JP6545924B2 - Roughened hardened body, laminate, printed wiring board and semiconductor device - Google Patents

Description

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

  As a manufacturing technique of 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 build-up type manufacturing method, the insulating layer is generally formed by thermally curing the resin composition. For example, Patent Document 1 discloses a technique for roughening a cured product obtained by thermally curing a resin composition containing silica particles to form an insulating layer.

  While there is a demand for further improvement in wiring density, the number of laminations tends to increase due to the buildup of the printed wiring board. However, with the increase in the number of laminations, cracks due to the difference in thermal expansion between the insulating layer and the conductor layer The occurrence of circuit distortion is a problem. As a technique for suppressing such problems of cracks and circuit distortion, for example, Patent Document 2 describes the thermal expansion coefficient 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

WO 2010/35451 specification Unexamined-Japanese-Patent No. 2010-202865

  In the technique described in Patent Document 1, an insulating layer exhibiting sufficient peel strength with respect to the conductor layer is realized by the detachment of the silica particles on the surface of the cured body in the roughening treatment. However, if a resin composition having a high content of inorganic filler such as silica particles is used to form an insulating layer having a low coefficient of thermal expansion, the surface of the hardened body after the roughening treatment will have a high degree of roughness. The present inventors have found that the peel strength to the conductor layer may also be reduced.

  An object of the present invention is to provide a roughened cured product which has low surface roughness and exhibits excellent peel strength to a conductor layer while maintaining the property that the content of the inorganic filler is high.

  The inventors of the present invention have found that the above-mentioned problems can be solved by setting the amounts of silicon atoms (Si) and oxygen atoms (O) on the surface of the roughened hardened body to a specific range as a result of earnestly examining the above problems. The present invention has been completed.

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

  According to the present invention, it is possible to provide a roughened cured product having a low surface roughness and exhibiting excellent peel strength to a conductor layer while maintaining the property that the content of the inorganic filler is high.

  Hereinafter, the present invention will be described in detail in line with its preferred embodiments.

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

The amount of Si on the surface of the roughened cured product of the present invention measured by X-ray photoelectron spectroscopy from the viewpoint of obtaining a roughened cured product exhibiting excellent peel strength to the conductor layer even if 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, still more preferably 18 atom% or less, particularly preferably 16 atom% or less, 14 atom% or less, 12 atom% or less, 10 atom% or less It is 8 atom% or less. The lower limit of the amount of Si 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 still more preferably 1 atom% or more.
In addition, the Si atom of the surface of a roughening hardening body originates in the inorganic filler mentioned later and its surface treating agent. Since Si atoms are nonpolar atoms that do not contribute to adhesion with the conductor layer (metal layer), the rough of the present invention is obtained from the viewpoint of obtaining a roughened cured product exhibiting excellent peel strength to the conductor layer. It is preferable that the amount of Si on the surface of the chemical-hardened body be as small as possible.

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, even more preferably 29 atom % Or more, particularly preferably 30 atom% or more. The upper limit of the amount of O is usually 65 atom% or less, preferably 60 atom% or less, more preferably 55 atom% or less, still more preferably 50 atom% or less, still 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.
In addition, O atom of the surface of a roughening hardening body originates in O atom containing components, such as an inorganic filler mentioned later, its surface treating agent, thermosetting resin, and a hardening agent. Since the O atom is a polar atom that contributes to the adhesion with the conductor layer (metal layer), the roughening curing of the present invention is performed from the viewpoint of obtaining a roughened cured body exhibiting excellent peel strength 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 product by X-ray photoelectron spectroscopy can be performed, for example, under the following measurement conditions using the following measurement apparatus.

〔measuring device〕
Device type: QUANTERA SXM (Full-vacuated full automatic scanning X-ray photoelectron spectrometer)
Ultimate vacuum: 7.0 × 10 ^-10 Torr
X-ray source: monochromized Al K α (1486.6 eV)
Spectrometer: electrostatic concentric hemispherical analyzer detector: multi-channel (32 Multi-Channel Detector)
Neutralization 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 μm HP (HP mode, 100.6 W, 20 kV)
Measurement area: 1400 μm × 100 μm
Signal capture angle: 45.0 °
Path energy: 280.0 eV

  The ratio (O / Si) of the amount of O to the amount of Si on the surface of the roughened hardened body is 2 from the viewpoint of obtaining a roughened hardened body that exhibits excellent peel strength to the conductor layer even if the surface has low roughness. 1 or more is preferable, 2.2 or more is more preferable, 2.4 or more is further preferable, and 2.6 or more is further preferable, 2.8 or more, and 3. Particularly preferably, it is 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 in the surface to the above range, the roughened cured product of the present invention can exhibit excellent peel strength to the conductor layer even if the surface has low roughness. In one embodiment, the arithmetic mean roughness Ra of the surface of the roughened cured product of the present invention is preferably less than 350 nm, more preferably 300 nm or less, still more preferably 250 nm or less, from the viewpoint of improving fine wiring formation 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 product of the present invention and the conductor layer 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. A specific example of the noncontact surface roughness tester is "WYKO NT3300" manufactured by Becoin Instruments.

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

  From the viewpoint of obtaining a roughened cured product in which the ratio of Si atoms to O atoms on the surface is in a desired range, the thermally cured product used to form the roughened cured product of the present invention is JIS K5600-5-4 ( The scratch hardness of the surface measured according to ISO 15184) is preferably H or more, more preferably 2H or more, still more preferably 3H or more, particularly preferably 4H or more . The upper limit of such scratch hardness is 8H, preferably 5H or less.

  The thermally cured product also preferably has a surface Si content 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 the amount of Si is not particularly limited, and may be 0 atom%.

