JP6919508B2 - Resin composition - Google Patents

Description

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

As a manufacturing technique for printed wiring boards, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by thermosetting 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. Later, 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 suppressing the coefficient of thermal expansion of the formed insulating layer by increasing the content of an inorganic filler such as silica particles in the resin composition.

International Publication No. 2010/35451 Japanese Unexamined Patent Publication 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 this, there is a demand for thinning the insulating layer.

Patent Document 1 describes that the silica particles on the surface of the cured product are desorbed in the roughening treatment to realize an insulating layer exhibiting sufficient peel strength with respect to the conductor layer. However, as a result of diligent studies by the present inventor, a uniform low-roughness roughened surface cannot be obtained simply by desorbing the silica particles, and the desorption traces due to variations in the size of the desorption traces of the silica particles and the like. It was found that a roughened surface having a non-uniform size can be obtained. When the insulating layer is a thin film, it penetrates the roughened surface of the insulating layer and the surface on the opposite side depending on the size of the desorption trace, and one conductor layer and the other conductor layer pass through the desorption trace. Conducts with each other, making it difficult to maintain insulation performance. On the other hand, the present inventor has found that when a hydrophobic resin such as an active ester compound is contained in a resin composition, a roughened surface having a low roughness can be formed by performing a roughening treatment.

By the way, via holes may be formed in the insulating layer for interlayer connection. Via holes are generally formed by laser machining. Laser machining can cause smears, which are usually removed during the roughening process. However, hydrophobic resins such as active ester compounds have high resistance to chemicals for roughening treatment. Therefore, when an active ester compound is used, the removal of smear tends to be insufficient. Insufficient removal of smear may block the via hole with smear, resulting in poor interlayer connection and poor conduction reliability.

When the 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 may be improved in order to improve the smear removal property. It is conceivable to make the roughening treatment conditions more severe, such as increasing the value. However, it is difficult to maintain the insulating performance because the inorganic filler contained in the resin composition is easily desorbed under severe conditions and becomes a roughened surface having a large desorption trace as in Patent Document 1. In some cases.

As described above, when the active ester compound is used, the formation of via holes by laser processing tends to be insufficient under normal roughening treatment conditions. On the other hand, under severe roughening treatment conditions, via holes can be stably formed by laser processing, but unintended holes are formed in the insulating layer due to desorption of the inorganic filler, and the insulating performance tends to be lowered. Therefore, when an active ester compound is used, it is difficult to achieve both insulation performance and laser workability.

Here, the laser workability indicates the ease of forming a via hole by a treatment including laser irradiation and subsequent roughening treatment.

These problems are particularly difficult to solve because, especially when the insulating layer is thin, unintended pore formation due to desorption of the inorganic filler is likely to occur during the roughening treatment.

The present invention has been devised in view of the above problems, and is a resin composition capable of achieving both insulation performance and laser processability even when the insulating layer is a thin film; a resin containing the above resin composition. An object of the present invention is to provide a resin sheet having a composition layer; a printed wiring board including an insulating layer formed by a cured product of the resin composition; and a semiconductor device containing a cured product of the resin composition. do.

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

[1] A resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler.
The component (C) is a resin composition having a coefficient of variation of 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 non-volatile 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 used for forming an insulating layer of a printed wiring board.
[5] Of [1] to [4], for forming a circuit in which the ratio (L / S) of the circuit width (L (μm)) to the width (S (μm)) between circuits is 10 μm / 10 μm or less. The resin composition according to 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 mean 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 vias by laser irradiation.
[8] An arbitrary 10 points on the surface of the cured product obtained by thermosetting the resin composition at 200 ° C. for 90 minutes were selected, and among the cross-sectional images perpendicular to the surface of the cured product at those points, an arbitrarily selected width of 100 μm. 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 according to any one of [1] to [7], which satisfies the relationship of R1 <1.4 × R2.
[9] An arbitrary 10 points on the surface of the cured product obtained by thermosetting the resin composition at 200 ° C. for 90 minutes were selected, and among the cross-sectional images perpendicular to the surface of the cured product at those points, an arbitrarily selected width of 100 μm. When observing a range of 5 μm in depth,
When the average particle size of the component (C) is R2 (μm),
The resin composition according to any one of [1] to [8], wherein the number of particles having a particle size of (1.2 × R2) μm or more is 4 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 containing a resin composition containing (C) an inorganic filler provided on the support are provided.
The resin composition contains (C) an inorganic filler of 50% by mass or more when the non-volatile component in the resin composition is 100% by mass.
Arbitrary 10 points on the surface of the cured product obtained by thermosetting the resin composition at 200 ° C. for 90 minutes were selected, and among the cross-sectional images perpendicular to the surface of the cured product at those points, the width was 100 μm and the depth was 5 μm. When observing the range of
When (C) the maximum particle size of the inorganic filler is R1 (μm) and (C) the average particle size of the inorganic filler is R2 (μm).
A resin sheet that satisfies the relationship of R1 <1.4 × R2.
[13] A support and a resin composition layer containing a resin composition containing (C) an inorganic filler provided on the support are provided.
The resin composition contains (C) an inorganic filler of 50% by mass or more when the non-volatile component in the resin composition is 100% by mass.
Arbitrary 10 points on the surface of the cured product obtained by thermosetting the resin composition at 200 ° C. for 90 minutes were selected, and among the cross-sectional images perpendicular to the surface of the cured product at those points, the width was 100 μm and the depth was 5 μm. When observing the range of
(C) When the average particle size of the inorganic filler is R2 (μm)
A resin sheet having 4 or less particles having a particle size of (1.2 × R2) μm or more.
[14] 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 insulating layer is a printed wiring board which is a cured product of the resin composition according to any one of [1] to [9].
[15] A semiconductor device including 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; the above. It is possible to provide a printed wiring board including an insulating layer formed of a cured product of the resin composition; and a semiconductor device containing the cured product of the resin composition.

