JP2019085494A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition or the like capable of achieving both insulation performance and laser processability when the insulating layer is a thin film. A resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, wherein the component (C) has a coefficient of variation of particle size distribution of 30% or less. A resin composition having an average particle size of 0.01 μm or more and 5 μm or less. [Selection diagram] None

Description

  The present invention relates to a resin composition. Furthermore, the present invention relates to a resin sheet, a printed wiring board and a semiconductor device using the resin composition.

  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, in Patent Document 1, a resin composition layer is laminated on an inner layer substrate using a resin sheet with a support including a support and a resin composition layer containing silica particles provided on the support. Thereafter, a technique is disclosed in which the resin composition layer is thermally cured, and the obtained cured product is roughened to form an insulating layer.

  Further, for example, Patent Document 2 discloses a technique for reducing the thermal expansion coefficient of an insulating layer to be formed by increasing the content of an inorganic filler such as silica particles in a resin composition.

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

  In recent years, in order to achieve miniaturization of electronic devices, further thinning of printed wiring boards has been promoted. Along with that, thinning of the insulating layer is required.

  Patent Document 1 describes that an insulating layer exhibiting sufficient peel strength with respect to a conductor layer is realized by the detachment of silica particles on the surface of a cured product in the roughening treatment. However, as a result of intensive studies by the present inventor, it is not possible to obtain a roughened surface with a uniform low roughness simply by desorption of silica particles, and desorption traces due to variations in the size of desorption traces of silica particles, etc. It was found that a roughened surface having an uneven size was obtained. When the insulating layer is a thin film, depending on the size of the desorption, the roughened surface of the insulating layer and the opposite surface may be penetrated, and one conductor layer and the other conductor layer may be separated through the detachment. And it becomes difficult to maintain the insulation performance. On the other hand, the present inventor has found that when the resin composition contains a hydrophobic resin such as an active ester compound, a roughened surface having a low roughness can be formed by performing the roughening treatment.

  By the way, a via hole may be formed in the insulating layer for interlayer connection. The via holes are generally formed by laser processing. In laser processing, smear may occur, but this smear is usually removed during the roughening process. However, hydrophobic resins such as active ester compounds have high resistance to a chemical solution for roughening treatment. Therefore, when an active ester compound is used, removal of smear tends to be insufficient. If the removal of the smear is insufficient, the via hole may be clogged with the smear, so that the interlayer connection may be poor and the conduction reliability may be deteriorated.

  When a roughening treatment is performed using a resin composition containing a hydrophobic resin such as an active ester compound, the chemical solution used for the roughening treatment may be made stronger than usual or the temperature to improve the smear removability. It is conceivable to make roughening treatment conditions more severe conditions, such as making However, the inorganic filler contained in the resin composition is likely to be detached under severe conditions, becoming a roughened surface with a large desorption trace as in Patent Document 1, and it is difficult to maintain insulation performance. It could have been.

  As described above, when the active ester compound is used, formation of the via hole by laser processing tends to be insufficient under the normal roughening treatment condition. On the other hand, under severe roughening conditions, formation of via holes by laser processing can be performed stably, but unintended holes are formed in the insulating layer due to detachment of the inorganic filler, and the insulation performance tends to be low. Therefore, when using an active ester compound, coexistence with insulation performance and laser processability is difficult.

  Here, the laser processability refers to the easiness of the formation of the via hole by the treatment including the laser irradiation and the subsequent roughening treatment.

  These problems are particularly difficult to solve, especially when the insulating layer is thin, since unintentional holes are likely to be formed during the roughening treatment due to the detachment of the inorganic filler.

  The present invention has been made in view of the above problems, and a resin composition capable of achieving both insulation performance and laser processability even if the insulating layer is a thin film; a resin containing the above resin composition A resin sheet having a composition layer; a printed wiring board including an insulating layer formed of a cured product of the above resin composition; and a semiconductor device including the cured product of the above resin composition; Do.

As a result of intensive studies to solve the above-mentioned problems, the inventor of the present invention has found that the above-mentioned problems can be solved by the resin composition containing (A) epoxy resin, (B) active ester compound, and (C) predetermined inorganic filler. It found out that it could solve, and completed the present invention.
That is, the present invention includes the following.

[1] A resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler,
The resin composition wherein the component (C) has a coefficient of variation in particle size distribution of 30% or less and an average particle size of 0.01 μm or more and 5 μm or less.
[2] The resin composition according to [1], wherein the content of the component (C) is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass.
[3] The resin composition according to [1] or [2], wherein the average particle size of the component (C) is 0.1 μm or more and 3 μm or less.
[4] The resin composition according to any one of [1] to [3], which is for forming an insulating layer of a printed wiring board.
[5] The circuit of [1] to [4], which is for circuit formation in which the ratio (L / S) of the circuit width (L (μm)) to the width between circuits (S (μm)) is 10 μm / 10 μm or less The resin composition as described in any one.
[6] The resin composition according to any one of [1] to [5], which is a resin composition for forming an insulating layer having a surface having an arithmetic average roughness (Ra) of 150 nm or less.
[7] The resin composition according to any one of [1] to [6], which is a resin composition for forming a via by laser irradiation.
[8] The resin composition was heat cured at 200 ° C. for 90 minutes for 10 arbitrary locations on the surface of the cured product, and 100 μm in width arbitrarily selected among cross-sectional images perpendicular to the surface of the cured product at that location. When observing a range of 5 μm in depth,
When the maximum particle size of the component (C) is R1 (μm) and the average particle size of the component (C) is R2 (μm),
The resin composition in any one of [1]-[7] which satisfy | fills the relationship of R1 <1.4 * R2.
[9] Arbitrary 10 parts on the surface of the cured product obtained by heat curing the resin composition at 90 ° C. for 90 minutes are selected, and a width 100 μm arbitrarily selected among cross-sectional images perpendicular to the surface of the cured product at that position. When observing a range of 5 μm in depth,
When the average particle size of the component (C) is R2 (μm),
The resin composition in any one of [1]-[8] whose number of particle | grains whose particle size is (1.2 * R2) micrometer or more is four or less.
[10] A resin sheet comprising a support, and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [9].
[11] The resin sheet according to [10], wherein the thickness of the resin composition layer is 15 μm or less.
[12] A support, and a resin composition layer provided on the support and containing (C) an inorganic filler-containing resin composition,
The resin composition contains (C) 50% by mass or more of the inorganic filler, assuming that the nonvolatile component in the resin composition is 100% by mass,
The resin composition was heat-cured at 200 ° C. for 90 minutes, and any 10 locations on the surface of the cured product were selected, and a cross-sectional image perpendicular to the surface of the cured product at that location was 100 μm wide and 5 μm deep arbitrarily selected. When observing the range of
Assuming that the maximum particle size of the (C) inorganic filler is R1 (μm) and the average particle size of the (C) inorganic filler is R2 (μm),
Resin sheet which satisfies the relationship of R1 <1.4 × R2.
[13] A support, and a resin composition layer provided on the support and containing a resin composition containing (C) an inorganic filler,
The resin composition contains (C) 50% by mass or more of the inorganic filler, assuming that the nonvolatile component in the resin composition is 100% by mass,
The resin composition was heat-cured at 200 ° C. for 90 minutes, and any 10 locations on the surface of the cured product were selected, and a cross-sectional image perpendicular to the surface of the cured product at that location was 100 μm wide and 5 μm deep arbitrarily selected. When observing the range of
(C) When the average particle diameter of the inorganic filler is R2 (μm),
The resin sheet whose number of particles having a particle size of (1.2 × R 2) μm or more is 4 or less.
[14] A printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
The printed wiring board, wherein the insulating layer is a cured product of the resin composition according to any one of [1] to [9].
[15] A semiconductor device comprising the printed wiring board according to [14].

  According to the present invention, even if the insulating layer is a thin film, a resin composition capable of achieving both insulation performance and laser processability; a resin sheet having a resin composition layer containing the above resin composition; A printed wiring board including an insulating layer formed of a cured product of a resin composition; and a semiconductor device including a cured product of the above resin composition can be provided.

FIG. 1 is a partial cross-sectional view schematically showing an example of a printed wiring board.

  Hereinafter, the present invention will be described in detail by way of embodiments and exemplifications. However, the present invention is not limited to the embodiments and exemplifications listed below, and can be implemented with arbitrary modifications without departing from the scope of the claims of the present invention and the equivalents thereof.

[Resin composition]
The resin composition of the present invention is a resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, and the component (C) has a coefficient of variation in particle size distribution. It is 30% or less, and the average particle diameter is 0.01 μm or more and 5 μm or less. By combining the above-mentioned (A) epoxy resin, (B) active ester compound, and (C) predetermined inorganic filler, it is possible to achieve both insulation performance and laser processability even if the insulating layer is a thin film. The desired effect of the present invention can be obtained, Even if the surface of the cured product of this resin composition is roughened under more severe conditions than usual, desorption of the (C) inorganic filler on the roughened surface is uniform and small. As a result, the insulating layer Even if thin, insulation reliability can be improved. Therefore, the hardened | cured material of this resin composition can be preferably used as an insulating layer of a printed wiring board taking advantage of the outstanding characteristic.