When roughening the thermosetting body to obtain a roughening cured body, the etching amount per unit surface area of the thermosetting body in the roughening treatment is a roughening hardening in which the ratio of Si atoms to O atoms on the surface is within a 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 It is particularly preferable that it 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 product of the present invention is preferably 3 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more, still more preferably 15 μm or more, particularly preferably 20 μm or more from the viewpoint of improving insulation. . The thickness of the roughened 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 from the viewpoint of thinning. .

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

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

<Thermosetting resin composition>
The roughening cured body of the present invention is obtained by roughening a thermosetting body of a thermosetting resin composition having an inorganic filler content of 50% by mass or more. The content of the inorganic filler in the thermosetting resin composition is preferably 55% by mass or more, and more preferably, from the viewpoint of sufficiently reducing the coefficient of thermal expansion of the roughened cured product (insulating layer) to be obtained. 60 mass% or more, more preferably 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 product of the present invention in which the ratio of Si atoms to O atoms on the surface is in a specific range, the content of the inorganic filler can be further increased without decreasing the peel strength 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 to more than mass%.

  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 mass%, from the viewpoint of preventing the reduction in mechanical strength of the thermosetting body of the thermosetting resin composition. % Or less, more preferably 85% by mass or less.

  As the inorganic filler, for example, silica, silicon nitride, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, titanium And barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like. Among these, silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like are particularly preferable. Moreover, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more. Examples of commercially available spherical fused silica include "SOC2" and "SOC1" manufactured by Admatechs Co., Ltd.

  The average particle diameter 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, 0.1 μm to 0.8 μm Even more preferred. The average particle size 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 type particle size distribution measuring device, and the median diameter can be measured as an average particle size. As a measurement sample, one in which an inorganic filler is dispersed in water by ultrasonic waves can be preferably used. As laser diffraction scattering type particle size distribution measuring apparatus, LA-500 etc. by Horiba, Ltd. can be used.

  The inorganic filler is an inorganic silane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound, a titanate coupling agent, or the like for improving moisture resistance. It is preferable to be processed by the above surface treatment agent. As a commercial item of a surface treatment agent, Shin-Etsu Chemical Co., Ltd. product "KBM403" (3-glycidoxypropyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. product "KBM 803" (3-mercapto propyl trimethoxy) is mentioned, for example. Silane), Shin-Etsu Chemical Co., Ltd. “KBE 903” (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. “KBM 573” (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyl disilazane) etc. are mentioned.

  In addition, after the inorganic filler surface-treated with the surface treatment agent is washed with a solvent (for example, methyl ethyl ketone (MEK)), 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 surface-treated inorganic filler, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solids, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, Horiba "EMIA-320V" etc. 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, from the viewpoint of preventing the melt viscosity of the resin varnish and the rise of the melt viscosity in the film form, 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 preferable.

In one embodiment, a thermosetting resin composition comprises the above-mentioned 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, Especially, an epoxy resin is preferable. The thermosetting resin composition may also contain a curing agent. In one embodiment, the thermosetting resin composition comprises 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, the epoxy resin which can be used as a material of a resin composition, a hardening | curing agent, and an additive are demonstrated.

(Epoxy resin)
As an epoxy resin, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, dicyclopentadiene epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, phenol novolak Type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine 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 resin Resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins and trimethylol type epoxy resins. The epoxy resin may be used singly or in combination of two or more.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, it is preferable that at least 50% by mass or more is an epoxy resin having two or more epoxy groups in one molecule. Among them, an epoxy resin having two or more epoxy groups in one molecule, a liquid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “liquid epoxy resin”), 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 the thermosetting resin composition is also improved.

  The liquid epoxy resin is preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, a phenol novolac epoxy resin, or a naphthalene epoxy resin, and more preferably a naphthalene epoxy resin. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “EXA4032SS”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “jER828EL” (bisphenol A manufactured by Mitsubishi Chemical Corporation) Type epoxy resin), “jER 807” (bisphenol F type epoxy resin), “jER 152” (phenol novolac type epoxy resin) and the like. These may be used alone or in combination of two or more.

  As the solid epoxy resin, tetrafunctional naphthalene type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, biphenyl type epoxy resin, or naphthalene ether type epoxy resin Preferably, 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” (a tetrafunctional naphthalene type epoxy resin), “N-690” (a cresol novolac type epoxy resin), manufactured by DIC Corporation. N-695 "(cresol novolac epoxy resin)," HP-7200 "(dicyclopentadiene epoxy resin)," EXA 7311 "," EXA 7311-G3 "," HP 6000 "(naphthylene epoxy resin), Nipponized Drug "EPPN-502H" (trisphenol epoxy resin), "NC7000L" (naphthol novolac epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl epoxy resin), “ESN 475” manufactured by Nippon Steel Chemical Co., Ltd. Tall novolak epoxy resin), "ESN485" (naphthol novolak type epoxy resin), "YX4000H" manufactured by Mitsubishi Chemical Corporation, "YX4000HK", "YL6121" (biphenyl type epoxy resin) and the like.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the mass ratio (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 4 in mass ratio. preferable. By setting the ratio of the liquid epoxy resin to the solid epoxy resin in such a range, i) suitable adhesiveness is provided when used in the form of an adhesive film described later, ii) used in the form of an adhesive film In this case, sufficient flexibility can be obtained, the handling property is improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii), the mass ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is 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.

  3 mass%-50 mass% are preferable, as for content of the epoxy resin in a thermosetting resin composition, 5 mass%-45 mass% are more preferable, 5 mass%-40 mass% are still more preferable, and 7 mass%. -35 mass% is particularly preferred.

(Hardening agent)
The curing agent is not particularly limited as long as it has a function of curing an epoxy resin, but for example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and a cyanate ester-based curing agent It can be mentioned. A hardening agent may be used individually by 1 type, or may use 2 or more types together.