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 with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples listed below, and may be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope 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 size is 0.01 μm or more and 5 μm or less. By containing the above-mentioned (A) epoxy resin, (B) active ester compound, and (C) a predetermined inorganic filler in combination, both insulation performance and laser workability can be achieved 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, the desorption marks of the (C) inorganic filler on the roughened surface are uniform and small, and as a result, the insulating layer is formed. Even if it is thin, the insulation reliability can be improved. Therefore, the cured product of this resin composition can be preferably used as an insulating layer of a printed wiring board by taking advantage of its excellent properties.

Further, the resin composition may further contain an arbitrary component in combination with the components (A) to (C). Optional components include, for example, (D) curing agent, (E) curing accelerator, (F) thermoplastic resin, (G) flame retardant, and (H) other additives.

<(A) Epoxy resin>
The resin composition contains (A) epoxy resin as (A) component. Examples of the epoxy resin (A) include bixilenol 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, and trisphenol type. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , Cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane Examples thereof include a dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, and a tetraphenylethane type epoxy resin. Of these, bisphenol A type epoxy resin and biphenyl type epoxy resin are preferable. One type of epoxy resin may be used alone, or two or more types may be used in combination.

The epoxy resin (A) preferably has two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, the resin composition includes a liquid epoxy resin at a temperature of 20 ° C. (hereinafter, also referred to as “liquid epoxy resin”) and a solid epoxy resin at a temperature of 20 ° C. (hereinafter, also referred to as “solid epoxy resin”). It is preferable to include them in combination. As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable. As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable. The liquid epoxy resin and the solid epoxy resin are preferably aromatic epoxy resins.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, an aliphatic epoxy resin, and an epoxy resin having a butadiene structure are preferable, and an aliphatic epoxy resin and a bisphenol A type epoxy resin are preferable. , Bisphenol F type epoxy resin is more preferable.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, "828US", "jER828EL", "825", and "Epicoat" manufactured by Mitsubishi Chemical Co., Ltd. 828EL "(bisphenol A type epoxy resin)," jER807 "," 1750 "(bisphenol F type epoxy resin)," jER152 "(phenol novolac type epoxy resin)," 630 "," 630LSD "(glycidylamine type epoxy resin) , "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" manufactured by Nagase Chemtex Co., Ltd. (glycidyl ester type epoxy resin), manufactured by Daicel Co., Ltd. "Ceroxide 2021P" (alicyclic epoxy resin with an ester skeleton), "PB-3600" (epoxy resin with a butadiene structure), "ZX1658", "ZX1658GS" (liquid 1,4-glycidyl) manufactured by Nippon Steel & Sumitomo Metal Corporation. Cyclohexane type epoxy resin), Mitsubishi Chemical's "630LSD" (glycidylamine type epoxy resin), DIC's "EXA-850CRP" (bisphenol A type epoxy resin), Mitsubishi Chemical's "YED-216D" ( (Adipose epoxy resin)," EP-3950S "," EP-3980S "manufactured by ADEKA (glycidylamine type epoxy resin);" ELM-100H "manufactured by Sumitomo Chemical Co., Ltd. (glycidylamine type epoxy resin) and the like. .. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the solid epoxy resin include bixilenol 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, and biphenyl. Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and bixilenol type epoxy resin, naphthalene type epoxy resin, bisphenol AF Type epoxy resin and naphthylene 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" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; DIC. "N-690" (cresol novolac type epoxy resin); DIC "N-695" (cresol novolac type epoxy resin); DIC "HP-7200" (dicyclopentadiene type epoxy resin); "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (HP6000) manufactured by DIC. Naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayaku Co., Ltd .; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; "ESN485" (naphthol novolac) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX8800" (anthracene type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd .; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YL7800" manufactured by Mitsubishi Chemical Co., Ltd. (Fluorene type epoxy resin); "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. and the like can be mentioned. These may be used individually by 1 type, or may be used in combination of 2 or more types.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (A), their quantity ratio (liquid epoxy resin: solid epoxy resin) is 1: 0.01 to 1:20 in terms of mass ratio. The range is preferred. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin in such a range, i) moderate adhesiveness is provided, ii) sufficient flexibility is obtained, handleability is improved, and iii. ) Effects such as being able to obtain a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the quantitative ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.05 to 1:15 in terms of mass ratio. Is more preferable, and the range of 1: 0.1 to 1:10 is even more preferable.

The content of the component (A) in the resin composition is preferably 1% by mass when the non-volatile 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, still more preferably 10% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is 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 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. Within this range, the crosslink density of the cured product becomes sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.

The weight average molecular weight of the component (A) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

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

The active ester compound has a function of curing the (A) epoxy resin, and generally has a reaction activity of phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds and the like. A compound having two or more ester groups having a high ester group in one molecule is preferably used. The active ester compound is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester 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, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenol, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable. Of these, 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 divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Commercially available products of the active ester compound include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H-65TM" as active ester compounds containing a dicyclopentadiene type diphenol structure. , "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. "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as a compound, "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylated product of phenol novolac, and "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound which is an acetylated product of phenol novolac. (Manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.), etc. ..