  Moreover, the said resin composition may be combined with the (A)-(C) component, and may further contain arbitrary components. Examples of optional components include (D) curing agent, (E) curing accelerator, (F) thermoplastic resin, (G) flame retardant, and (H) other additives.

<(A) Epoxy resin>
The resin composition contains (A) an epoxy resin as the (A) component. (A) As an epoxy resin, for example, bixylenol type epoxy resin, 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 type Epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin Cresol novolac epoxy resin, biphenyl epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin Heterocyclic epoxy resins, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. Among them, bisphenol A epoxy resin and biphenyl epoxy resin are preferable. The epoxy resin may be used alone or in combination of two or more.

  The (A) epoxy resin preferably has 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, the resin composition is an epoxy resin which is liquid at a temperature of 20 ° C. (hereinafter also referred to as “liquid epoxy resin”) and an epoxy resin which is solid at a temperature of 20 ° C. (hereinafter also referred to as “solid epoxy resin”). It is preferable to include in combination. The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule. The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule. The liquid epoxy resin and the solid epoxy resin are preferably aromatic epoxy resins.

  As liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, ester skeleton Aliphatic epoxy resin, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidyl amine type epoxy resin, aliphatic epoxy resin, and epoxy resin having butadiene structure are preferable, and aliphatic epoxy resin, bisphenol A type epoxy resin And bisphenol F-type epoxy resin are more preferable.

  Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, "828US" manufactured by Mitsubishi Chemical Corp., "jER828EL", "825", "epicoat" “828 EL” (bisphenol A epoxy resin), “jER 807”, “1750” (bisphenol F epoxy resin), “jER 152” (phenol novolac epoxy resin), “630”, “630 LSD” (glycidyl amine epoxy resin) , “ZX1059” (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon Steel Sumikin Chemical Co., Ltd., “EX-721” manufactured by Nagase ChemteX (glycidyl ester epoxy resin), manufactured by Daicel "Ceroxide 021P "(alicyclic epoxy resin having an ester skeleton)," PB-3600 "(epoxy resin having a butadiene structure)," ZX1658 "manufactured by Nippon Steel Sumikin Chemical Co., Ltd.," ZX1658GS "(liquid 1,4-glycidyl cyclohexane type Epoxy resin), "630LSD" (glycidyl amine type epoxy resin) manufactured by Mitsubishi Chemical Corp., "EXA-850 CRP" manufactured by DIC (bisphenol A epoxy resin), "YED-216D" manufactured by Mitsubishi Chemical Corp. (aliphatic) Epoxy resin), "EP-3950S" manufactured by ADEKA, "EP-3980S" (glycidyl amine type epoxy resin); "ELM-100H" manufactured by Sumitomo Chemical (glycidyl amine type epoxy resin), etc. may be mentioned. These may be used singly or in combination of two or more.

  As solid epoxy resin, bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl Type epoxy resin, naphthalene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin is preferable, and bixylenol type epoxy resin, naphthalene type epoxy resin, bisphenol AF Type epoxy resin, and naphthalene ether type epoxy resin are more preferable.

  Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin) manufactured by DIC; “HP-4700” manufactured by DIC, “HP-4710” (naphthalene type tetrafunctional epoxy resin); “N-690” (cresol novolac epoxy resin); “N-695” (cresol novolac epoxy resin) manufactured by DIC; “HP-7200” (dicyclopentadiene type epoxy resin) manufactured by DIC; “HP-7200HH”, “HP-7200H”, “EXA-7311”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S”, “HP6000” manufactured by DIC Corporation Naphthylene ether type epoxy resin); “EPPN-502H” (Trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Resin); “NC7000L” (naphthol novolac epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; Chemical made "ESN 475 V" (naphthalene type epoxy resin); Nippon Steel & Sumikin Chemical make "ESN 485" (naphthol novolac type epoxy resin); Mitsubishi Chemical company made "YX4000H", "YX 4000", "YL 6121" (biphenyl type Epoxy resin); “YX4000HK” (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. “YX 8800” (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; “PG-100” manufactured by Osaka Gas Chemical Co., Ltd., “CG- 500 "; YL manufactured by Mitsubishi Chemical Corporation 760 "(bisphenol AF type epoxy resin);" YL 7800 "(fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corp .;" jER 1010 "manufactured by Mitsubishi Chemical Corp. (solid bisphenol A type epoxy resin);" jER 1031S manufactured by Mitsubishi Chemical Corp. " (Tetraphenylethane type epoxy resin) etc. are mentioned. These may be used alone or in combination of two or more.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (A), their mass ratio (liquid epoxy resin: solid epoxy resin) is 1: 0.01 to 1:20 in mass ratio A range is preferred. By setting the ratio of the liquid epoxy resin to the solid epoxy resin in this range, i) adequate tackiness is provided, ii) sufficient flexibility is obtained, and the handleability is improved, and iii The effect is obtained that a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of the above i) to iii), the mass ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.05 to 1:15 by mass ratio Is more preferable, and the range of 1: 0.1 to 1:10 is more preferable.

The content of the component (A) in the resin composition is preferably 1 mass when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. % Or more, more preferably 5% by mass or more, further preferably 10% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less.
In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass unless otherwise specified.

  The epoxy equivalent of the component (A) is preferably 50 to 5,000, more preferably 50 to 3,000, still more preferably 80 to 2,000, and still more preferably 110 to 1,000. By being in this range, the crosslink density of the cured product is sufficient, and an insulating layer with a small surface roughness can be provided. In addition, an epoxy equivalent can be measured according to JISK7236, and is a mass of resin containing an epoxy group of 1 equivalent.

  The weight average molecular weight of the component (A) is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. Here, the weight average molecular weight of an epoxy resin is a weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) method.

<(B) Active ester compound>
The resin composition contains (B) an active ester compound as the (B) component. The use of an active ester compound usually results in poor smear removability. However, since the resin composition of the present invention contains (C) an inorganic filler described later, high insulation performance can be achieved even if roughening treatment is performed under more severe conditions than usual. Therefore, since roughening treatment can be performed under more severe conditions than usual, high laser processability can be achieved.

  As an active ester compound, it has a function to cure the (A) epoxy resin, and in general, the reaction activity of phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. Compounds having two or more high ester groups in one molecule are preferably used. The active ester compound is preferably obtained by the 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 compound obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester compound 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, Benzenetriol, dicyclopentadiene type diphenol compounds, phenol novolac and the like can be mentioned. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensation of two molecules of phenol with one molecule of dicyclopentadiene.

  Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of a phenol novolac, an active ester compound containing a benzoylated compound of a phenol novolac, Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" represents a bivalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

  As a commercial item of an active ester compound, as an active ester compound containing a dicyclopentadiene type diphenol structure, "EXB9451", "EXB 9460", "EXB 9460S", "HPC-8000-65T", "HPC-8000H-65TM" “EXB-8000L-65TM” (manufactured by DIC), “EXB-8150-60T” as an active ester compound containing a naphthalene structure, “EXB9416-70BK” (manufactured by DIC), an active ester containing an acetylated product of phenol novolac “DC 808” (Mitsubishi Chemical Co., Ltd.) as a compound, “YLH1026” (Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylated phenol novolak, and an active ester compound as an acetylated phenol novolac "DC 808" (Mitsubishi Chemical Co., Ltd.), an active ester-based curing agent which is a benzyl novolak of phenol novolak "YLH1026" (Mitsubishi Chemical Co., Ltd.), "YLH 1030" (Mitsubishi Chemical Co., Ltd.), And the like.

  The quantitative ratio of (A) epoxy resin to (B) active ester compound is 1: 0.01 to 1 in the ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of active ester compound]. The range of 1: 5 is preferable, 1: 0.05 to 1: 2 is more preferable, and 1: 0.1 to 1: 1 is more preferable. Here, the reactive group of the active ester compound is an active ester group. Further, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the mass of solid content of each epoxy resin by the epoxy equivalent and totaling for all the epoxy resins, and the total number of reactive groups of the active ester compound The value obtained by dividing the solid content mass of each active ester compound by the reactive group equivalent is the total value of all active ester compounds. By setting the ratio of the epoxy resin to the active ester compound in such a range, the heat resistance of the cured product of the resin composition is further improved.

  The content of the active ester compound (B) is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. . The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less. By setting the content of the component (B) in such a range, it is possible to obtain a cured product excellent in smear removability.

<(C) Inorganic filler>
The resin composition contains (C) an inorganic filler as the (C) component. Usually, the (C) inorganic filler is contained in the form of particles in the resin composition. The average particle diameter of the (C) inorganic filler is 0.01 μm or more, preferably 0.05 μm or more, and more preferably 0.1 μm or more, 0.3 or more. The upper limit is 5 μm or less, preferably 3 μm or less, more preferably 1 μm or less, or 0.5 μm or less. (C) When the average particle size of the inorganic filler is less than or equal to the upper limit, insulation reliability can be improved even if the insulating layer is thin. Moreover, by being more than a lower limit, the fillability of the (C) inorganic filler in a resin composition increases more, and the desired effect of this invention can be acquired notably.