  From the viewpoints of heat resistance and water resistance, as the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure is preferable. Further, from the viewpoint of adhesion (peeling 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 them, it is preferable to use a triazine skeleton-containing phenol novolac resin as a curing agent from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion (peeling strength) with a conductor layer.

  Specific examples of the phenolic curing agent and naphthol curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395" manufactured by Tohto Kasei Co., Ltd. And “GDP-6140” manufactured by DIC Corporation, “LA7052”, “LA7054”, “LA3018”, and Gunei Chemical Industry Co., Ltd., and the like.

  From the viewpoint of adhesion (peel strength) to the conductor layer, active ester curing agents are also preferable. Although details will be described later, it is desirable to use an active ester-based curing agent even if the temperature conditions for thermosetting the thermosetting resin composition are “non-step” conditions or “step” conditions. It is possible to easily obtain a thermosetting body having a scratch hardness and easily realize a roughening hardened body in which the ratio of Si atoms to O atoms on the surface is in a desired range.

  The active ester curing agent is not particularly limited, but generally an ester group having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters and esters of heterocyclic hydroxy compounds is contained in one molecule. Compounds having two or more of them are preferably used. The active ester curing agent is preferably obtained by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based 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. As a phenol compound or naphthol compound, for example, hydroquinone, resorcine, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, Benzene triol, dicyclopentadienyl diphenol, phenol novolac and the like can be mentioned.

  As an active ester curing agent, an active ester compound containing a dicyclopentadienyl diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated compound of phenol novolac, an active ester containing benzoylated compound of phenol novolac Compounds are preferable, and active ester compounds containing a naphthalene structure, and active ester compounds containing a dicyclopentadienyl diphenol structure are more preferable.

  As a commercial item of the active ester-based curing agent, as an active ester compound having a dicyclopentadienyl diphenol structure, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T” (DIC Corporation) Products), “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 acetylated products of phenol novolac, phenol novolac Examples of the active ester compound containing a benzoyl compound include “YLH1026” (manufactured by Mitsubishi Chemical Corporation).

  Specific examples of the benzoxazine-based curing agent include “HFB 2006 M” manufactured by Showa Highpolymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  As a cyanate ester-based curing agent, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylene bis (2,6-dimethylphenyl cyanate), 4,4 '-Ethylidene diphenyl dicyanate, hexafluoro bisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1, 1-bis (4- cyanate phenyl methane), bis (4- cyanate 3,5- dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatophenyl-1- (methylethylidene)) benzene, bis (4-cyanatophenyl) thioether, and bis (4-cyanatophenyl) ether, phenol Novolak and Ku Polyfunctional cyanate resins derived from zol novolac etc., prepolymers in which these cyanate resins are partially triazineated, etc. Specific examples of cyanate ester-based curing agents include “PT30” manufactured by Lonza Japan Co., Ltd. and "PT60" (all are phenol novolac type polyfunctional cyanate ester resins), "BA 230" (a prepolymer in which a part or all of bisphenol A dicyanate is triazinated to form a trimer), and the like.

  The ratio by weight of the epoxy resin to the curing agent is preferably in the range of 1: 0.2 to 1: 2, as a ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of curing agent], 1: 0.3 to 1: 1.5 is more preferable, and 1: 0.4 to 1: 1 is further preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, which differs depending on the type of the curing agent. Further, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the mass of the solid content of each epoxy resin by the epoxy equivalent, for all the epoxy resins, and the total number of reactive groups of the curing agent is It is the value which totaled the value which remove | divided the solid content mass of each hardening | curing agent by reaction group equivalent for all the hardening | curing agents. By setting the ratio of the epoxy resin to the curing agent in such a range, the heat resistance of the thermosetting body of the thermosetting resin composition is further improved.

  In one embodiment, the thermosetting resin composition used to form the roughened cured product of the present invention comprises the above-described inorganic filler, an epoxy resin, and a curing agent. The thermosetting resin composition contains silica as an inorganic filler, 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: 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 1: 0.8 to 1: 2.6. It is preferable to include one or more selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, and an active ester-based curing agent as the curing agent. With regard to the thermosetting resin composition layer containing such specific components in combination, the preferred content of the inorganic filler, the epoxy resin, and the curing agent is as described above, but above all, the content of the inorganic filler Is preferably 50% by mass to 95% by mass, the content of the epoxy resin is preferably 3% by mass to 50% by mass, the content of the inorganic filler is 50% by mass to 90% by mass, the content of the epoxy resin 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)
It is preferable that the thermosetting resin composition contains a thermoplastic resin from the viewpoint of easily realizing a roughened cured product in which the ratio of Si atoms to O atoms on the surface is in a desired range. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamide imide resin, polyether sulfone resin, and polysulfone resin. Among these, phenoxy resin and polyvinyl acetal resin are preferable. The thermoplastic resin may be used alone or in combination of two or more.

  The weight average molecular weight of the thermoplastic resin in terms of polystyrene 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 polystyrene equivalent weight average molecular weight of the thermoplastic resin is measured by gel permeation chromatography (GPC). Specifically, the polystyrene equivalent weight average molecular weight of the thermoplastic resin can be measured by using 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. 804 L / K-804 L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and calculated using a standard polystyrene calibration curve.

  As the phenoxy resin, for example, bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene The phenoxy resin which has 1 or more types of frame | skeleton selected from frame | skeleton, and the group which consists of trimethyl cyclohexane frame | skeleton is mentioned. The terminal of the phenoxy resin may be any functional group such as phenolic hydroxyl group and 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 of which are bisphenol A skeleton-containing phenoxy resins), “YX8100” (bisphenol S skeleton-containing phenoxy resins), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). Other examples include “FX280” and “FX293” manufactured by Tohto Kasei Co., Ltd., “YL7553” manufactured by Mitsubishi Chemical Corporation, “YL6794”, “YL7213”, and the like. YL7290 "and" YL7482 "can be mentioned.