The amount ratio of (A) epoxy resin to (B) active ester compound is the ratio of [total number of epoxy groups in epoxy resin]: [total number of reactive groups in active ester compound], from 1: 0.01 to The range of 1: 5 is preferable, 1: 0.05 to 1: 2 is more preferable, and 1: 0.1 to 1: 1 is even more preferable. Here, the reactive group of the active ester compound is an active ester group. The total number of epoxy groups in the epoxy resin is the total number of all epoxy resins obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, and is the total number of reactive groups in the active ester compound. , The value obtained by dividing the solid content mass of each active ester compound by the reaction group equivalent is the total value for all the active ester compounds. By setting the amount ratio of the epoxy resin and the active ester compound within 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, still more preferably 5% by mass or more, when the non-volatile component in the resin composition is 100% by mass. .. 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) within such a range, it is possible to obtain a cured product having excellent smear removing property.

<(C) Inorganic filler>
The resin composition contains (C) an inorganic filler as a component (C). Usually, the (C) inorganic filler is contained in the resin composition in the form of particles. The average particle size of the inorganic filler (C) is 0.01 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, and 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 not more than this upper limit, the insulation reliability can be improved even if the insulating layer is thin. Further, when it is at least the lower limit, the filling property of the (C) inorganic filler in the resin composition is further enhanced, and the desired effect of the present invention can be remarkably obtained.

(C) The average particle size of the particles of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, a laser diffraction / scattering type particle size distribution measuring device can be used to create a particle size distribution of particles on a volume basis, and the average particle size can be measured as a median diameter from the particle size distribution. As the measurement sample, those in which the 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, or the like can be used.

In the inorganic filler, the coefficient of variation of the particle size distribution is 30% or less, preferably 20% or less, more preferably 10% or less, 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. Therefore, even if the roughening treatment is performed under more severe conditions than usual (C) and the inorganic filler is desorbed, the desorption trace of the roughened surface becomes uniform, and even if the insulating layer is a thin film, desorption is performed. Depending on the size of the trace, it is possible to prevent the roughened surface of the insulating layer and the surface on the opposite side from penetrating. As a result, the insulation reliability can be improved even if the insulating layer is thin. The particle size distribution is a volume-based particle size distribution.

(C) The coefficient of variation of the particle size distribution of the particles of the inorganic filler can be obtained by dividing the standard deviation of the average particle size by the arithmetic mean of the average particle size and multiplying 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, still 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. Is. By keeping the standard deviation and the arithmetic mean within such a range, the coefficient of variation can be within a predetermined range.

Arbitrary 10 points on the surface of the cured product obtained by thermosetting the resin composition at 200 ° C. for 90 minutes were selected, and among the cross-sectional images perpendicular to the surface of the cured product at those points, the width was 100 μm and the depth was 5 μm. 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 size R1 and the average particle size R2 preferably satisfy the relationship of the following formula (1), more preferably satisfy the relationship of the following formula (2), and the relationship of the following formula (3). It is even more preferable to meet. By satisfying such a relationship between the maximum particle size R1 and the average particle size R2, even if the roughening treatment is performed under more severe conditions than usual (C) and the inorganic filler is desorbed, the roughened surface is desorbed. The traces are reduced, and as a result, insulation reliability can be improved even if the insulating layer is thin. The above cross-sectional image can be observed using, for example, 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 x R2 (1)
R1 <1.3 x R2 (2)
R1 <1.2 x R2 (3)

Arbitrary 10 points on the surface of the cured product obtained by thermosetting the resin composition at 200 ° C. for 90 minutes were selected, and among the cross-sectional images perpendicular to the surface of the cured product at those points, the width was 100 μm and the depth was 5 μm. Consider the case of observing the range of. In this case, the average particle size of the (C) inorganic filler is R2 (μm). At this time, it is preferable that the number of particles having a particle size of (1.2 × R2) μm or more is small. The specific number is preferably 4 or less, more preferably 3 or less, and further preferably 2 or less and 1 or less. When the number of (C) inorganic fillers having a particle size 1.2 times or more the average particle size of the (C) inorganic filler observed within a predetermined range is within such a range, the roughening treatment is performed. Even if (C) the inorganic filler is desorbed under more severe conditions than usual, the desorption trace of the roughened surface becomes small, and as a result, the insulation reliability can be improved even if the insulating layer is thin. The above cross-sectional image can be observed using, for example, a FIB-SIM composite device, and the number of particles having an average particle size R2 and a particle size of (1.2 × R2) μm or more can be measured from the image. ..

(C) An inorganic compound is used as the material of the inorganic filler. Examples of the material of the inorganic filler (C) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and 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 , Zirconium oxide, barium titanate, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like. Among these, silica is particularly preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. (C) As the inorganic filler, one kind may be used alone, or two or more kinds may be used in combination 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-S50", and "KE-" manufactured by Nippon Shokubai Co., Ltd. "P30"; "SP60-05", "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatex Co., Ltd .; "YA010C" manufactured by Denka Co., Ltd. UFP-30 "; Tokuyama's" Silfil NSS-3N "," Sylfil NSS-4N "," Sylfil NSS-5N "; Admatex's" SC2500SQ "," SO-C4 "," SO-C2 " , "SO-C1"; and the like.