  (C) The average particle size of the particles of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of particles is created on a volume basis by a laser diffraction scattering type particle size distribution measuring device, and the average particle size can be measured as a median diameter from the particle size distribution. As the measurement sample, one in which particles are dispersed in a solvent such as water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, “LA-500” manufactured by Horiba, Ltd., “SALD-2200” manufactured by Shimadzu Corporation, etc. can be used.

  The coefficient of variation of the particle size distribution of the (C) inorganic filler is 30% or less, preferably 20% or less, more preferably 10% or less, and still more preferably 5% or less. The lower limit is not particularly limited, but may be 0% or more. The coefficient of variation of the particle size distribution is preferably as close to 0% as possible. By setting the coefficient of variation of the particle size distribution of the (C) inorganic filler within such a range, the particle size distribution of the (C) inorganic filler becomes sharp. For this reason, even if the roughening treatment is performed under more severe conditions than usual (C), even if the inorganic filler is desorbed, desorption marks on the roughened surface become uniform, and even if the insulating layer is a thin film, desorption is performed. Depending on the size of the mark, penetration of the roughened surface of the insulating layer and the opposite surface can be suppressed. As a result, the insulation reliability can be improved even if the insulation layer is thin. The particle size distribution is a volume based particle size distribution.

  (C) The variation coefficient of the particle size distribution of the particles of the inorganic filler can be determined by multiplying the standard deviation of the average particle diameter by the arithmetic mean of the average particle diameter by 100 (%). The standard deviation is preferably 0.0001 or more, more preferably 0.001 or more, still more preferably 0.01 or more, preferably 0.5 or less, more preferably 0.1 or less, more preferably It is 0.05 or less. The arithmetic mean is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, preferably 5 or less, more preferably 3 or less, still more preferably 1 or less. It is. By making the standard deviation and the arithmetic mean within such ranges, the coefficient of variation can be made within a predetermined range.

The resin composition was heat-cured at 200 ° C. for 90 minutes, and any 10 locations on the surface of the cured product were selected, and a cross-sectional image perpendicular to the surface of the cured product at that location was 100 μm wide and 5 μm deep arbitrarily selected. Consider the case of observing the range of In this case, the maximum particle size of the (C) inorganic filler is R1 (μm), and the average particle size of the (C) inorganic filler is R2 (μm). At this time, the maximum particle diameter R1 and the average particle diameter R2 preferably satisfy the relationship of the following equation (1), more preferably satisfy the relationship of the following equation (2), and the relationship of the following equation (3) It is further preferable to satisfy. By satisfying the relationship between the maximum particle diameter R1 and the average particle diameter R2, the roughening treatment is carried out under more severe conditions than usual, and even if the (C) inorganic filler is detached, detachment of the roughened surface is caused. As the marks become smaller, the insulation reliability can be improved even if the insulation layer is thin. The above cross-sectional image can be observed, for example, using a FIB-SIM composite device, and the maximum particle size R1 and the average particle size R2 can be measured from the image.
R1 <1.4 × R2 (1)
R1 <1.3 × R2 (2)
R1 <1.2 × R2 (3)

  The resin composition was heat-cured at 200 ° C. for 90 minutes, and any 10 locations on the surface of the cured product were selected, and a cross-sectional image perpendicular to the surface of the cured product at that location was 100 μm wide and 5 μm deep arbitrarily selected. Consider the case of observing the range of In this case, the average particle diameter of the (C) inorganic filler is R2 (μm). At this time, it is preferable that the number of particles having a particle diameter of (1.2 × R 2) μm or more be small. The specific number is preferably 4 or less, more preferably 3 or less, and still more preferably 2 or less, or 1 or less. When the number of (C) inorganic fillers having a particle diameter of 1.2 times or more of the average particle diameter of (C) inorganic fillers observed within a predetermined range is within such a range, roughening treatment is performed. Even if the (C) inorganic filler is desorbed under more severe conditions than usual, desorption of the roughened surface is reduced. As a result, the insulation reliability can be improved even if the insulating layer is thin. The above cross-sectional image can be observed, for example, using an FIB-SIM composite device, and the number of particles having an average particle diameter R2 and a particle diameter of (1.2 × R2) μm or more can be measured from the image. .

  (C) An inorganic compound is used as a material of an inorganic filler. (C) As the inorganic filler material, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide And zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferable from the viewpoint of significantly achieving the desired effects of the present invention. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Moreover, spherical silica is preferable as silica. The (C) inorganic filler may be used singly or in combination of two or more at an arbitrary ratio.

  Examples of the (C) inorganic filler as described above include “Sea Hoster KE-S10”, “Sea Hoster KE-S20”, “Sea Hoster KE-S30”, “Sea Hoster KE-S 50”, “KE-S 50”, manufactured by Nippon Shokuhin Co., Ltd. P30 ";" SP60-05 "and" SP507-05 "manufactured by Nippon Steel & Sumikin Materials Co., Ltd .;" YC100C "," YA050C "," YA050C-MJE "and" YA010C "manufactured by Admatex Co., Ltd .; UFP-30 ";" Sylfil NSS-3N "," Sylfil NSS-4N "," Sylfil NSS-5N "manufactured by Tokuyama Corp .;" SC2500SQ "," SO-C4 "," SO-C2 "manufactured by Admatechs Co., Ltd. , "SO-C1"; and the like.

  (C) The inorganic filler can be adjusted, for example, by classification to be within the range of the variation coefficient of the predetermined particle diameter distribution and within the range of the predetermined average particle diameter.

  The (C) inorganic filler is preferably surface-treated with a suitable surface treatment agent. The surface treatment can improve the moisture resistance and the dispersibility of the (C) inorganic filler. As a surface treatment agent, for example, a fluorine-containing silane coupling agent, an aminosilane based coupling agent, an epoxysilane based coupling agent, a mercaptosilane based coupling agent, a silane based coupling agent, an alkoxysilane compound, an organosilazane compound, a titanate The coupling agent etc. are mentioned.

  As a commercial item of the surface treatment agent, for example, “KBM 22” (dimethyl dimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM 403” (3-glycidoxypropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Shin-Etsu Chemical Co., Ltd. "KBM 803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical "KBE 903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM 573" (N-phenyl-3-aminopropyltrimethoxy) Silane), Shin-Etsu Chemical "KBM5783" (N-phenyl-3-aminooctyl trimethoxysilane), Shin-Etsu Chemical "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical "KBM 103" (Phenyltrimethoxysilane), Shin-Etsu Chemical "KBM-4803" ( Chain epoxy type silane coupling agent), and the like. Among them, a nitrogen atom-containing silane coupling agent is preferable, an aminosilane-based coupling agent containing a phenyl group is more preferable, and N-phenyl-3-aminoalkyltrimethoxysilane is more preferable. Moreover, a surface treatment agent may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

The extent of surface treatment with a surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (C) inorganic filler. Carbon content per unit surface area of the inorganic filler (C), (C) from the viewpoint of the dispersibility of the inorganic filler improved, preferably 0.02 mg / ^{m 2} or more, more preferably 0.1 mg / ^{m 2} or more, Particularly preferably, it is 0.2 mg / m ² or more. On the other hand, the amount of carbon is preferably 1 mg / m ² or less, more preferably 0.8 mg / m ² or less, particularly preferably from the viewpoint of suppressing the melt viscosity of the resin composition and the increase in the melt viscosity in sheet form. Is less than 0.5 mg / m ² .

  The amount of carbon per unit surface area of the inorganic filler (C) is obtained by washing the inorganic filler (D) after the surface treatment with a solvent (for example, methyl ethyl ketone (hereinafter sometimes abbreviated as “MEK”)). , Can measure. Specifically, sufficient amount of methyl ethyl ketone and (C) inorganic filler surface-treated with a surface treatment agent are mixed, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. Then, after removing a supernatant liquid and making solid content dry, the carbon quantity per unit surface area of the (C) inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

  The amount of the (C) inorganic filler in the resin composition is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass, with respect to 100% by mass of non-volatile components in the resin composition. It is the above, Preferably it is 80 mass% or less, More preferably, it is 75 mass% or less, More preferably, it is 70 mass% or less. (C) When the amount of the inorganic filler is in the above range, the thin film insulation can be improved. Furthermore, according to the present invention, even when the thin film contains a large amount of inorganic filler, it is possible to improve the insulation reliability.

<(D) Hardening agent>
The resin composition may contain (D) a curing agent as an optional component. However, the (B) active ester compound is not included in the (D) curing agent. The curing agent (D) is not particularly limited as long as it has a function of curing the epoxy resin (A), and examples thereof include phenol-based curing agents, naphthol-based curing agents, benzoxazine-based curing agents, and cyanate ester-based curing agents. Curing agents, carbodiimide type curing agents and the like can be mentioned. Among them, from the viewpoint of improving insulation reliability, the (D) curing agent is preferably any one or more of a phenol-based curing agent, a naphthol-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent. It is more preferable to include a phenolic curing agent. 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 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.