  As polyvinyl acetal resin, polyvinyl butyral resin is preferable, As a specific example, electrified butyral 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., Sekisui Chemical Co., Ltd. Elek BH series, BX series, KS series, BL series, BM series etc.

  As a specific example of a polyimide resin, Shin-Nika Chemical Co., Ltd. "Rika coat SN20" and "Rika coat PN20" are mentioned. Specific examples of the polyimide resin also include a 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), and a polysiloxane skeleton Modified polyimides such as contained polyimides (described in JP-A-2002-12667 and JP-A-2000-319386) may, for example, be mentioned.

  As a specific example of a polyamide imide resin, Toyobo Co., Ltd. product "Viromax HR11NN" and "Viromax HR16NN" are mentioned. Specific examples of the polyamideimide resin also 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, Sumitomo Chemical Co., Ltd. "PES5003P" etc. are mentioned.

  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 product in which the ratio of Si atoms to 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%.

  As a curing accelerator, a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, etc. are mentioned, for example. From the viewpoint of easily achieving a roughened cured product in which the ratio of Si atoms to O atoms on the surface is in a desired range, amine curing accelerators and imidazole curing accelerators are more preferable as the curing accelerator.

  As a phosphorus-based curing accelerator, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate Tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate and the like.

  Examples of the amine-based curing accelerator include triethylamine, trialkylamines such as tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo Examples include (5,4,0) -undecene and the like, with preference given to 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene.

  Examples of the imidazole-based 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-5 hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyone And imidazole compounds such as 3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and adducts of the imidazole compound with an epoxy resin, and 2-ethyl-4-methylimidazole, 1-benzyl-2-ylimidazole. Phenylimidazole is preferred.

  As the guanidine-based curing accelerator, for example, dicyandiamide, 1-methyl guanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-phenyl guanidine, 1- (o-tolyl) guanidine, dimethyl guanidine, diphenyl guanidine, trimethyl guanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Dec-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.

  The curing accelerator may be used alone or in combination of two or more. In a preferred embodiment, the curing accelerator contained in the heat-effect resin composition is at least one selected from the group consisting of an amine curing accelerator and an imidazole curing accelerator. The content of the curing accelerator in the thermosetting resin composition may be in the range of 0.05% by mass to 3% by mass, based on 100% by mass of the total of the non-volatile components of the epoxy resin and the curing agent. preferable.

  Examples of the flame retardant include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides and the like. The flame retardant may be used alone or in combination of two or more. 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 1.5% by mass or more 8 mass% is more preferable.

  As the rubber particles, for example, those which do not dissolve in an organic solvent described later and are not compatible 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 the rubber component does not dissolve in an organic solvent or resin, and forming it into particles.

  Examples of the rubber particles include core-shell rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell rubber particles are rubber particles having a core layer and a shell layer, and for example, a two-layer structure in which the shell layer of the outer layer is composed of a glassy polymer and the core layer of the inner layer is composed of a rubbery polymer, The shell layer of the outer layer is composed of a glassy polymer, the middle layer is composed of a rubbery polymer, and the core layer is composed of a glassy polymer. The glassy polymer layer is composed of, for example, methyl methacrylate polymer and the like, and the rubbery polymer layer is composed of, for example, butyl acrylate polymer (butyl rubber) and the like. The rubber particles may be used alone or in combination of two or more.

  The average particle size of the rubber particles is preferably in the range of 0.005 μm to 1 μm, and more preferably in the range of 0.2 μm to 0.6 μm. The average particle size of the rubber particles can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in a suitable organic solvent by ultrasonic waves or the like, and the particle size distribution of rubber particles is made based on mass using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.) It can measure by making the median diameter into an average particle diameter. The content of rubber particles in the thermosetting resin composition is preferably 1% by mass to 10% by mass, and 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 optionally contain other additives, and as such other additives, for example, organic Organic metal compounds such as copper compounds, organic zinc compounds and organic cobalt compounds, and resin additives such as organic fillers, thickeners, antifoaming agents, leveling agents, adhesion imparting agents, coloring agents, and curable resins are listed. Be

  The roughened cured body of the present invention can be used as a roughened cured body (roughened cured body for insulating layer of printed wiring board) for forming the insulating layer of the printed wiring board. Among them, in the manufacture of a printed wiring board by a build-up method, it can be suitably used as a roughened cured body (roughened cured body for a build-up insulating layer of a printed wiring board) for forming an insulating layer. It can be more preferably used as a cured product for forming a conductor layer (roughed cured product for a buildup insulating layer of a printed wiring board on which a conductor layer is formed by plating).

  When the roughened cured product of the present invention is used for a printed wiring board, the thermosetting resin composition used to form the roughened cured product of the present invention can be easily and efficiently laminated on a circuit board From the viewpoint, it is preferable 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 hardened body of a multilayer structure, you may use the thermosetting resin composition layer of a multilayer structure. In this case, the content of the inorganic filler may be 50% by mass or more in the entire thermosetting resin composition layer.

  As the support, a film made of a plastic material is suitably used. Examples of plastic materials include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), and polycarbonates (hereinafter And may be abbreviated as “PC”), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. Among them, 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.

  In the support, the surface on the side to be bonded to the thermosetting resin composition layer may be subjected to a matting treatment and a corona treatment. Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface of the side joined to a thermosetting resin composition layer.