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

The inorganic filler (C) is preferably surface-treated with an appropriate surface treatment agent. By surface treatment, the moisture resistance and dispersibility of the (C) inorganic filler can be enhanced. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilane compounds, organosilazane compounds, and titanates. Examples include system coupling agents.

Commercially available surface treatment agents include, for example, "KBM22" (dimethyldimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "KBM5783" (N-phenyl-3-aminooctyllimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" manufactured by Shin-Etsu Chemical Co., Ltd. (Phenyltrimethoxysilane), "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type silane coupling agent) and the like can be mentioned. Of these, 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 even more preferable. In addition, one type of surface treatment agent may be used alone, or two or more types may be used in combination at an arbitrary ratio.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of (C) the 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, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, the amount of carbon is preferably 1 mg / m ² or less, more preferably 0.8 mg / m ² or less, particularly preferably. Is 0.5 mg / m ² or less.

The amount of carbon per unit surface area of the (C) inorganic filler is determined after the surface-treated (D) inorganic filler is washed with a solvent (for example, methyl ethyl ketone (hereinafter, may be abbreviated as “MEK”)). , Can be measured. Specifically, a sufficient amount of methyl ethyl ketone and the (C) inorganic filler surface-treated with a surface treatment agent are mixed and ultrasonically cleaned at 25 ° C. for 5 minutes. Then, after removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the (C) inorganic filler can be measured using a carbon analyzer. As the 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, based on 100% by mass of the non-volatile component in the resin composition. The above is preferably 80% by mass or less, more preferably 75% by mass or less, and further preferably 70% by mass or less. When the amount of the inorganic filler (C) is within the above range, the thin film insulating property can be improved. Further, according to the present invention, it is possible to improve the insulation reliability even when the thin film contains a large amount of inorganic filler.

<(D) Hardener>
The resin composition may contain (D) a curing agent as an arbitrary 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 is, for example, a phenol-based curing agent, a naphthol-based curing agent, a benzoxazine-based curing agent, and a cyanate ester-based curing agent. Examples thereof include a curing agent and a carbodiimide-based curing agent. 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 contain a phenolic curing agent. The curing agent may be used alone or in combination of two or more.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion 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 the naphthol-based curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN" manufactured by Nippon Kayaku Co., Ltd. "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395" manufactured by Nippon Steel & Sumitomo Metal Corporation , DIC Corporation "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" and the like.

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

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidene diphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Examples thereof include polyfunctional cyanate resins derived from novolak and cresol novolak, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), and "BA230" manufactured by Ronza Japan. , "BA230S75" (a prepolymer in which a part or all of bisphenol A disyanate is triazined to form a trimer) and the like.

Specific examples of the carbodiimide-based 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 the epoxy resin to the (D) curing agent is [total number of epoxy groups in the epoxy resin]: [total number of reactive groups in the curing agent]. The ratio is preferably in the range of 1: 0.01 to 1: 2, more preferably 1: 0.01 to 1: 1 and even more preferably 1: 0.05 to 1: 0.5. Here, the reactive group of the curing agent is an active hydroxyl group or the like, and differs depending on the type of the curing agent. The total number of epoxy groups in the epoxy resin is the total number of all epoxy resins obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, and the total number of reactive groups in the curing agent is The value obtained by dividing the solid content mass of each curing agent by the reaction group equivalent is the total value for all curing agents. By setting the amount ratio of the epoxy resin and the curing agent within such a range, the heat resistance of the cured product of the resin composition is further improved.

When the resin composition contains (B) active ester compound and (D) curing agent, the amount ratio of the epoxy resin to (B) active ester compound and (D) curing agent is [total of epoxy groups of epoxy resin. Number]: The ratio of [total number of reactive groups of the components (B) and (D)] is preferably in the range of 1: 0.01 to 1: 5, more preferably 1: 0.01 to 1: 3. It is more preferably 1: 0.01 to 1: 1.5. By setting the amount ratio of the epoxy resin to the component (B) and the component (D) within 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, and further, when the non-volatile component in the resin composition is 100% by mass. It is preferably 0.5% by mass or more, more preferably 1% by 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 keeping the content of the curing agent (D) within such a range, the heat resistance of the cured product of the resin composition is further improved.

<(E) Curing accelerator>
The resin composition may contain (E) a curing accelerator as an arbitrary component. By using a curing accelerator, curing can be accelerated when the resin composition is cured.

Examples of the (E) curing accelerator 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.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like. Of these, triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo. (5,4,5) -Undecene, 4-pyrrolidinopyridine and the like can be mentioned. Of these, 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-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 2-. Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl imidazolium trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 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-phenylimidazoline and other imidazole compounds, imidazole compounds and epoxy resins Adduct body can be mentioned. Of these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation; "2E4MZ" manufactured by Shikoku Kasei Co., Ltd., and the like.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and the like. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like can be mentioned. Of these, dicyandiamide and 1,5,7-triazabicyclo [4.4.0] deca-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 an organic cobalt complex such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, an organic copper complex such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples thereof include organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. 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 based on 100% by mass of the resin component of the resin composition from the viewpoint of significantly obtaining the desired effect of the present invention. It 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, still more preferably 0. It is 5.5% by mass or less.