  Specific examples of the phenol-based curing agent and naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7851” manufactured by Meiwa Kasei Co., “NHN” manufactured by Nippon Kayaku Co., Ltd. "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. And “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500” and the like manufactured by DIC Corporation.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Highpolymer Co., Ltd. and “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 resin derived from tetrazole novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (phenol novolac-type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), "BA230" manufactured by Lonza Japan Co., Ltd. And “BA 230 S 75” (a prepolymer in which part or all of bisphenol A dicyanate is triazinated to form a trimer), and the like.

  Specific examples of the carbodiimide type curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

  When the resin composition contains (D) a curing agent, the amount ratio of epoxy resin to (D) curing agent is [total number of epoxy groups of epoxy resin]: [total number of reactive groups of curing agent] The ratio of 1: 0.01 to 1: 2 is preferable, 1: 0.01 to 1: 1 is more preferable, and 1: 0.05 to 1: 0.5 is more preferable. Here, the reactive group of the curing agent is an active hydroxyl 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 cured product of the resin composition is further improved.

  When the resin composition contains (B) an active ester compound and (D) a curing agent, the quantitative ratio of the epoxy resin to the (B) active ester compound and (D) curing agent is [the total of epoxy groups of epoxy resin The ratio of [number of total of reactive groups of (B) and (D) components] is preferably in the range of 1: 0.01 to 1: 5, and more preferably 1: 0.01 to 1: 3. More preferred is 1: 0.01 to 1: 1.5. By setting the ratio of the epoxy resin to the component (B) and the component (D) in such a range, the heat resistance of the cured product of the resin composition is further improved.

  When the resin composition contains (D) a curing agent, the content of the (D) curing agent is preferably 0.1% by mass or more, more preferably 100% by mass of the non-volatile component in the resin composition. Preferably it is 0.5 mass% or more, More preferably, it is 1 mass% or more. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 8% by mass or less. By setting the content of the curing agent (D) in such a range, the heat resistance of the cured product of the resin composition is further improved.

<(E) Hardening accelerator>
The resin composition may contain (E) a curing accelerator as an optional component. By using a curing accelerator, curing can be promoted when curing the resin composition.

  Examples of the curing accelerator (E) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators are more preferable. The curing accelerator may be used alone or in combination of two or more.

  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. Among them, triphenyl phosphine and tetrabutyl phosphonium decanoate are preferable.

  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, 4-pyrrolidinopyridine etc. are mentioned. Among them, 4-dimethylaminopyridine, 1,8-diazabicyclo (5,4,0) -undecene and 4-pyrrolidinopyridine are preferable.

  Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 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-one Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-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-methyl-3-benzylimidazolium chloride, 2-methylimidazoline 2-phenylimidazole compounds of imidazoline and the like and an imidazole compound and adduct of the epoxy resin. Among them, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

  A commercial item may be used as an imidazole series hardening accelerator, for example, "P200-H50" by Mitsubishi Chemical Co., Ltd .; "2E4MZ" by Shikoku Kasei Co., Ltd .; etc. are mentioned.

  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. Among them, dicyandiamide and 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferable.

  Examples of the metal-based curing accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, zinc (II) acetylacetonate Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, organic manganese complexes such as manganese (II) acetylacetonate, and the like. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

  When the resin composition contains (E) a curing accelerator, the amount of the (E) curing accelerator is preferably 100% by mass of the resin component of the resin composition from the viewpoint of obtaining the desired effect of the present invention. The content is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, preferably 3% by mass or less, more preferably 1% by mass or less, further preferably 0 .5 mass% or less.

<(F) Thermoplastic resin>
The resin composition may contain (F) a thermoplastic resin as an optional component. (F) As a thermoplastic resin, for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamide imide resin, polyether imide resin, poly sulfone resin, polyether sulfone resin, polyphenylene ether resin, polycarbonate resin And polyether ether ketone resins, polyester resins and the like, and phenoxy resins are preferable. The thermoplastic resin may be used alone or in combination of two or more.

  (F) The polystyrene equivalent weight average molecular weight of the thermoplastic resin is preferably 30000 or more, more preferably 35000 or more, and still more preferably 40000 or more. The upper limit is preferably 100,000 or less, more preferably 70000 or less, and still more preferably 60000 or less. (F) 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 (F) thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L manufactured by Showa Denko KK as a column. The column temperature can be measured at 40 ° C. using chloroform or the like as the mobile phase, and / K-804L can be 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. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include “1256” and “4250” (all of which are bisphenol A skeleton-containing phenoxy resins), “YX 8100” (bisphenol S skeleton-containing phenoxy resin), and “YX 6954” (bisphenol acetophenone) manufactured by Mitsubishi Chemical Corporation. Other examples include “FX280” and “FX293” manufactured by Nippon Steel Sumikin Chemical Co., Ltd., “YL7500BH30” manufactured by Mitsubishi Chemical Corporation, “YX6954BH30”, “YX7553”, “YX7553BH30”, and “YL7769BH30”. “YL6794”, “YL7213”, “YL7290”, “YL7482” and the like.

  As polyvinyl acetal resin, polyvinyl formal resin, polyvinyl butyral resin is mentioned, for example, Polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, "electric charge butyral 4000-2", "electric charge butyral 5000-A", "electric charge butyral 6000-C" and "electric charge butyral 6000-EP" manufactured by Denki Kagaku Kogyo K.K. S-LEC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, BM series and the like manufactured by Chemical Industry Co., Ltd. may be mentioned.

  As a specific example of a polyimide resin, "Rika coat SN20" and "Rika coat PN20" by Shin Nippon Rika Co., Ltd. are mentioned. Specific examples of the polyimide resin also include a linear polyimide (polyimide described in JP-A-2006-37083) obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride, and a polysiloxane skeleton Modified polyimides such as contained polyimides (polyimides described in JP-A-2002-12667 and JP-A-2000-319386) can be mentioned.

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

  As a specific example of polyether sulfone resin, Sumitomo Chemical Co., Ltd. "PES5003P" etc. are mentioned. As a specific example of polyphenylene ether resin, oligo phenylene ether styrene resin "OPE-2St 1200" made by Mitsubishi Gas Chemical Co., Ltd., etc. may be mentioned.

  Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

  Among them, as the (F) thermoplastic resin, phenoxy resin and polyvinyl acetal resin are preferable. Thus, in a preferred embodiment, the thermoplastic resin comprises one or more selected from the group consisting of phenoxy resin and polyvinyl acetal resin. Among them, as the thermoplastic resin, a phenoxy resin is preferable, and a phenoxy resin having a weight average molecular weight of 30,000 or more is particularly preferable.

  When the resin composition contains (F) a thermoplastic resin, the amount of the (F) thermoplastic resin is 100% by mass of non-volatile components in the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. When it carries out, Preferably it is 0.1 mass% or more, More preferably, it is 0.5 mass% or more, More preferably, it is 1 mass% or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.

<(G) Flame retardant>
The resin composition may contain (G) a flame retardant as an optional component. Examples of the flame retardant (G) include phosphazene compounds, organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides and the like, with phosphazene compounds being preferred. The flame retardant may be used alone or in combination of two or more.

  The phosphazene compound is a cyclic compound having nitrogen and phosphorus as constituent elements, and the phosphazene compound is preferably a phosphazene compound having a phenolic hydroxyl group. Specific examples of phosphazene compounds include, for example, “SPH-100”, “SPS-100”, “SPB-100”, “SPE-100” manufactured by Otsuka Chemical Co., Ltd., “FP-100” manufactured by Fushimi Pharmaceutical Co., Ltd., "FP-110", "FP-300", "FP-400" etc. are mentioned.

  As a flame retardant other than a phosphazene compound, you may use a commercial item, for example, "HCA-HQ" by Sanko-sha, "PX-200" by Daihachi Chemical Industry Co., Ltd., etc. are mentioned. As the flame retardant, those which are difficult to hydrolyze are preferable. For example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphophenanthrene-10-oxide is preferable.

  When the resin composition contains (G) a flame retardant, the amount of the (G) flame retardant is 100% by mass of the nonvolatile component in the resin composition from the viewpoint of obtaining the desired effect of the present invention remarkably. Preferably it is 0.1 mass% or more, More preferably, it is 0.5 mass% or more, More preferably, it is 1 mass% or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.

<(H) Optional additive>
The resin composition may further contain optional additives as optional components in addition to the components described above. Examples of such additives include organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds; thickeners; antifoaming agents; leveling agents; adhesion imparting agents; resin additives such as colorants Can be mentioned. One of these additives may be used alone, or two or more thereof may be used in combination in an arbitrary ratio.

<Physical Properties of Resin Composition, Applications>
Since the hardened | cured material of the resin composition mentioned above can perform a roughening process on severe conditions, it shows the characteristic of being excellent in smear removability. Therefore, this cured product is also excellent in laser processability. Therefore, by using the resin composition of the present invention, an insulating layer excellent in laser processability can be obtained. For example, an insulating layer is formed using the above-described resin composition, and a roughening treatment is performed after a via hole is formed using a laser. In this case, the maximum smear length from the wall surface of the bottom of the via hole can be usually less than 3 μm.