  The thickness of the support is not particularly limited, but a range of 5 μm to 75 μm is preferable, and a range of 10 μm to 60 μm 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 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, applying the resin varnish on a support using a die coater or the like, and further heating or blowing with a hot air, etc. It can manufacture by drying an organic solvent by this, and forming 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, ethyl acetate, butyl acetate, cellosolve acetate, acetates such as propylene glycol monomethyl ether acetate and carbitol acetate, Examples include carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. The organic solvents may be used alone or in combination of two or more.

  The drying conditions are not particularly limited, but the 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. Although different depending on the boiling point of the organic solvent in the resin varnish, for example, in the case of using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, 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 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 adhesion of dust and the like to the surface of the thermosetting resin composition layer and scratches. The adhesive film can be wound and stored in a roll, and can be used by peeling off the protective film when producing the roughened cured product of the present invention.

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

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

The thermosetting of the thermosetting resin composition in the step (A) may be carried out under the 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. When the thermosetting resin composition is thermally cured under the step conditions, it is not limited to two-stage heating (T ₁ → T ₂ ), but may be three stages (T ₁ → T ₂ → T ₃ ) or more stages. It may be heating.

  It is preferable that the thermosetting resin composition be thermally cured under the step conditions, from the viewpoint that a roughened cured product having a ratio of Si atoms to O atoms on the surface in a desired range can be easily realized. When an active ester-based curing agent is used as the curing agent, the ratio of Si atoms to O atoms on the surface is within the desired range even when the thermosetting resin composition is thermally cured under non-step conditions or step conditions. A roughened hardened 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, 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 still more preferably in the range of 15 minutes to 60 minutes. Range. The temperature raising rate from room temperature to the above 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.

In the case of thermosetting the thermosetting resin composition under the step conditions, for example, after heating for 10 minutes or more at a temperature T ₁ (where 50 ° C. ≦ T ₁ <150 ° C.), the temperature T ₂ (where 150 ° C. ≦ T) _The heating may be carried out at 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 preferably 60 ° C. ≦ T ₁ ≦ 130 ° C., more preferably 70 ° C. ≦ T ₁ ≦ 120 ° C., 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 step condition, temperature _{T 2,} depending on the composition of the thermosetting resin composition, preferably from _{155 ℃ ≦ T 2 ≦ 230 ℃} , more preferably _{160 ℃ ≦ T 2 ≦ 220 ℃} , more preferably 170 ° C. ≦ _{T 2} ≦ 210 meet ° C..

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

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 the step conditions, the heating rate from room temperature to the temperature T ₁ is not particularly limited, but is preferably 1.5 ° C./min to 30 ° C./min, more preferably 2 ° C./min to 30 ° C./min. Further, heating rate from temperature _{T 1} of the temperature _{T 2} is preferably 1.5 ° C. / min to 30 ° C. / min, more preferably 2 ° C. / min to 30 ° C. / min, more preferably 4 ° C. / min -20 ° C / min, even more preferably 4 ° C / min to 10 ° C / min.

  The thermosetting of the thermosetting resin composition may be carried out under normal pressure or under reduced pressure, but a roughened cured body having a ratio of Si atoms to O atoms in the surface in a desired range is easily From the viewpoint of realization, it is preferable to carry out at an air pressure in the range 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).

  The thermosetting body thus formed has a high surface scratch hardness measured according to JIS K 5600-5-4 (ISO 15184) as described above, and a surface measured by X-ray photoelectron spectroscopy. The amount of Si tends to be low. The surface of such a thermally cured product is appropriately roughened in the roughening treatment in step (B) described later, so that an excessive increase in surface roughness can be suppressed. 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 hardened body exhibiting high peel strength to the conductor layer is realized even if the surface has low roughness. be able to.

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

  For example, the surface of the cured product can be roughened by performing a swelling treatment with a swelling solution, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution in this order. The swelling liquid is not particularly limited, and examples thereof include an alkaline solution, a surfactant solution and the like, preferably an alkaline solution, and as the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. As a swelling liquid marketed, Swelling dip security g P made from Atotech Japan Co., Ltd., swelling dip security G SBU etc. are mentioned, for example. Although the swelling process by a swelling liquid is not specifically limited, For example, it can carry out by immersing hardened | cured material in a 30-90 degreeC swelling liquid for 1 minute-20 minutes. From the viewpoint of suppressing the swelling of the resin of the cured product to an appropriate level, it is preferable to immerse the cured product 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 permanganic acid 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 carried out by immersing the cured product in the oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 minutes 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 permanganic acid solutions such as Concentrate Compact P and Dosing Solutions Securigans P manufactured by Atotech Japan Co., Ltd. In addition, as the neutralization solution, an acidic aqueous solution is preferable, and as a commercial product, for example, Reduction Sholeucine Securigant P manufactured by Atotech Japan Co., Ltd. can be mentioned. The treatment with the neutralization solution can be carried out by immersing the treated surface roughened with the oxidizing agent solution in the neutralization solution at 30 to 80 ° C. for 5 minutes to 30 minutes. From the viewpoint of workability and the like, it is preferable to immerse the object roughened with the oxidizing agent solution in a neutralization solution at 40 to 70 ° C. for 5 minutes to 20 minutes.

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

[Laminate]
The laminate of the present invention comprises the roughened cured product of the present invention and a conductor layer formed on the surface of the roughened cured product.

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

  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 hardened body is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of a nickel-chromium alloy.