<(F) Thermoplastic resin>
The resin composition may contain (F) a thermoplastic resin as an arbitrary component. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, and polycarbonate resin. , Polyether ether ketone resin, polyester resin and the like, and phenoxy resin is preferable. The thermoplastic resin may be used alone or in combination of two or more.

The polystyrene-equivalent weight average molecular weight of the (F) thermoplastic resin is preferably 30,000 or more, more preferably 35,000 or more, and further preferably 40,000 or more. The upper limit is preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 60,000 or less. (F) The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, (F) the polystyrene-equivalent weight average molecular weight of the thermoplastic resin was determined by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L manufactured by Showa Denko Co., Ltd. as a column. / K-804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as a mobile phase.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetphenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantan skeleton, and terpen. Examples thereof include a phenoxy resin having one or more skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an 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" (both bisphenol A skeleton-containing phenoxy resin), "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" (bisphenol acetophenone) manufactured by Mitsubishi Chemical Corporation. (Skeletal-containing phenoxy resin), and in addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Corporation, "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30" manufactured by Mitsubishi Chemical Co., Ltd. , "YL6794", "YL7213", "YL7290", "YL7482" and the like.

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "electric butyral 4000-2", "electric butyral 5000-A", "electric butyral 6000-C", "electric butyral 6000-EP", and Sekisui manufactured by Denki Kagaku Kogyo Co., Ltd. Examples thereof include Eslek BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Chemical Industries.

Specific examples of the polyimide resin include "Rikacoat SN20" and "Rikacoat PN20" manufactured by Shin Nihon Rika Co., Ltd. Specific examples of the polyimide resin include a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), and a polysiloxane skeleton. Examples thereof include modified polyimides such as contained polyimides (polyimides described in JP-A-2002-12667 and JP-A-2000-319386).

Specific examples of the polyamide-imide resin include "Vilomax HR11NN" and "Vilomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamide-imide resin include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Hitachi Chemical Industries, Ltd.

Specific examples of the polyether sulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of the polyphenylene ether resin include oligophenylene ether styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, Ltd.

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

Among them, as the (F) thermoplastic resin, a phenoxy resin and a polyvinyl acetal resin are preferable. Therefore, in a preferred embodiment, the thermoplastic resin comprises one or more selected from the group consisting of phenoxy resins and polyvinyl acetal resins. 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 the non-volatile component in the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. If so, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by 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 arbitrary component. Examples of the flame retardant (G) include phosphazene compounds, organophosphorus flame retardants, organonitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides and the like, and phosphazene compounds are preferable. The flame retardant may be used alone or in combination of two or more.

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

As the flame retardant other than the phosphazene compound, a commercially available product may be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd. and "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd. As the flame retardant, one that is hard to hydrolyze is preferable, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable.

When the resin composition contains (G) flame retardant, the amount of (G) flame retardant is 100% by mass when the non-volatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. It is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by 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) Arbitrary additive>
The resin composition may further contain an arbitrary additive as an arbitrary component in addition to the above-mentioned components. Examples of such additives include organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; thickeners; defoamers; 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 of these additives may be used in combination at any ratio.

<Physical characteristics and uses of resin composition>
Since the cured product of the above-mentioned resin composition can be roughened under severe conditions, it exhibits a characteristic of being excellent in smear removal property. Therefore, this cured product is also excellent in laser workability. Therefore, by using the resin composition of the present invention, an insulating layer having excellent laser processability can be obtained. For example, an insulating layer is formed using the above-mentioned resin composition, via holes are formed using a laser, and then roughening treatment is performed. In this case, the maximum smear length from the wall surface at the bottom of the via hole can usually be less than 3 μm.

Further, according to the resin composition described above, even if the thickness of the cured product is thin, the insulating performance is excellent, so that it is possible to exhibit the characteristic that the resistance value is high. Therefore, by using the resin composition of the present invention, an insulating layer of a thin film having a high resistance value can be obtained. For example, using the resin composition described above, the resistance value of the insulating property evaluation substrate E is measured by the method described in Examples. In this case, the resistance value obtained, usually 1 × be more than 10 ⁷ Omega.

Further, the surface of the cured product of the above-mentioned resin composition after the roughening treatment can exhibit the characteristic that the arithmetic mean roughness (Ra) is low. Therefore, by using the resin composition of the present invention, it is possible to provide an insulating layer having a low arithmetic mean roughness even if a wet desmear treatment is performed. For example, using the resin composition described above, the arithmetic mean roughness (Ra) of the roughened substrate D is measured by the method described in Examples. In this case, the obtained arithmetic mean roughness is usually 150 nm or less, preferably 130 nm or less, and 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.

Further, the surface of the cured product of the above-mentioned resin composition after the roughening treatment can exhibit a characteristic that the maximum height roughness (Rz) is low because the desorption traces become 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 if a wet desmear treatment is performed. For example, using the resin composition described above, the maximum height roughness (Rz) of the roughened substrate D is measured by the method described in Examples. In this case, the maximum height roughness obtained is usually 1000 nm or less, preferably 500 nm or less, and 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.

In addition, the cured product of the above-mentioned resin composition can exhibit a characteristic of high elongation at break point. Therefore, by using the resin composition of the present invention, it is usually possible to provide an insulating layer having a high elongation at break. For example, using the resin composition described above, the elongation at break point of the cured product B for evaluation is measured by the method described in Examples. In this case, the obtained break point elongation is usually 1.5% or more, preferably 2.0% or more, and more preferably 2.5% or more. The upper limit is not particularly limited and may be 10% or less.

