) from the viewpoint of easily realizing the roughened cured body in step (b).

The conditions for the laminating treatment are not particularly limited, and known conditions used for forming an insulating layer of a printed wiring board using an adhesive film can be employed. For example, it can be performed by pressing a heated metal plate such as a SUS mirror plate from the support side of the adhesive film. In this case, it is preferable not to press the metal plate directly, but to press through an elastic material such as heat-resistant rubber so that the adhesive film sufficiently follows the circuit irregularities of the circuit board. The pressing temperature is preferably in the range of 70 ° C. to 140 ° C., the pressing pressure is preferably in the range of 1 kgf / cm ^{2 to} 11 kgf / cm ² (0.098 MPa to 1.079 MPa), and the pressing time is preferably The range is from 5 seconds to 3 minutes. The laminating process is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. Lamination treatment can be performed using a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like.

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

  In other embodiment, the printed wiring board of this invention can be manufactured using the above-mentioned resin varnish. In such an embodiment, the resin varnish is uniformly applied on the circuit board by a die coater or the like, and after the thermosetting resin composition layer is formed on the circuit board by heating and drying, the above-mentioned “step ( A roughening hardening body of this invention can be formed on a circuit board by implementing A) "and a" process (B). " The organic solvent used for the resin varnish and the heating and drying conditions may be the same as those described for the production of the adhesive film.

  Next, a conductor layer is formed on the surface of the roughened cured body formed on the circuit board. The production of the printed wiring board may further include a step of forming a via in the insulating layer, a step of removing a resin residue (smear) inside the via, and the like. These steps can be performed according to various methods used for manufacturing a printed wiring board, which are known to those skilled in the art.

  The printed wiring board of the present invention advantageously realizes fine circuit wiring without generation of cracks or circuit distortion.

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

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

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

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

[Preparation of samples for measurement and evaluation]
(1) Base treatment of circuit board of glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, “R5715ES” manufactured by Matsushita Electric Works Co., Ltd.) on which an inner layer circuit is formed Both surfaces were immersed in “CZ8100” manufactured by MEC Co., Ltd. and etched by 1 μm to roughen the copper surface.

(2) Laminating treatment of adhesive film The thermosetting resin composition layer of the adhesive film produced in Examples and Comparative Examples was used using a batch type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Co., Ltd.). Was laminated on both sides of the inner layer circuit board so as to be bonded to the inner layer circuit board. Lamination was performed by pressing for 30 seconds at 100 ° C. and a pressure of 0.74 MPa after reducing the pressure to 30 hPa or less by reducing the pressure for 30 seconds.

(3) Thermosetting of the thermosetting resin composition layer After laminating the thermosetting resin composition layer, the thermosetting resin composition layer is thermoset to form thermosetting bodies on both surfaces of the inner circuit board. did. At that time, for Examples 1 to 4 and Comparative Examples 1 and 2, the thermosetting resin composition layer was thermally cured after peeling the PET film as the support. Regarding Example 5, the thermosetting resin composition layer was thermoset with the PET film as a support adhered.
Thermosetting of the thermosetting resin composition layer was performed under the following step conditions for Examples 1, 2, 4 and 5, and under the following non-step conditions for Example 3 and Comparative Examples 1 and 2, respectively.
Step condition: Temperature increased from room temperature (20 ° C) at 10 ° C / min and held at 100 ° C for 30 minutes, then heated at 10 ° C / min and held at 180 ° C for 30 minutes Non-step condition: Room temperature (20 ° C) From 10 ° C / min and hold at 180 ° C for 30 minutes

  About the obtained thermosetting body, while scratching hardness, surface Si amount, and surface O amount were measured, the etching amount per unit surface area was evaluated.

(4) Roughening treatment The inner layer circuit board on which the thermosetting body is formed on both surfaces is added to a swelling liquid (Atotech Japan Co., Ltd. “Swelling Dip Securigant P”, sodium hydroxide aqueous solution containing diethylene glycol monobutyl ether). Immerse at 5 ° C. for 5 minutes, then oxidant (Atotech Japan Co., Ltd. “Concentrate Compact P”, aqueous solution with potassium permanganate concentration of about 6 mass%, sodium hydroxide concentration of about 4 mass%) at 80 ° C. for 20 minutes. Immerse for a minute. Then, after washing with water for 1 minute, it was immersed in a neutralizing solution (Atotech Japan Co., Ltd. “Reduction Sholycine Securigant P”, hydroxylamine sulfate aqueous solution) at 40 ° C. for 5 minutes, and then roughly coated on both sides of the inner circuit board. A cured product was formed.
About the obtained roughening hardening body, surface Si amount, surface O amount, and arithmetic mean roughness Ra of the surface were measured.