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

  The conductor layer can be formed by dry plating or wet plating. Examples of dry plating include known methods such as vapor deposition, sputtering and ion plating. In the case of wet plating, for example, electroless plating and electrolytic plating are combined to form a metal layer. Alternatively, a plating resist having a pattern reverse to that of the metal layer (conductor layer) may be formed, and the metal layer may be formed only by electroless plating. As a method of forming a wiring pattern, for example, a subtractive method, a semi-additive method or the like 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 still more preferably 3 to 20 μm from the viewpoint of microwiring 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 product 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, it is 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, or the like.
Although the laminate of the present invention exhibits such high peel strength despite the fact that the arithmetic mean 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 It is
In the present invention, the peel strength between the roughened cured product and the conductor layer is the peel strength (90 degree peel strength) when the conductive layer is peeled off in the direction perpendicular to the roughened cured product (90 degrees direction). It can be determined by measuring the peel strength when the conductor layer is peeled off in the direction perpendicular to the roughening cured body (90 degrees direction) with a tensile tester. As a tension tester, "AC-50C-SL" made from TSE Co., Ltd. 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 of the cured product of the present invention.

  In one embodiment, the printed wiring board of the present invention can be manufactured using the above-mentioned adhesive film. In such an embodiment, after the laminating process is performed 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 to carry out the present process. The roughened cured product of the invention can be formed on a circuit board. When the adhesive sheet has a protective film, it can be subjected to production after removing the protective film. In addition, although peeling of a support body may be implemented between a lamination process and a process (A) and may be implemented after a process (A), the ratio of Si atom of a surface and O atom is a desired range. It is preferable to carry out between a lamination process and a process (A) from a viewpoint of implement | achieving easily the roughening hardening body which exists in (4).

The conditions for the lamination process are not particularly limited, and any known conditions used to form an insulating layer of a printed wiring board using an adhesive film can be adopted. For example, it can carry out by pressing metal plates, such as a heated SUS end plate, from the support body side of adhesive film. In this case, it is preferable not to press the metal plate directly but to perform pressing via an elastic material such as heat-resistant rubber so that the adhesive film sufficiently follows the circuit irregularities of the circuit board. The press temperature is preferably in the range of 70 ° C. to 140 ° C., the press 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 press time is preferably It is in the range of 5 seconds to 3 minutes. The lamination process is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. The lamination process can be carried out using a commercially available vacuum laminator. As a vacuum laminator marketed, a vacuum pressure type laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nichigo Morton Co., Ltd., etc. may be mentioned.

  In the present invention, the "circuit board" is mainly patterned on one side 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, or a thermosetting polyphenylene ether substrate. It refers to one in which a conductor layer (circuit) is formed. Further, when manufacturing a printed wiring board, 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 another embodiment, the printed wiring board of the present invention can be manufactured using the above-mentioned resin varnish. In such an embodiment, a resin varnish is uniformly applied on a circuit board by a die coater or the like, heated and dried to form a thermosetting resin composition layer on the circuit board, and then the above-mentioned “step ( "A)" and "Step (B)" can be carried out to form the roughened cured product of the present invention on a circuit board. 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 roughening cured body formed on the circuit board. The manufacturing 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 known to those skilled in the art that are used in the manufacture of printed wiring boards.

  The printed wiring board of the present invention advantageously realizes the fine wiring of the circuit without the occurrence of the crack and the circuit distortion.

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

  Examples of such semiconductor devices include various semiconductor devices provided for electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft etc.), etc. .

  EXAMPLES Hereinafter, the present invention will be specifically described by way of 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 sample for measurement and evaluation]
(1) Substrate treatment of circuit board A glass cloth-based epoxy resin double-sided copper-clad laminated board (copper foil thickness 18 μm, substrate thickness 0.3 mm, "R5715 ES" manufactured by Matsushita Electric Works Co., Ltd.) on which inner layer circuits are formed Both surfaces were immersed in “CZ8100” manufactured by MEC Co., Ltd., and etched for 1 μm to roughen the copper surface.

(2) Lamination treatment of adhesive film A thermosetting resin composition layer was produced using the adhesive films prepared in the examples and comparative examples as a batch type vacuum pressure laminator ("MVLP-500" manufactured by Meishin Co., Ltd.). The laminate was laminated on both sides of the inner layer circuit board so as to bond with the inner layer circuit board. The lamination treatment was performed by reducing the pressure for 30 seconds to make the pressure 13 hPa or less, and pressing for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.

(3) Thermosetting of the thermosetting resin composition layer After lamination processing of the thermosetting resin composition layer, the thermosetting resin composition layer is thermosetted to form thermosetting bodies on both sides of the inner layer circuit board did. At that time, with respect to Examples 1 to 4 and Comparative Examples 1 and 2, the thermosetting resin composition layer was thermally cured after the PET film as a support was peeled off. With respect to Example 5, the thermosetting resin composition layer was thermally cured in the state where the PET film as the support was attached.
The thermosetting of the thermosetting resin composition layer was carried out 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.
Step conditions: Temperature rising from room temperature (20 ° C.) at 10 ° C./min and holding at 100 ° C. for 30 minutes, temperature rising at 10 ° C./min, holding at 180 ° C. for 30 minutes Non-step conditions: Room temperature (20 ° C.) Temperature from 10 ° C / min to 30 min at 180 ° C

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

(4) Coarsening treatment The inner layer circuit board having a thermally cured product formed on both sides is treated with a swelling solution (Atotech Japan Co., Ltd. "Swelling Dip Security G", sodium hydroxide aqueous solution containing diethylene glycol monobutyl ether). Soak at 80 ° C for 20 minutes in an oxidizing agent (Atotech Japan Ltd. "Concentrate Compact P", an aqueous solution of potassium permanganate concentration of about 6% by mass, sodium hydroxide concentration of about 4% by mass). Soak for a minute. Then, after washing with water for 1 minute, the substrate is immersed in a neutralization solution (Atotech Japan Co., Ltd. "Reduction choleucine secligant P", an aqueous solution of hydroxylamine sulfate) for 5 minutes at 40 ° C to roughen the inner layer circuit board on both sides. A hardened body was formed.
The amount of Si on the surface, the amount of O on the surface, and the arithmetic mean roughness Ra of the surface were measured for the obtained roughened cured product.