Further, since the resin composition described above is excellent in insulating performance even if the thickness of the cured product is thin, it provides an insulating layer capable of forming a fine wiring circuit. Therefore, the resin composition of the present invention is suitable as a resin composition for forming a circuit in which the ratio (L / S) of the circuit width (L (μm)) to the width between circuits (S (μm)) is small. 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), and more preferably 2 μm / 2 μm (4 μm pitch or less) or less.

Taking advantage of the above-mentioned advantages, the insulating layer can be formed by the cured product of the resin composition. Therefore, the resin composition of the present invention has a resin composition for forming a circuit 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. It can be suitably used as a material, and can be suitably used as a resin composition for forming an insulating layer having a surface having an arithmetic average roughness (Ra) of 150 nm or less, and vias are formed by laser irradiation. It can be suitably used as a resin composition for forming vias by laser irradiation of a printed wiring board. Further, 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 an insulating layer of a printed wiring board), and can be suitably used between layers of the printed wiring board. It can be more preferably used as a resin composition for forming an insulating layer (resin composition for an interlayer insulating layer of a printed wiring board). Further, since the resin composition of the present invention provides an insulating layer having good component embedding property, it can be suitably used even when the printed wiring board is a component-embedded circuit board.

[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 the resin composition. According to the resin composition described above, the insulation performance is excellent even if the thickness of the cured product is thin, so that the thickness of the resin composition layer can be reduced.

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

As a preferred embodiment of the resin composition layer, as the resin composition layer, from the viewpoint of improving the thin film insulating property, when the non-volatile component in the resin composition is 100% by mass, the resin composition is (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 among the cross-sectional images perpendicular to the surface of the cured product at those locations. When observing a range of width 100 μm and depth 5 μm arbitrarily selected, (C) the maximum particle size of the inorganic filler is R1 (μm), and (C) the average particle size of the inorganic filler is R2 (μm). ), The relationship of the above equation (1) is satisfied. Details such as the relationship between the above R1 and the above R2 are as described above.

As another preferred embodiment of the resin composition layer, as the resin composition layer, from the viewpoint of improving the thin film insulating property, when the non-volatile component in the resin composition is 100% by mass, the resin composition is (1) 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 obtain a cross-sectional image perpendicular to the surface of the cured product at those locations. When observing a range of width 100 μm and depth 5 μm arbitrarily selected, the particle size is (1.2 × R2) μm when the average particle size of the (C) inorganic filler is R2 (μm). The number of the above particles is 4 or less. Details such as the number are as described above.

Examples of the support include a film made of a plastic material, a metal foil, and a paper pattern, 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, the plastic material may be, for example, polyethylene terephthalate (hereinafter, may be abbreviated as "PET") or polyethylene naphthalate (hereinafter, abbreviated as "PEN"). Polyethylene such as (.); Polyethylene (hereinafter sometimes abbreviated as "PC"); Acrylic polymer such as polymethylmethacrylate (hereinafter sometimes abbreviated as "PMMA"); Cyclic polyolefin; Triacetylcellulose (hereinafter referred to as "PMMA"). "TAC" may be abbreviated.); Polyether sulfide (hereinafter, may be abbreviated as "PES"); Polyether ketone; Polyethylene; and the like. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil. Of these, copper foil is preferable. 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.) may be used. You may use it.

The surface of the support to be joined to the resin composition layer may be subjected to a treatment such as a matte treatment, a corona treatment, or an antistatic treatment.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. Examples of commercially available release agents include "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, which are alkyd resin-based release agents. Examples of the support with a release layer include "Lumirror T60" manufactured by Toray Industries, Inc.; "Purex" manufactured by Teijin Ltd.; "Unipee" manufactured by Unitika Ltd., and the like.

The thickness of the support is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

The resin sheet can be produced, for example, by applying a resin composition onto a support using a coating device such as a die coater. Further, 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 produce a resin sheet. By using a solvent, the viscosity can be adjusted and the coatability can be improved. When a resin varnish is used, the resin varnish is usually dried after coating to form a resin composition layer.

Examples of the organic solvent include 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 solvent may be used alone or in combination of two or more at any ratio.

Drying may be carried out by a known method such as heating or blowing hot air. 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 depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition is obtained by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes. A material layer can be formed.

The resin sheet may include any layer other than the support and the resin composition layer, if necessary. For example, in the resin sheet, a protective film similar to the support may be provided on the surface of the resin composition layer that is 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 dust and the like from adhering 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. In addition, the resin sheet can be rolled up and stored.

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

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, 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 (thickness of the insulating layer between the first and second conductor layers) is the main surface of the first conductor layer 1 as shown by an example in FIG. It refers to the thickness t1 of the insulating layer 3 between the main surface 21 of the 11 and the second conductor layer 2. The first and second conductor layers are adjacent conductor layers via an insulating layer, and the main surface 11 and the main surface 21 face each other.

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

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

The "inner layer substrate" used in the step (I) is a member that becomes a substrate of a printed wiring board, and is, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. And so on. Further, the substrate may have a conductor layer on one side or both sides thereof, and the conductor layer may be patterned. An inner layer substrate in which a conductor layer (circuit) is formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board". Further, an intermediate product in which an insulating layer and / or a conductor layer should be formed when the printed wiring board is manufactured is also included in the "inner layer substrate" in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components can be used.