Moreover, according to the resin composition mentioned above, since it is excellent in insulation performance, even if thickness of hardened | cured material is thin, the characteristic that resistance value is high can be shown. Therefore, by using the resin composition of the present invention, a thin film insulating layer having a high resistance value can be obtained. For example, the resistance value of the board | substrate E for insulating evaluation is measured by the method as described in an Example using the resin composition mentioned above. In this case, the obtained resistance value can usually be made 1 × 10 ⁷ Ω or more.

  Moreover, the hardened | cured material surface after the roughening process of the resin composition mentioned above can show the characteristic that arithmetic mean roughness (Ra) is low. Therefore, by using the resin composition of the present invention, an insulating layer with a low arithmetic mean roughness can be obtained even when wet desmear treatment is performed. For example, measurement of arithmetic mean roughness (Ra) of the roughening board | substrate D is performed by the method as described in an Example using the resin composition mentioned above. In this case, the arithmetic mean roughness obtained is usually 150 nm or less, preferably 130 nm or less, more preferably 100 nm or less. The lower limit of the arithmetic mean roughness is not particularly limited, and may be 1 nm or more.

  Moreover, the hardened | cured material surface after the roughening process of the resin composition mentioned above can show the characteristic that the maximum height roughness (Rz) is low, since a detachment | desorption mark becomes uniform. Therefore, by using the resin composition of the present invention, it is possible to provide an insulating layer having a low maximum height roughness even when wet desmear treatment is performed. For example, using the resin composition described above, the measurement of the maximum height roughness (Rz) of the roughened substrate D is performed by the method described in the examples. In this case, the maximum height roughness to be obtained is usually 1000 nm or less, preferably 500 nm or less, more preferably 400 nm or less. The lower limit of the maximum height roughness is not particularly limited, and may be 1 nm or more.

  Moreover, the hardened | cured material of the resin composition mentioned above can show the characteristic that elongation at break is high. Therefore, by using the resin composition of the present invention, an insulating layer having a high elongation at break can usually be provided. For example, the elongation at break of the cured product B for evaluation is measured by the method described in the examples using the above-described resin composition. In this case, the elongation at break obtained is usually 1.5% or more, preferably 2.0% or more, more preferably 2.5% or more. The upper limit is not particularly limited, and may be 10% or less.

  Moreover, since the resin composition mentioned above is excellent in insulation performance, even if the thickness of a hardened | cured material is thin, it brings about the insulating layer which can form a fine wiring circuit. Therefore, the resin composition of the present invention is suitably used as a resin composition for forming a circuit having a small ratio (L / S) of the circuit width (L (μm)) to the width between circuits (S (μm)). It can be used. The above ratio (L / S) is usually 10 μm / 10 μm or less (20 μm pitch or less), preferably 5 μm / 5 μm or less (10 μm pitch or less), more preferably 2 μm / 2 μm (4 μm pitch or less) or less.

  The insulating layer can be formed by the cured product of the above-mentioned resin composition by utilizing the advantages described above. Therefore, the resin composition of the present invention is a resin composition for forming a circuit having a ratio (L / S) of circuit width (L (μm)) to width between circuits (S (μm)) of 10 μm / 10 μm or less It can be suitably used as a resin composition and can be suitably used as a resin composition for forming an insulating layer having a surface having an arithmetic mean roughness (Ra) of 150 nm or less, and via formation by laser irradiation Can be suitably used as a resin composition (resin composition for forming a via by laser irradiation of a printed wiring board). In addition, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for insulating layer of the printed wiring board), and between the layers of the printed wiring board It can be used more suitably as a resin composition (resin composition for interlayer insulation layers of a printed wiring board) for forming an insulation layer. Further, the resin composition of the present invention can be suitably used even when the printed wiring board is a component-embedded circuit board because the resin composition of the present invention provides a good insulating layer for the component embedding property.

[Resin sheet]
The resin sheet of the present invention has a support and a resin composition layer provided on the support. The resin composition layer is a layer containing the resin composition of the present invention, and is usually formed of a resin composition. According to the resin composition described above, since the insulation performance is excellent even if the thickness of the cured product is thin, it is possible to reduce the thickness of the resin composition layer.

  The thickness of the resin composition layer is preferably 15 μm or less, more preferably 13 μm or less, and still more preferably from the viewpoint of thinning the printed wiring board and providing a cured product having excellent insulation properties even if it is a thin film. 10 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may usually be 1 μm or more, 2 μm or more, or the like.

  As a preferred embodiment of the resin composition layer, from the viewpoint of improving the thin film insulation as the resin composition layer, when the resin composition contains 100% by mass of nonvolatile components in the resin composition, (C ) Select any 10 locations on the surface of the cured product containing 50% by mass or more of the inorganic filler and heat curing the resin composition at 200 ° C for 90 minutes, and of the cross-sectional images perpendicular to the surface of the cured material at that location When the range of 100 μm in width and 5 μm in depth selected is observed, the maximum particle size of (C) inorganic filler is R1 (μm), and the average particle size of (C) inorganic filler is R2 (μm) When the above equation is satisfied, the relationship of the above equation (1) is satisfied. The details of the relationship between the above R1 and the above R2 are as described above.

  As another preferable embodiment of the resin composition layer, as the resin composition layer, from the viewpoint of improving thin film insulation, when the resin composition contains 100% by mass of nonvolatile components in the resin composition, C) Select 10 arbitrary locations on the surface of the cured product containing 50% by mass or more of the inorganic filler and heat curing the resin composition at 200 ° C. for 90 minutes, and cross sectional images perpendicular to the surface of the cured material at that location Among them, when the range of 100 μm width and 5 μm depth selected arbitrarily is observed, the average particle diameter of the (C) inorganic filler is R 2 (μm), the particle diameter is (1.2 × R 2) μm The number of particles above is four or less. The details of the number and the like are as described above.

  Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter abbreviated as "PEN"). Polycarbonates (hereinafter sometimes abbreviated as "PC"); Acrylic polymers such as polymethyl methacrylate (hereinafter sometimes abbreviated as "PMMA"); Cyclic polyolefins; Triacetylcellulose (below) They may be abbreviated as "TAC"); polyether sulfide (hereinafter sometimes abbreviated as "PES"); polyether ketone; polyimide; and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When using metal foil as a support body, copper foil, aluminum foil, etc. are mentioned as metal foil, for example. Among them, copper foil is preferred. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) You may use.

  The surface of the support to be bonded to the resin composition layer may be subjected to treatments such as mat treatment, corona treatment, antistatic treatment and the like.

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. As the release agent used for the release layer of the support with release layer, for example, one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin can be mentioned. . As a commercial item of a mold release agent, "SK-1", "AL-5", "AL-7" etc. which are alkyd resin type mold release agents and are made by Lintec Corporation are mentioned, for example. Further, examples of the release layer-provided support include “Lumirror T60” manufactured by Toray Industries, Inc .; “Purex” manufactured by Teijin Limited; “UniPeel” manufactured by Unitika; and the like.

  The thickness of the support is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when using the 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 resin sheet can be produced, for example, by applying the resin composition onto a support using a coating apparatus such as a die coater. In addition, if necessary, the resin composition may be dissolved in an organic solvent to prepare a resin varnish, and the resin varnish may be applied to manufacture a resin sheet. By using a solvent, the viscosity can be adjusted to improve the coatability. When a resin varnish is used, the resin varnish is generally dried after application to form a resin composition layer.

  Organic solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitol such as cellosolve and butyl carbitol Solvents; Aromatic hydrocarbon solvents such as toluene and xylene; Amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone; and the like. The organic solvents may be used alone or in combination of two or more at any ratio.

  Drying may be carried out by known methods such as heating and hot air blowing. The drying conditions are such that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it changes also with the boiling points of the organic solvent in a resin varnish, when using the resin varnish containing 30 mass%-60 mass% organic solvent, for example, resin composition by making it dry at 50 degreeC-150 degreeC for 3 minutes-10 minutes Object layer can be formed.

  The resin sheet may optionally contain any layer other than the support and the resin composition layer. For example, in the resin sheet, a protective film conforming to the support may be provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can prevent adhesion of dust and the like to the surface of the resin composition layer and scratches. When the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. Also, the resin sheet can be wound and stored in a roll shape.

[Printed wiring board]
The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention, a first conductor layer, and a second conductor layer. The insulating layer is provided between the first conductor layer and the second conductor layer, and insulates the first conductor layer from the second conductor layer (the conductor layer is referred to as a wiring layer). is there).

  The insulating layer is formed of a cured product of the resin composition of the present invention. The thickness of the insulating layer between the first and second conductor layers is preferably 15 μm or less, more preferably 13 μm or less, and still more preferably 10 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more. The distance between the first conductor layer and the second conductor layer (the thickness of the insulating layer between the first and second conductor layers) is the main surface of the first conductor layer 1 as shown in an example in FIG. The thickness t1 of the insulating layer 3 between the main surface 21 of the second conductor layer 2 and the second conductive layer 11 is referred to. The first and second conductor layers are conductor layers adjacent to each other via the insulating layer, and the main surface 11 and the main surface 21 face each other.

  The total thickness t2 of the insulating layer is preferably 15 μm or less, more preferably 13 μm or less, and still more preferably 10 μm or less. The lower limit is not particularly limited, but may usually be 1 μm or more, 1.5 μm or more, 2 μm or more.