(5) Formation of conductor layer A conductor layer was formed on the surface of the roughened cured body according to the semi-additive method.
That is, the inner layer circuit board having the roughened cured product 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 product. Then, after performing an annealing process by heating at 150 ° C. for 30 minutes, an etching resist was formed on the plating seed layer, and the plating seed layer was patterned by etching. Then, copper sulfate electrolytic plating was performed to form a copper layer having a thickness of 30 ± 5 μm, and then annealing treatment was performed 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 in accordance with JIS K5600-5-4. The pencil used for the measurement was "uni" manufactured by Mitsubishi Pencil Co., Ltd.

<Evaluation of the amount of etching per unit surface area of a thermosetting body>
The etching amount per unit surface area of the thermosetting body was evaluated according to the following.
That is, the resin varnish prepared in Examples and Comparative Examples is referred to as a PET film coated with an alkyd resin-based release layer (PET film coated with “AL-5” manufactured by Lintec Co., Ltd., hereinafter referred to as “PET with release layer” The solution was uniformly applied by a die coater and dried at 75 ° C. for 3 minutes to form a thermosetting resin composition layer having a thickness of 10 μm. Then, heat is obtained by heating under the above-mentioned "step conditions" for Examples 1, 2, 4 and 5 and under the above "non-step conditions" for Example 3 and Comparative Examples 1 and 2. The Thereafter, the PET with release layer was peeled off and dried at 130 ° C. for 15 minutes. The mass immediately after drying (initial mass (X1)) 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 above “Preparation of sample for measurement and evaluation” column. After the roughening treatment, it was washed with water and dried at 130 ° C. for 15 minutes. The mass (mass after roughening treatment (X2)) immediately after drying of the obtained roughened sample was measured. And the etching amount per unit surface area of each thermosetting object was calculated | required by the following formula.

Amount of etching per unit surface area (g / m ² ) = (X 1 -X 2) / surface area of cured product

<Measurement of surface Si content and surface O content>
The amount of surface Si and the amount of surface O of the thermosetting body were measured by X-ray photoelectron spectroscopy using the following measuring apparatus and measuring conditions. The surface Si amount and the surface O amount of the roughened hardened body were also measured in the same manner.
〔measuring device〕
Device type: QUANTERA SXM (Full-vacuated full automatic scanning X-ray photoelectron spectrometer)
Ultimate vacuum: 7.0 × 10 ^-10 Torr
X-ray source: monochromized Al K α (1486.6 eV)
Spectrometer: Electrostatic concentric hemispherical analyzer Detector: Multi-channel (32 Multi-Channel Detector)
Neutralization 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 μm HP (HP mode, 100.6 W, 20 kV)
Measurement area: 1400 μm × 100 μm
Signal capture angle: 45.0 °
Path energy: 280.0 eV

<Measurement of Arithmetic Average Roughness Ra>
Arithmetic mean roughness Ra of the surface of the roughened hardened body is measured in a 121 μm × 92 μm measurement range by a VSI contact mode, 50 × lens using a non-contact surface roughness meter (“WYKO NT3300” manufactured by B-Coin Instruments Co., Ltd.) It calculated | required by the obtained numerical value. The average value of 10 points was determined for each roughened cured product.

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

Preparation Example 1
(1) Preparation of resin varnish 1 10 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, Mitsubishi Chemical Corporation "jER 828EL"), biphenyl type epoxy resin (epoxy equivalent 269, Nippon Kayaku Co., Ltd. "NC 3000 L" 20 parts, 6 parts of tetrafunctional naphthalene type epoxy resin (epoxy equivalent 163, DIC Corporation “HP 4700”), and phenoxy resin (Mitsubishi Chemical Corporation “YL7553BH30”, MEK having a solid content of 30% by mass A 1: 1 solution of cyclohexanone, 10 parts by weight-average molecular weight 35000, was heated and dissolved 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, 15 parts of a triazine-containing phenol novolac curing agent (hydroxyl group equivalent weight 125, "LA7054" manufactured by DIC Corporation, 60 mass% solid MEK solution), naphtholic curing agent (hydroxyl content equivalent weight 215) Toho Kasei Co., Ltd. product "SN-485", MEK solution of 60% of solid content 15 parts, Amine-based curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution of 5 mass% of solid content) 1 part 0.3 part of imidazole-based curing accelerator (1-benzyl-2-phenylimidazole, “1B2PZ” manufactured by Shikoku Kasei Kogyo Co., Ltd., MEK solution having a solid content of 5% by mass), a flame retardant (manufactured by Sanko Co., Ltd.) HCA-HQ ", 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (average particle size 2 μm) 5 parts, aminosilane based coupler 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., 15 parts by weight of ethanol and toluene with a solid content of 15% by weight) are mixed and uniformly dispersed by a high-speed rotary mixer The resin varnish 1 was prepared.
(2) Preparation of Adhesive Film 1 As a support, a PET film having a thickness of 38 μm was prepared. The resin varnish 1 obtained in the above (1) is uniformly coated on the surface of the support by a die coater so that the thickness of the thermosetting resin composition layer after drying is 40 μm, The adhesive film 1 was produced by drying at 120 degreeC (average 100 degreeC) for 6 minutes.

Preparation Example 2
Dicyclopentadiene type phenol novolac type curing agent (hydroxyl equivalent weight 192, group) instead of 15 parts of naphtholic curing agent (hydroxyl equivalent weight 215, Toho Kasei Co., Ltd. “SN-485”, MEK solution with solid content of 60%) A resin varnish 2 was prepared in the same manner as in Preparation Example 1 except that 16 parts of “GDP-6140” (manufactured by Eisai Chemical Co., Ltd., MEK solution with a solid content of 50%) was used.
An adhesive film 2 was produced in the same manner as in Production Example 1 using the obtained resin varnish 2.