The inner layer substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. Examples of the member for heat-pressing the resin sheet to the inner layer substrate (hereinafter, also referred to as “heat-bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). It is preferable not to press the heat-bonded member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

The inner layer substrate and the resin sheet may be laminated by a vacuum laminating method. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa, and the heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions at a pressure of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurizing laminator manufactured by Meiki Co., Ltd., a vacuum applicator manufactured by Nikko Materials, and a batch type vacuum pressurizing laminator.

After laminating, the laminated resin sheet may be smoothed by pressing the heat-bonded member from the support side under normal pressure (under atmospheric pressure), for example. The press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination. The smoothing process can be performed by a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

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

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

The thermosetting conditions of the resin composition layer are not particularly limited, and the conditions usually adopted when forming the insulating layer of the printed wiring board may be used.

For example, the thermosetting conditions of the resin composition layer differ 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., and 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 even more preferably 15 minutes to 90 minutes.

Before the resin composition layer is thermoset, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is heated at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 115 ° C. or lower, more preferably 70 ° C. or higher and 110 ° C. or lower). Preheating may be performed 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).

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

The step (III) is a step of drilling 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 by 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 a cured product of the resin composition of the present invention, it is excellent in laser workability. Therefore, step (III) is preferably carried out using a laser. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board. The specific diameter of the hole is, for example, preferably 70 μm or less, more preferably 50 μm or less, 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 shall be set within a range in which the smear generated in the step (III) can be removed and (C) the penetration of the insulating layer due to the unintended detachment trace of the inorganic filler can be suppressed. Is preferable. As specific procedures and conditions, known procedures and conditions usually used when forming an insulating layer of a printed wiring board can be adopted. Further, since the insulating layer is formed of a cured product of the resin composition containing (B) the active ester compound and (C) the inorganic filler, the roughening treatment can be performed using a chemical solution stronger than usual. ..

The roughening treatment of the insulating layer can be carried out, for example, a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling solution used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, preferably an alkaline solution, and the alkaline solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. preferable. Examples of commercially available swelling liquids include "Swelling Dip Security SBU" and "Swelling Dip Security SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 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 in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan. The neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan. The treatment with the neutralizing solution can be performed by immersing the treated surface that has been roughened with an oxidizing agent in the neutralizing solution at 30 ° C. to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object roughened with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 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, and when the conductor layer is formed on the inner layer substrate, the conductor layer is the first conductor layer. The step (V) is a step of forming the 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 the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, etc.). A layer formed of a nickel alloy and a copper / titanium alloy) can be mentioned. Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper, etc. An alloy layer of a nickel alloy or a copper-titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single copper layer is preferable. A metal layer is more preferred.

The conductor layer may have a single-layer structure, a single metal layer made of different types of metals or alloys, or a multi-layer structure in which two or more alloy layers are laminated. When the conductor layer has a multi-layer 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 surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. It is preferably formed by the method. Hereinafter, an example of forming the conductor layer by the semi-additive method will be shown.

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

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

The printed wiring board manufactured by using the resin sheet of the present invention has an embodiment including 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. May be 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 by using the printed wiring board of the present invention.

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

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conduction point" is a "place for transmitting an electric signal in the printed wiring board", and the place may be a surface or an embedded place. Further, 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 in manufacturing a 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, and a bumpless build-up layer. Examples thereof include a mounting method using (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, the "mounting method using the bumpless build-up layer (BBUL)" means "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board". Is.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Further, the operations described below were performed in an environment of normal temperature and pressure unless otherwise specified.

<Measurement of average particle size and coefficient of variation of inorganic filler>
The average particle size R2 of the inorganic filler and the coefficient of variation were measured by the above method.

<Example 1: Preparation of resin composition 1>
10 parts of bisphenol A type epoxy resin (Mitsubishi Chemical "828US", epoxy equivalent about 180), 20 parts of biphenyl type epoxy resin (Mitsubishi Chemical "YX4000H", epoxy equivalent about 190), and bisphenol AF type epoxy resin ( Mitsubishi Chemical's "YL7760", epoxy equivalent about 238) 10 parts, phosphazene resin (Otsuka Chemical's "SPS-100") 3 parts, phenoxy resin (Mitsubishi Chemical's "YX7553BH30", solid content 30% by mass MEK And 10 parts of a 1: 1 solution of cyclohexanone) was 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, a toluene solution having an active group equivalent of about 223 and a solid content of 65% by mass), a phenolic curing agent ("LA" manufactured by DIC). -3018-50P ", active group equivalent about 151, solid content 50% 2-methoxypropanol solution) 16 parts, curing accelerator (4-dimethylaminopyridine (DMAP), solid content 5% by mass MEK solution) 6 parts , Spherical silica particles surface-treated with an amine-based silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (“Seahoster KE-S20” manufactured by Nippon Catalyst Co., Ltd., particle size distribution variation coefficient 5.0%, average grain 170 parts (diameter 0.2 μm) were mixed, uniformly dispersed with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP020” manufactured by ROKICHNO) to prepare a resin composition 1.

<Example 2: Preparation of resin composition 2>
In Example 1, 6 parts of the curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass) was used, and 6 parts of the curing accelerator (4-pyrrolidinopyridine (PPY), solid content of 5% by mass) was used. 1-methoxy2-propanol solution) was changed to 6 parts. A resin composition 2 was produced in the same manner as in Example 1 except for the above items.