(5) Formation of conductor layer According to a semi-additive method, a conductor layer was formed on the surface of the roughened cured body.
That is, the inner layer circuit board having the roughened cured body formed on both surfaces was immersed in an electroless copper plating solution containing a palladium compound (Pd) to form a plating seed layer on the surface of the roughened cured body. Then, after annealing for 30 minutes at 150 ° C., an etching resist was formed on the plating seed layer, and the plating seed layer was patterned by etching. Subsequently, copper sulfate electroplating was performed to form a copper layer having a thickness of 30 ± 5 μm, and then annealed at 180 ° C. for 60 minutes to form a conductor layer on the surface of the roughened cured body.

<Measurement of scratch hardness>
The scratch hardness of the surface of the thermosetting body was measured according to JIS K5600-5-4. The pencil used for the measurement was “uni” manufactured by Mitsubishi Pencil Co., Ltd.

<Evaluation of etching amount per unit surface area of thermoset>
The etching amount per unit surface area of the thermoset was evaluated according to the following.
That is, the resin varnishes prepared in Examples and Comparative Examples are PET films with alkyd resin release layers (PET films coated with “AL-5” manufactured by Lintec Corporation, hereinafter referred to as “PET with release layers”). ) And uniformly coated with a die coater and dried at 75 ° C. for 3 minutes to form a thermosetting resin composition layer having a thickness of 10 μm. Next, with respect to Examples 1, 2, 4 and 5, the thermosets were obtained by heating under the above “step conditions” and with respect to Examples 3 and 1 and 2 under the above “non-step conditions”. It was. Thereafter, the PET with a release layer was peeled off and dried at 130 ° C. for 15 minutes. The mass (initial mass (X1)) immediately after drying of the obtained sample was measured. Next, the surface of the thermosetting body was roughened under the same conditions as “(4) Roughening treatment” in the column “Preparation of measurement / evaluation sample”. After the roughening treatment, it was washed with water and dried at 130 ° C. for 15 minutes. The mass immediately after drying of the obtained roughened sample (the mass after the roughening treatment (X2)) was measured. And the etching amount per unit surface area of each thermosetting body was calculated | required by the following formula.

Etching amount per unit surface area (g / m ² ) = (X1−X2) / surface area of cured product

<Measurement of surface Si amount and surface O amount>
The surface Si amount and the surface O amount of the thermoset were measured by X-ray photoelectron spectroscopy using the following measuring apparatus and measurement conditions. The surface Si amount and surface O amount of the roughened cured body were measured in the same manner.
〔measuring device〕
Device type: QUANTERA SXM (Fully automatic scanning X-ray photoelectron spectrometer manufactured by ULVAC-PHI)
Ultimate vacuum: 7.0 × 10 ⁻¹⁰ Torr
X-ray source: monochromatic Al Kα (1486.6 eV)
Spectrometer: Electrostatic concentric hemispherical analyzer Detector: Multi-channel type (32 Multi-Channel Detector)
Neutralizing gun setting Electron: 1.0 V (20 μA), ion: 10.0 V (7 mA)
〔Measurement condition〕
[Survey spectrum (wide scan)]
X-ray beam diameter: 100 μmΦ (HP mode, 100.6 W, 20 kV)
Measurement area: 1400 μm × 100 μm
Signal capture angle: 45.0 °
Pass energy: 280.0eV

<Measurement of arithmetic average roughness Ra>
Arithmetic average roughness Ra of the surface of the roughened cured body is measured using a non-contact type surface roughness meter ("WYKO NT3300" manufactured by BEIKO INSTRUMENTS Co., Ltd.) with a VSI contact mode and a 50 × lens and a measurement range of 121 μm × 92 μm. It calculated | required by the obtained numerical value. For each roughened cured body, an average value of 10 points was determined.