[Preparation Example 3]
(1) Preparation of resin varnish 3 15 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, Mitsubishi Chemical Corporation "jER 828EL"), and biphenyl type epoxy resin (epoxy equivalent 291; Nippon Kayaku Co., Ltd. " 15 parts of NC 3000 H ′ ′) was heated and 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 active ester curing agent (active ester equivalent 223, “HPC-8000-65T”, 65% solid solution in toluene, made by DIC Co., Ltd.), triazine-containing cresol novolac resin ( Phenol equivalent weight 151, DIC Corporation “LA3018-50P”, 6 parts of solid content 50% 2-methoxypropanol solution, amine curing accelerator (4-dimethylaminopyridine (DMAP), solid content 5% by mass 1 part MEK solution, spherical silica (average particle diameter 0.5 μm, surface-treated with an aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. “KBM 573”), average particle diameter 0.5 μm, “SOC 2” 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 An adhesive film 3 was produced in the same manner as in Production Example 1 using the resin varnish 3 obtained in (1) above.

[Preparation Example 4]
Spherical silica (average particle diameter 0.5 μm, average particle diameter 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd.) surface-treated with an aminosilane-based coupling agent (“KBM 573” manufactured by Shin-Etsu Chemical Co., Ltd.) A resin varnish 4 was prepared in the same manner as in Preparation Example 1 except that the compounding amount of 39 mg / m ² ) was changed from 140 parts to 200 parts.
An adhesive film 4 was produced in the same manner as in Production Example 1 using the obtained resin varnish 4.

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

[Preparation Example 6]
In the same manner as in Preparation Example 1 except that 10 parts of phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corp., a 1: 1 solution of MEK having a solid content of 30% by mass, and a weight average molecular weight of 35000) was not used. Resin varnish 6 was prepared.
An adhesive film 6 was produced in the same manner as in Production Example 1 using the obtained resin varnish 6.

  The composition of the thermosetting resin composition layer is collectively shown in Table 1 about the produced adhesive films 1 to 6.

Example 1
A printed wiring board was manufactured using the adhesive film 1 in accordance with the procedure of the above-mentioned [Preparation of sample for measurement and evaluation]. Each evaluation result is shown in Table 2.

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

Example 3
A printed wiring board was manufactured using the adhesive film 3 in accordance with the procedure of the above-mentioned [Preparation of sample for measurement and evaluation]. Each evaluation result is shown in Table 2.

Example 4
A printed wiring board was manufactured using the adhesive film 4 in accordance with the procedure of the above-mentioned [Preparation of sample for measurement and evaluation]. Each evaluation result is shown in Table 2.

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

Comparative Example 1
A printed wiring board was manufactured using the adhesive film 5 in accordance with the procedure of the above-mentioned [Preparation of samples for measurement and evaluation]. Each evaluation result is shown in Table 2.

Comparative Example 2
A printed wiring board was manufactured using the adhesive film 6 in accordance with the procedure of the above-mentioned [Preparation of samples for measurement and evaluation]. Each evaluation result is shown in Table 2.

  From Table 2, the roughened cured products of Examples 1 to 5 in which the amount of Si on the surface is 25 atom% or less and the amount of O is 25 atom% or more measured by X-ray photoelectron spectroscopy have a surface roughness of It is confirmed to exhibit low and excellent peel strength to the conductor layer. On the other hand, the roughened cured products of Comparative Examples 1 and 2 in which the ratio of Si atoms to O atoms in the surface is not within the desired range exhibit sufficient peel strength to the conductor layer despite the high surface roughness. Not be confirmed.

Claims (9)

A roughened cured body obtained by roughening a thermosetting body of a thermosetting resin composition having an inorganic filler content of 50% by mass or more,
The inorganic filler is silica,
The amount of Si on the surface measured by X-ray photoelectron spectroscopy is 25 atom% or less, and the amount of O on the surface is 25 atom% or more,
The thermosetting resin composition including a phenoxy resin,
Roughened cured product (except in the case where the thermosetting resin composition contains an active ester curing agent). A roughened cured body obtained by roughening a thermosetting body of a thermosetting resin composition having an inorganic filler content of 50% by mass or more,
The inorganic filler is silica,
The amount of Si on the surface measured by X-ray photoelectron spectroscopy is 25 atom% or less, and the amount of O on the surface is 25 atom% or more,
The thermosetting resin composition, 0.1 weight thermoplastic resin% to 20 wt% including when the total of the nonvolatile components of the thermosetting resin composition is 100 mass%,
Roughened cured product (except in the case where the thermosetting resin composition contains an active ester curing agent).   The roughening cured body according to claim 1 or 2, wherein the thermosetting resin composition contains a curing accelerator selected from an amine curing accelerator and an imidazole curing accelerator.   The roughened hardened body according to any one of claims 1 to 3, wherein the ratio of the amount of O to the amount of Si on the surface (O / Si) is 2.1 or more. The roughening hardened body as described in any one of Claims 1-4 whose arithmetic mean roughness Ra of the surface is 300 nm or less. A layered product provided with the roughening hardening body according to any one of claims 1 to 5 and a conductor layer formed on the surface of the roughening hardening body. The laminate according to claim 6 , wherein the peel strength between the roughened cured product and the conductor layer is 0.3 kgf / cm or more. The printed wiring board by which the insulating layer was formed by the roughening hardening body as described in any one of Claims 1-5 . A semiconductor device comprising the printed wiring board according to claim 8 .