The printed wiring board can be manufactured by a method including the following steps (I) and (II) using the above-mentioned resin sheet.
(I) Step of laminating the resin composition layer of the resin sheet so as to bond with the inner layer substrate on the inner layer substrate (II) Step of thermally curing the resin composition layer to form an insulating layer

  The "inner layer substrate" used in step (I) is a member to be a substrate of a printed wiring board, and for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate Etc. The substrate may have a conductor layer on one side or both sides, and the conductor layer may be patterned. The inner layer substrate in which a conductor layer (circuit) is formed on one side or both sides of the substrate may be referred to as "inner layer circuit board". Further, an intermediate product to which an insulating layer and / or a conductor layer is to be further formed in the production of a printed wiring board is also included in the “inner layer substrate” in the present invention. When the printed wiring board is a component built-in circuit board, an inner layer substrate containing components can be used.

  The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet from the support side to the inner layer substrate. Examples of the member (hereinafter, also referred to as “heat-pressing member”) for heat-pressing the resin sheet to the inner layer substrate include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). In addition, it is preferable to press via an elastic material such as heat resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the inner layer substrate, instead of directly pressing the heat pressure-bonding member on the resin sheet.

  The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0 The heat compression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure conditions of a pressure of 26.7 hPa or less.

  Lamination can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressure type laminator manufactured by Nikkiso Co., Ltd., a vacuum applicator manufactured by Nikko Materials, a batch type vacuum pressure laminator, etc. may be mentioned.

  After lamination, the laminated resin sheet may be subjected to a smoothing treatment by normal pressure (atmospheric pressure), for example, by pressing the heat pressure-bonding member from the support side. The pressing conditions for the smoothing treatment can be the same as the heating and pressing conditions for the above-mentioned lamination. The smoothing treatment can be performed by a commercially available laminator. In addition, you may perform lamination | stacking and smoothing processing continuously using said commercially available vacuum laminator.

  The support may be removed between step (I) and step (II) and may be removed after step (II).

  In the step (II), the resin composition layer is thermally cured to form an insulating layer.

  The heat curing conditions of the resin composition layer are not particularly limited, and conditions generally employed for forming an insulating layer of a printed wiring board may be used.

  For example, the heat curing conditions of the resin composition layer vary depending on the type of the resin composition and the like, but the curing temperature is preferably 120 ° C. to 240 ° C., more preferably 150 ° C. to 220 ° C., further preferably 170 ° C. to 200 ° C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 90 minutes.

  Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to heat curing of the resin composition layer, the resin composition layer is heated at a temperature of 50.degree. C. or more and less than 120.degree. C. (preferably 60.degree. C. or more and 115.degree. C. or less, more preferably 70.degree. C. or more and 110.degree. C. or less). It may be preheated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes).

  When producing a printed wiring board, the steps of: (III) drilling holes in the insulating layer; (IV) roughening the insulating layer; and (V) forming the conductor layer may be further performed. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used for producing a printed wiring board. When the support is removed after the step (II), the removal of the support may be performed between the step (II) and the step (III), between the step (III) and the step (IV), or It may be carried out between IV) and step (V). In addition, if necessary, the formation of the insulating layer and the conductor layer in the steps (II) to (V) may be repeated to form a multilayer wiring board. In this case, the thickness of the insulating layer between the conductor layers (t1 in FIG. 1) is preferably in the above range.

  The step (III) is a step of forming holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (III) may be carried out using, for example, a drill, a laser, a plasma or the like depending on the composition of the resin composition used for forming the insulating layer. Since the insulating layer is formed of the cured product of the resin composition of the present invention, it has excellent laser processability. Thus, step (III) is preferably carried out using a laser. The size and shape of the holes may be appropriately determined according to the design of the printed wiring board. The specific diameter of the holes is, for example, preferably 70 μm or less, more preferably 50 μm or less, and still more preferably 20 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more.

  Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment should be set in such a range that the smear generated in the step (III) can be removed and (C) penetration of the insulating layer due to unintended detachment of the inorganic filler can be suppressed. Is preferred. The specific procedures and conditions can adopt known procedures and conditions generally used in forming an insulating layer of a printed wiring board. In addition, since the insulating layer is formed of a cured product of a resin composition containing (B) an active ester compound and (C) an inorganic filler, roughening treatment can be performed using a stronger chemical solution than usual. .

  For the roughening treatment of the insulating layer, for example, swelling treatment with a swelling solution, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution can be performed in this order. The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution, a surfactant solution and the like, preferably an alkaline solution, and examples of the alkaline solution include sodium hydroxide solution and potassium hydroxide solution. preferable. As a swelling liquid marketed, "Swelling dip security G" and "Swelling dip security SBU" by Atotech Japan Ltd., 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 an insulating layer in the swelling liquid of 30 degreeC-90 degreeC for 1 minute-20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer for 5 minutes to 15 minutes in a swelling liquid at 40 ° C to 80 ° C. The oxidizing agent used for the roughening treatment is not particularly limited, and examples thereof include alkaline permanganic acid solutions in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer 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 CP" and "Dosing Solution Security P" manufactured by Atotech Japan Co., Ltd. Moreover, as a neutralization liquid used for roughening treatment, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Security G" manufactured by Atotech Japan Co., Ltd. may be mentioned. The treatment with the neutralization solution can be carried out by immersing the treated surface roughened with the oxidizing agent in the neutralization solution at 30 ° C. to 80 ° C. for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing the target subjected to the roughening treatment with the oxidizing agent in a neutralization solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  Step (V) is a step of forming a conductor layer. When the conductor layer is not formed on the inner layer substrate, the step (V) is a step of forming the first conductor layer. When the conductor layer is formed on the inner layer substrate, the conductor layer is the first conductor layer. Step (V) is a step of forming a second conductor layer.

  The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. 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, palladium, silver or copper single metal layer, nickel-chromium alloy, copper, from the viewpoint of versatility of conductor layer formation, cost, easiness of patterning, etc. An alloy layer of nickel alloy, copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy is more preferable, single copper Metal layers are 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 insulating layer 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 generally 3 μm to 35 μm, preferably 5 μm to 30 μm, depending on the desired printed wiring board design.

  In one embodiment, the conductor layer may be formed by plating. For example, the conductor layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method, and from the viewpoint of manufacturing simplicity, semi-additive It is preferable to form by a method. Hereinafter, the example which forms a conductor layer by a semiadditive method is shown.

  First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, on the formed plating seed layer, a mask pattern is formed to expose a part of the plating seed layer corresponding to the desired wiring pattern. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

  The resin sheet of the present invention can also be suitably used when the printed wiring board is a component-embedded circuit board because the resin sheet of the present invention also provides an insulating layer having good component embedding properties. The component built-in circuit board can be manufactured by a known manufacturing method.

  The printed wiring board manufactured using the resin sheet of the present invention is an aspect provided with an insulating layer which is a cured product of the resin composition layer of the resin sheet, and an embedded wiring layer embedded in the insulating layer, It is also good.

[Semiconductor device]
The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

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

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) at a conductive portion of a printed wiring board. The "conductive location" is a "location for transmitting an electrical signal in a printed wiring board", and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The mounting method of the semiconductor chip at the time of manufacturing the semiconductor device is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, a bumpless buildup layer The mounting method by (BBUL), the mounting method by an anisotropic conductive film (ACF), the mounting method by a nonconductive film (NCF), etc. are mentioned. Here, "the mounting method using a bumpless build-up layer (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board to connect the semiconductor chip and the wiring on the printed wiring board". It is.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass" unless otherwise specified. Moreover, the operation described below was performed in an environment of normal temperature and normal pressure unless otherwise specified.

<Measurement of average particle size of inorganic filler, coefficient of variation>
The measurement of the average particle diameter R2 of the inorganic filler and the coefficient of variation was performed by the method described above.

Example 1 Preparation of Resin Composition 1
10 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation “828US”, epoxy equivalent weight about 180), 20 parts of biphenyl type epoxy resin (Mitsubishi Chemical Co. “YX4000H”, epoxy weight equivalent about 190), bisphenol AF type epoxy resin ( 10 parts of Mitsubishi Chemical's "YL 7760", epoxy equivalent weight of 238, 3 parts of phosphazene resin ("OSP Chemical""SPS-100"), phenoxy resin (Mitsubishi Chemical's "YX7553BH30", MEK having a solid content of 30% by mass And 10 parts of a 1: 1 solution of cyclohexanone were heated and dissolved in 60 parts of MEK with stirring.

  After cooling to room temperature, 40 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC, an active group equivalent of about 223, a toluene solution with a solid content of 65% by mass), and a phenolic curing agent ("LA" manufactured by DIC) -3018-50P ", active group equivalent weight about 151, 50 parts solid content in 50% 2-methoxypropanol solution 16 parts, curing accelerator (4-dimethylaminopyridine (DMAP), solid content 5% by weight MEK solution) 6 parts Spherical silica particles surface-treated with an amine-based silane coupling agent ("KBM 573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("Sea Hoster KE-S20" manufactured by Nippon Shokubai Co., Ltd.) After mixing 170 parts of a diameter of 0.2 μm and uniformly dispersing with a high-speed rotary mixer, a cartridge filter ("SHP020" manufactured by ROKITECHNO) Filtered to prepare a resin composition 1.