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

[Production Example 1]
(1) Preparation of resin varnish 1 10 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “jER828EL” manufactured by Mitsubishi Chemical Corporation), biphenyl type epoxy resin (epoxy equivalent 269, manufactured by Nippon Kayaku Co., Ltd. “NC3000L” ”) 20 parts, 6 parts of tetrafunctional naphthalene type epoxy resin (epoxy equivalent 163,“ HP4700 ”manufactured by DIC Corporation), and phenoxy resin (“ YL7553BH30 ”manufactured by Mitsubishi Chemical Corporation), MEK having a solid content of 30 mass% 10 parts of a 1: 1 solution of cyclohexanone, weight average molecular weight 35000) was dissolved by heating in a mixed solvent of 5 parts of MEK, 5 parts of cyclohexanone and 15 parts of solvent naphtha while stirring. After cooling to room temperature, there were 15 parts of a triazine-containing phenol novolac type curing agent (hydroxyl equivalent 125, “LA7054 manufactured by DIC Corporation, MEK solution having a solid content of 60% by mass), naphtholic curing agent (hydroxyl equivalent 215). , 15 parts of “SN-485” manufactured by Tohto Kasei Co., Ltd., MEK solution having a solid content of 60%, 1 part of amine curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass) , Imidazole curing accelerator (1-benzyl-2-phenylimidazole, “1B2PZ” manufactured by Shikoku Kasei Kogyo Co., Ltd., MEK solution having a solid content of 5 mass%), 0.3 part of flame retardant (manufactured by Sanko Co., Ltd. “ HCA-HQ ”, 10 parts of 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm), aminosilane-based coupling Grayed agent (Shin-Etsu Chemical Co., Ltd., "KBM573") surface-treated with spherical silica (average particle size 0.5 [mu] m, Co. Admatechs Co. "SOC2" carbon amount per unit area 0.39 mg / m ² ) 140 parts of polyvinyl butyral resin ("KS-1" manufactured by Sekisui Chemical Co., Ltd., ethanol and toluene 1: 1 solution with a solid content of 15% by weight) are mixed and dispersed uniformly with a high-speed rotary mixer. Thus, a resin varnish 1 was prepared.
(2) Production of Adhesive Film 1 A PET film having a thickness of 38 μm was prepared as a support. On the surface of the support, the resin varnish 1 obtained in the above (1) was uniformly applied by a die coater so that the thickness of the thermosetting resin composition layer after drying was 40 μm, The adhesive film 1 was produced by drying at 120 ° C. (average 100 ° C.) for 6 minutes.

[Production Example 2]
Instead of 15 parts of a naphthol-based curing agent (hydroxyl equivalent 215, “SN-485” manufactured by Tohto Kasei Co., Ltd., MEK solution having a solid content of 60%), a dicyclopentadiene type phenol novolac curing agent (hydroxyl equivalent 192, group) Resin varnish 2 was prepared in the same manner as in Production Example 1 except that 16 parts of “GDP-6140” manufactured by Eiken Industry Co., Ltd., MEK solution having a solid content of 50% was used.
Using the obtained resin varnish 2, an adhesive film 2 was produced in the same manner as in Production Example 1.

[Production Example 3]
(1) Preparation of resin varnish 3 15 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “jER828EL” manufactured by Mitsubishi Chemical Corporation) and biphenyl type epoxy resin (epoxy equivalent 291, manufactured by Nippon Kayaku Co., Ltd.) NC3000H ") was dissolved in a mixed solvent of 15 parts of MEK and 15 parts of cyclohexanone with stirring. After cooling to room temperature, 20 parts of an active ester curing agent (active ester equivalent 223, “HPC-8000-65T” manufactured by DIC Corporation, 65% solid toluene solution), triazine-containing cresol novolak resin ( Phenol equivalent 151, DIC Corporation “LA3018-50P”, 6 parts of a solid content 50% 2-methoxypropanol solution), amine curing accelerator (4-dimethylaminopyridine (DMAP), solid content 5% by mass MEK solution) 1 part, spherical silica surface treated with aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle diameter 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd., unit area) carbon amount 0.39 mg ^/ m 2) 110 parts per, phenoxy resin (Mitsubishi Chemical Co., Ltd. "YL7553BH30" Solid content 30% by weight of MEK and cyclohexanone 1: 1 solution, the weight average molecular weight 35000) 7 parts were mixed, and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 3.
(2) Production of Adhesive Film 3 Adhesive film 3 was produced in the same manner as in Production Example 1 using resin varnish 3 obtained in (1) above.

[Production Example 4]
Spherical silica surface treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd.) Resin varnish 4 was prepared in the same manner as in Production Example 1 except that the amount of 39 mg / m ² ) was changed from 140 parts to 200 parts.
Using the obtained resin varnish 4, an adhesive film 4 was produced in the same manner as in Production Example 1.