Example 2 Preparation of Resin Composition 2
In Example 1, 6 parts of a curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass) and a curing accelerator (4-pyrrolidinopyridine (PPY), a solid content of 5% by mass It changed into 6 parts of 1-methoxy 2-propanol solutions. A resin composition 2 was produced in the same manner as in Example 1 except for the matters described above.

Example 3 Preparation of Resin Composition 3
In Example 1, spherical silica particles surface-treated with an amine-based silane coupling agent ("KBM 573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("Sea Hoster KE-S20" manufactured by Nippon Shokuhin Co., Ltd.) Spherical silica particles (Shifester KE-S30 manufactured by Nippon Shokubai Co., Ltd.), 170% of which have an average particle diameter of 0.2 μm and surface-treated with an amine-based silane coupling agent (“KBM 573” manufactured by Shin-Etsu Chemical Co., Ltd.) The variation coefficient of the diameter distribution was changed to 3.1 parts (average particle diameter 0.3 μm) and 170 parts. A resin composition 3 was produced in the same manner as in Example 1 except for the matters described above.

Example 4 Preparation of Resin Composition 4
In Example 3, 40 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC, an active group equivalent weight of about 223, a toluene solution with a solid content of 65% by mass) is added to an active ester compound ("EXB9416-70BK" manufactured by DIC) , The active group equivalent was changed to about 37 parts of about 274, and the solid content of 70 mass% MIBK (methyl isobutyl ketone) solution. A resin composition 4 was produced in the same manner as in Example 3 except for the matters described above.

Example 5 Preparation of Resin Composition 5
In Example 3, 10 parts of a carbodiimide-based curing agent (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution having an active group equivalent weight of about 216 and a solid content of 50% by mass) was added. A resin composition 5 was produced in the same manner as in Example 3 except for the matters described above.

Comparative Example 1: Preparation of Comparative Resin Composition 1
In Example 1,
1) 40 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC, an active group equivalent weight of about 223, a toluene solution having a solid content of 65% by mass) and a naphthol-based curing agent ("SN" manufactured by Nippon Steel Sumikin Chemical Co., Ltd.) Change to -485 ", active group equivalent weight about 215) 7.2 parts,
2) 16 parts of a phenol-based curing agent ("LA-3018-50P" manufactured by DIC, an active group equivalent weight of about 151, a 50% solids content 2-methoxypropanol solution) was added to a phenol-based curing agent ("LA-" manufactured by DIC) 7054 ", active group equivalent of about 124, changed to 12 parts of MEK solution of 60% solids,
3) Spherical silica particles surface-treated with an amine-based silane coupling agent ("KBM 573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("Sea Hoster KE-S20" manufactured by Nippon Shokubai Co., Ltd.) The particle size of 0.2 μm) was changed to 110 parts.
Comparative resin composition 1 was produced in the same manner as in Example 1 except for the matters described above.

Comparative Example 2: Preparation of Comparative Resin Composition 2
In Comparative Example 1, spherical silica particles ("Si Hoster KE-S20" manufactured by Nippon Shokuhin Co., Ltd.) surface-treated with an amine-based silane coupling agent ("KBM 573" manufactured by Shin-Etsu Chemical Co., Ltd.) Spherical silica particles (Shifester KE-S30 manufactured by Nippon Shokubai Co., Ltd.), 110% of which have an average particle diameter of 0.2 μm and surface-treated with an amine silane coupling agent (“KBM 573” manufactured by Shin-Etsu Chemical Co., Ltd.) The variation coefficient of the diameter distribution was changed to 3.1 parts (average particle diameter 0.3 μm) 110 parts. A resin composition 2 for comparison was produced in the same manner as in Comparative Example 1 except for the above matters.

Comparative Example 3: Preparation of Comparative Resin Composition 3
In Example 1, spherical silica particles surface-treated with an amine-based silane coupling agent ("KBM 573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("Sea Hoster KE-S20" manufactured by Nippon Shokuhin Co., Ltd.) Spherical particles (“SO-C1” manufactured by Admatechs Co., Ltd.) having a surface treated with 170% of an average particle diameter of 0.2 μm and an amine-based silane coupling agent (“KBM 573” manufactured by Shin-Etsu Chemical Co., Ltd.) Coefficient of variation 41%, average particle diameter 0.3 .mu.m, and 170 parts). Comparative resin composition 3 was produced in the same manner as in Example 1 except for the matters described above.

<Production of Resin Sheet A>
A PET film (“Lumirror R80” manufactured by Toray Industries, Inc., “Lumirror R80” manufactured by Toray Industries, Inc., 38 μm in thickness, 130 ° C. softening point, hereinafter “releasing PET”) as a support. I have prepared).

  Each resin composition is uniformly coated on release PET with a die coater so that the thickness of the resin composition layer after drying is 6 μm, and dried at 80 ° C. for 1 minute, on release PET. A resin composition layer was obtained. Next, on the surface of the resin composition layer not bonded to the support, a rough surface of a polypropylene film ("Alfan MA-411" manufactured by Oji F-TEX, thickness 15 μm) is bonded to the resin composition layer as a protective film. Stacked to do. Thereby, resin sheet A which consists of mold release PET (support body), a resin composition layer, and a protective film in order was obtained.

<Measurement of elongation at break>
The protective film of the produced resin sheet A was peeled off, and the resin composition layer was thermally cured by heating at 200 ° C. for 90 minutes, and then the support was peeled off. The obtained cured product is referred to as "cured product for evaluation B". The cured product B for evaluation was subjected to a tensile test by a TENSILON universal testing machine ("RTC-1250A" manufactured by ORIENTEC Co., Ltd.) in accordance with Japanese Industrial Standard (JIS K7127) to measure the elongation at break.

<Measurement of particle size of inorganic filler in cross section of hardened material>
Of the cross-sectional image perpendicular to the surface of the cured product B for evaluation, the cross-sectional observation was performed using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nano Technology Co., Ltd.) in an arbitrarily selected width of 100 μm and a depth of 5 μm. . In each FIB-SEM image, the maximum particle size R1 (μm) of the inorganic filler in the range of 100 μm in width and 5 μm in depth, and the number of particles having a particle size of (1.2 × R2) μm or more were measured. The particle size was calculated by plotting two points of the diameter and calculating using the above-mentioned apparatus. This operation was performed at 10 randomly selected places, and the average value of each was shown in the table.

<Evaluation of Arithmetic Average Roughness (Ra), Maximum Height Roughness (Rz), Thickness of Insulating Layer, and Insulating Property>
(1) Base treatment of inner layer circuit board Glass cloth base epoxy resin both sides having a circuit conductor (copper) formed with a wiring pattern of L / S (line / space) = 2 μm / 2 μm as an inner layer circuit board on both sides A copper-clad laminate (copper foil thickness 3 μm, substrate thickness 0.15 mm, “HL 832 NSF LCA” manufactured by Mitsubishi Gas Chemical Co., Ltd., 255 × 340 mm size) was prepared. Both surfaces of the inner layer circuit board were subjected to organic coating treatment of the copper surface with a surface treatment solution ("FlatBOND-FT" manufactured by MEC Co., Ltd.).

(2) Lamination of resin sheet Peel off the protective film from each of the prepared resin sheets A, and use a batch type vacuum pressure laminator (Nikko Materials Co., Ltd., 2-stage buildup laminator, CVP 700) to obtain a resin composition layer. It laminated on both sides of an inner layer circuit board so that an inner layer circuit board might be touched. The lamination was performed by reducing the pressure for 30 seconds to make the air pressure 13 hPa or less, and pressure bonding at 130 ° C. and a pressure of 0.74 MPa for 45 seconds. Next, heat pressing was performed at 120 ° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Thermosetting of resin composition layer The inner layer circuit board on which the resin sheet is laminated is placed in an oven at 100 ° C. for 30 minutes, then transferred to an oven at 180 ° C. for 30 minutes and thermally cured for 30 minutes. An insulating layer of 5 μm was formed. This is a substrate C.

(4) Step of Roughening Treatment The release PET of the substrate C was peeled off, and the insulating layer was subjected to desmearing treatment as roughening treatment. In addition, as a desmear process, the following wet desmear process was implemented.

Wet desmear treatment:
Swelling solution ("Swelling dip Security Gent P" manufactured by Atotech Japan Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C for 5 minutes, then an oxidant solution ("Concentrate Compact CP" manufactured by Atotech Japan Ltd.) Finally, the solution is neutralized with an aqueous solution of potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4% at 80 ° C for 20 minutes. Finally, the neutralization solution ("Reduction Solution Securityg P" manufactured by Atotech Japan, sulfuric acid aqueous solution) After immersion at 40 ° C. for 5 minutes, it was dried at 80 ° C. for 15 minutes. This is referred to as a roughened substrate D.