[Production Example 5]
1 part of amine-based curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass) and imidazole-based curing accelerator (1-benzyl-2-phenylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) 1B2PZ ", MEK solution having a solid content of 5% by mass) 0.3 parts instead of phosphorus-based curing accelerator (tetraphenylphosphonium tetra-p-tolylborate," TPP-MK "manufactured by Hokuko Sangyo Co., Ltd.) Resin varnish 5 was prepared in the same manner as in Production Example 1 except that was used.
Using the obtained resin varnish 5, an adhesive film 5 was produced in the same manner as in Production Example 1.

[Production Example 6]
Except not using 10 parts of phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, solid solution of MEK and cyclohexanone with a solid content of 30% by mass, weight average molecular weight 35000), the same as in Production Example 1 Resin varnish 6 was prepared.
Using the obtained resin varnish 6, an adhesive film 6 was produced in the same manner as in Production Example 1.

  About the produced adhesive films 1-6, the composition of a thermosetting resin composition layer is put together in Table 1, and is shown.

<Example 1>
Using the adhesive film 1, a printed wiring board was produced according to the procedure of [Preparation of measurement / evaluation sample]. Each evaluation result is shown in Table 2.

<Example 2>
Using the adhesive film 2, a printed wiring board was produced according to the above-mentioned procedure [Preparation of measurement / evaluation sample]. Each evaluation result is shown in Table 2.

<Example 3>
Using the adhesive film 3, a printed wiring board was produced according to the procedure of [Preparation of measurement / evaluation sample]. Each evaluation result is shown in Table 2.

<Example 4>
Using the adhesive film 4, a printed wiring board was produced according to the procedure of [Preparation of measurement / evaluation sample]. Each evaluation result is shown in Table 2.

<Example 5>
Using the adhesive film 2, a printed wiring board was produced according to the above-mentioned procedure [Preparation of measurement / evaluation sample]. Each evaluation result is shown in Table 2.

<Comparative Example 1>
Using the adhesive film 5, a printed wiring board was produced according to the procedure of [Preparation of measurement / evaluation sample]. Each evaluation result is shown in Table 2.

<Comparative example 2>
A printed wiring board was produced using the adhesive film 6 according to the procedure of [Preparation of measurement / evaluation sample]. Each evaluation result is shown in Table 2.

  From Table 2, the roughened cured bodies of Examples 1 to 5 having a surface Si amount of 25 atom% or less and an O amount of 25 atom% or more measured by X-ray photoelectron spectroscopy have a surface roughness. It is confirmed that it exhibits low and excellent peel strength with respect to the conductor layer. On the other hand, the roughened cured bodies of Comparative Examples 1 and 2 in which the ratio of Si atoms and O atoms on the surface is not in the desired range exhibit sufficient peel strength with respect to the conductor layer even though the surface roughness is high. It is confirmed that it does not.

Claims (10)

A roughened cured body obtained by roughening a thermoset of a thermosetting resin composition having an inorganic filler content of 50% by mass or more,
A roughened cured body having a surface Si amount of 25 atom% or less and a surface O amount of 25 atom% or more measured by X-ray photoelectron spectroscopy.   The roughening hardening body of Claim 1 whose ratio (O / Si) of O amount with respect to Si amount of the surface is 2.1 or more.   The roughening hardening body of Claim 1 or 2 whose scratch hardness (JIS K5600-5-4) of the surface of a thermosetting body is H or more.   The roughening hardening body as described in any one of Claims 1-3 whose Si amount of the surface of a thermosetting body measured by the X ray photoelectron spectroscopy is less than 2 atom%. Etching amount per unit surface area in the roughening treatment is 2 g / m ² or less, roughened cured body according to any one of claims 1-4.   The roughening hardening body as described in any one of Claims 1-5 whose arithmetic mean roughness Ra of the surface is 300 nm or less.   A laminate comprising the roughened cured body according to any one of claims 1 to 6 and a conductor layer formed on a surface of the roughened cured body.   The laminate according to claim 7, wherein the peel strength between the roughened cured body and the conductor layer is 0.3 kgf / cm or more.   The printed wiring board by which the insulating layer was formed with the roughening hardening body as described in any one of Claims 1-6.   A semiconductor device comprising the printed wiring board according to claim 9.