(5) Step of Forming Conductor Layer (5-1) Electroless Plating Step In order to form a conductor layer on the surface of the insulating layer of the roughened substrate D, a plating step including the following steps 1 to 6 (Atotech Japan Co., Ltd. The conductor layer was formed by performing a copper plating step) using a chemical solution manufactured by the manufacturer.

1. Alkali cleaning (cleaning and charge control of the surface of the insulating layer provided with via holes)
The surface of the roughened substrate D was washed at 60 ° C. for 5 minutes using a Cleaning Cleaner Securiganth 902 (trade name).
2. Soft etching (cleaning in the via hole)
The surface of the roughened substrate D was treated with a sulfuric acid-acid aqueous sodium peroxodisulfate solution at 30 ° C. for 1 minute.
3. Pre-dip (adjustment of the charge on the surface of the insulating layer for Pd application)
The surface of the roughened substrate D is pre. It processed at room temperature for 1 minute using Dip Neoganth B (brand name).
4. Activator application (Pd application to the surface of the insulating layer)
The surface of the roughened substrate D was treated at 35 ° C. for 5 minutes using Activator Neoganth 834 (trade name).
5. Reduction (reduction of Pd applied to the insulating layer)
The surface of the roughened substrate D was treated with Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. It processed at 30 degreeC for 5 minutes using the liquid mixture with (brand name).
6. Electroless copper plating process (Cu is deposited on the surface of the insulating layer (Pd surface))
The surface of the roughened substrate D is a mixture of Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name) The solution was treated at 35 ° C. for 20 minutes. The thickness of the formed electroless copper plating layer was 0.8 μm.

(5-2) Electrolytic plating process Then, the electrolytic copper plating process was performed on the conditions with which copper is filled in a via hole using the chemical | medical solution made from Atotech Japan company. Thereafter, using a land pattern of 1 mm in diameter conducted to the via hole and a circular conductor pattern of 10 mm in diameter not connected to the lower layer conductor as a resist pattern for patterning by etching, a thickness of 10 μm on the surface of the insulating layer To form a conductor layer having lands and conductor patterns. Next, annealing was performed at 200 ° C. for 90 minutes. This substrate is referred to as “insulation evaluation substrate E”.

(6) Measurement of Arithmetic Average Roughness (Ra) and Maximum Height Roughness (Rz) The roughened substrate D was subjected to a VSI contact mode, using a non-contact surface roughness meter (WYKO NT3300 manufactured by Becoin Instruments), The Ra value and Rz value were determined by numerical values obtained with a 50 × lens as a measurement range of 121 μm × 92 μm. Each was measured by calculating the average of 10 randomly selected points.

(7) Measurement of Thickness of Insulating Layer Between Conductor Layers The cross-sectional observation of the insulating property evaluation substrate E was performed using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nano Technology Inc.). In detail, the cross section in the direction perpendicular to the surface of the conductor layer was scraped with FIB (focused ion beam), and the insulating layer thickness between the conductor layers was measured from the cross-sectional SEM image. For each sample, five cross-sectional SEM images randomly selected were observed, and the average value was taken as the thickness (μm) of the insulating layer between the conductor layers, and the results are shown in the following table.

(8) Evaluation of Insulation Reliability (Insulating Property) of Insulating Layer The circular conductor side of 10 mm in diameter of the substrate E for evaluating insulation obtained as described above is used as a positive electrode and connected to a land of 1 mm in diameter. Using a highly accelerated life test device ("PM 422" manufactured by ETAC) with the grid conductor (copper) side as the-electrode, 200 hours elapsed under the conditions of 130 ° C, 85% relative humidity, 3.3 V DC voltage application The insulation resistance value at that time was measured by an electrochemical migration tester ("ECM-100" manufactured by J-RAS). This measurement is performed six times, and in all six test pieces, when the resistance value is 10 ⁷ Ω or more is "○", and even if it is less than 10 ⁷ Ω, "X", and the evaluation result and the insulation resistance The values are shown in the following table. The insulation resistance value described in the following table is the lowest value of the insulation resistance values of the six test pieces.

<Preparation of substrate for laser processability evaluation>
(1) Via hole formation For the substrate C, using a CO ₂ laser beam machine (YB-HCS03T04) manufactured by Matsushita Welding Systems Co., Ltd., the insulating layer is drilled at a frequency of 2000 Hz and a pulse width of 8 μs and a condition of 3 shots. A via hole having a top diameter (diameter) of the via hole on the surface of the insulating layer of 25 μm and a diameter of the bottom of the via hole at the bottom of the insulating layer of 20 μm was formed.

(2) Step of Roughening Treatment The mold release PET was peeled off, and the insulating layer was subjected to desmearing treatment as roughening treatment. In addition, as a desmear process, the following wet desmear process was implemented.

Wet desmear treatment:
Swelling solution ("Swelling dip Security Gent P" manufactured by Atotech Japan Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C for 5 minutes, then an oxidant solution ("Concentrate Compact CP" manufactured by Atotech Japan Ltd.) Finally, the solution is neutralized with an aqueous solution of potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4% at 80 ° C for 20 minutes. Finally, the neutralization solution ("Reduction Solution Securityg P" manufactured by Atotech Japan, sulfuric acid aqueous solution) After immersion at 40 ° C. for 5 minutes, it was dried at 80 ° C. for 15 minutes.

<Evaluation of laser processability>
The periphery of the bottom of the via hole was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall of the bottom of the via hole was measured from the obtained image. The case where the maximum smear length was less than 3 μm was regarded as “o”, and the case where the maximum smear length was 3 μm or more was evaluated as “x”.

  In Examples 1 to 5, even when the components (D) to (G) are not contained, it is confirmed that the results are similar to those of the above-described examples although there is a difference in degree.

Claims (15)

A resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler,
The resin composition wherein the component (C) has a coefficient of variation in particle size distribution of 30% or less and an average particle size of 0.01 μm or more and 5 μm or less.   The resin composition according to claim 1, wherein the content of the component (C) is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass.   The resin composition of Claim 1 or 2 whose average particle diameter of (C) component is 0.1 micrometer or more and 3 micrometers or less.   The resin composition according to any one of claims 1 to 3, which is for forming an insulating layer of a printed wiring board.   5. The circuit according to any one of claims 1 to 4, wherein the ratio (L / S) of the circuit width (L (μm)) to the width between circuits (S (μm)) is 10 μm / 10 μm or less. The resin composition as described.   The resin composition according to any one of claims 1 to 5, which is a resin composition for forming an insulating layer having a surface having an arithmetic average roughness (Ra) of 150 nm or less.   The resin composition according to any one of claims 1 to 6, which is a resin composition for forming a via by laser irradiation. The resin composition was heat-cured at 200 ° C. for 90 minutes, and any 10 locations on the surface of the cured product were selected, and a cross-sectional image perpendicular to the surface of the cured product at that location was 100 μm wide and 5 μm deep arbitrarily selected. When observing the range of
When the maximum particle size of the component (C) is R1 (μm) and the average particle size of the component (C) is R2 (μm),
The resin composition of any one of Claims 1-7 satisfy | filled the relationship of R1 <1.4 * R2. The resin composition was heat-cured at 200 ° C. for 90 minutes, and any ten locations on the surface of the cured product were selected, and a cross-sectional image perpendicular to the surface of the cured material at that location was 100 μm wide and 5 μm deep selected arbitrarily. When observing the range
When the average particle size of the component (C) is R2 (μm),
The resin composition according to any one of claims 1 to 8, wherein the number of particles having a particle size of (1.2 x R2) or more is 4 or less.   The resin sheet containing a support body and the resin composition layer containing the resin composition of any one of Claims 1-9 provided on this support body.   The resin sheet according to claim 10, wherein the thickness of the resin composition layer is 15 μm or less. A support, and a resin composition layer provided on the support and containing (C) a resin composition containing an inorganic filler,
The resin composition contains (C) 50% by mass or more of the inorganic filler, assuming that the nonvolatile component in the resin composition is 100% by mass,
The resin composition was heat-cured at 200 ° C. for 90 minutes, and any 10 locations on the surface of the cured product were selected, and a cross-sectional image perpendicular to the surface of the cured product at that location was 100 μm wide and 5 μm deep arbitrarily selected. When observing the range of
Assuming that the maximum particle size of the (C) inorganic filler is R1 (μm) and the average particle size of the (C) inorganic filler is R2 (μm),
Resin sheet which satisfies the relationship of R1 <1.4 × R2. A support, and a resin composition layer provided on the support and containing (C) a resin composition containing an inorganic filler,
The resin composition contains (C) 50% by mass or more of the inorganic filler, assuming that the nonvolatile component in the resin composition is 100% by mass,
The resin composition was heat-cured at 200 ° C. for 90 minutes, and any 10 locations on the surface of the cured product were selected, and a cross-sectional image perpendicular to the surface of the cured product at that location was 100 μm wide and 5 μm deep arbitrarily selected. When observing the range of
(C) When the average particle diameter of the inorganic filler is R2 (μm),
The resin sheet whose number of particles having a particle size of (1.2 × R 2) μm or more is 4 or less. A printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
The printed wiring board, wherein the insulating layer is a cured product of the resin composition according to any one of claims 1 to 9.   A semiconductor device comprising the printed wiring board according to claim 14.

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