<Example 3: Preparation of resin composition 3>
In Example 1, spherical silica particles surface-treated with an amine-based silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (“Seahoster KE-S20” manufactured by Nippon Catalyst Co., Ltd., coefficient of variation of particle size distribution 5.0. %, Average particle size 0.2 μm) 170 parts are surface-treated with an amine-based silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) Spherical silica particles (“Seahoster KE-S30” manufactured by Nippon Catalyst Co., Ltd.). The coefficient of variation of the diameter distribution was 3.1%, and the average particle size was 0.3 μm). A resin composition 3 was prepared in the same manner as in Example 1 except for the above items.

<Example 4: Preparation of resin composition 4>
In Example 3, 40 parts of the active ester compound (“HPC-8000-65T” manufactured by DIC, a toluene solution having an active group equivalent of about 223 and a solid content of 65% by mass) was added to the active ester compound (“EXB9416-70BK” manufactured by DIC). , The active group equivalent was about 274, and the solid content was changed to 37 parts of MIBK (methyl isobutyl ketone) solution) having a solid content of 70% by mass. A resin composition 4 was prepared in the same manner as in Example 3 except for the above items.

<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 of about 216 and a solid content of 50% by mass) was further added. A resin composition 5 was prepared in the same manner as in Example 3 except for the above items.

<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 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 & Sumitomo Metal Chemical Co., Ltd. -485 ”, active group equivalent about 215) changed to 7.2 parts,
2) 16 parts of a phenolic curing agent (“LA-3018-50P” manufactured by DIC, a 2-methoxypropanol solution having an active group equivalent of about 151 and a solid content of 50%) was added to a phenolic curing agent (“LA-” manufactured by DIC). 7054 ”, MEK solution with active group equivalent of about 124 and solid content of 60%) changed to 12 parts.
3) Spherical silica particles surface-treated with an amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("Seahoster KE-S20" manufactured by Nippon Catalyst Co., Ltd., coefficient of variation of particle size distribution 5.0%, average Particle size 0.2 μm) 170 parts was changed to 110 parts.
A comparative resin composition 1 was prepared in the same manner as in Example 1 except for the above items.

<Comparative Example 2: Preparation of Comparative Resin Composition 2>
In Comparative Example 1, spherical silica particles surface-treated with an amine-based silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (“Seahoster KE-S20” manufactured by Nippon Catalyst Co., Ltd., coefficient of variation of particle size distribution 5.0. %, Average particle size 0.2 μm) 110 parts are surface-treated with an amine-based silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) Spherical silica particles (“Seahoster KE-S30” manufactured by Nippon Catalyst Co., Ltd.). The coefficient of variation of the diameter distribution was 3.1%, and the average particle size was 0.3 μm). A comparative resin composition 2 was prepared in the same manner as in Comparative Example 1 except for the above items.

<Comparative Example 3: Preparation of Comparative Resin Composition 3>
In Example 1, spherical silica particles surface-treated with an amine-based silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“Seahoster KE-S20” manufactured by Nippon Catalyst Co., Ltd., particle size distribution variation coefficient 5.0. %, Average particle size 0.2 μm) 170 parts are surface-treated with an amine-based silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), spherical silica (“SO-C1” manufactured by Admatex Co., Ltd., particle size distribution). The fluctuation coefficient was 41%, the average particle size was 0.3 μm, and the average particle size was changed to 170 parts. A comparative resin composition 3 was prepared in the same manner as in Example 1 except for the above items.

<Preparation of resin sheet A>
As a support, a PET film ("Lumilar R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C., hereinafter "Release PET") treated with an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Corporation). There are times when.) Was prepared.

Each resin composition is uniformly applied on the 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 the release PET. A resin composition layer was obtained. Next, a rough surface of a polypropylene film (“Alfan MA-411” manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) as a protective film is bonded to the surface of the resin composition layer that is not bonded to the support. Laminated so as to. As a result, a resin sheet A composed of a release PET (support), a resin composition layer, and a protective film was obtained.

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

<Measurement of particle size of inorganic filler in cross section of cured product>
Of the cross-sectional images perpendicular to the surface of the cured product B for evaluation, a cross-sectional observation was performed using an arbitrarily selected range of width 100 μm and depth 5 μm using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology Inc.). .. In each FIB-SEM image, the maximum particle size R1 (μm) of the inorganic filler in the range of width 100 μm and depth 5 μm, 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 that are the diameters and calculating using the above device. This operation was performed at any 10 randomly selected locations, and the average value of each was shown in the table.

<Evaluation of Arithmetic Mean Roughness (Ra), Maximum Height Roughness (Rz), Insulation Layer Thickness, and Insulation>
(1) Base treatment of inner layer circuit board Glass cloth base material with epoxy resin on both sides having a circuit conductor (copper) formed with a wiring pattern of L / S (line / space) = 2 μm / 2 μm as the inner layer circuit board A copper-clad laminate (copper foil thickness 3 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemicals Co., Ltd. “HL832NSF LCA”, 255 × 340 mm size) was prepared. Both sides of the inner layer circuit board were treated with an organic coating on the copper surface with a surface treatment liquid (“FlatBOND-FT” manufactured by MEC).

(2) Laminating of resin sheets The protective film is peeled off from each of the produced resin sheets A, and the resin composition layer is formed by using a batch type vacuum pressure laminator (2-stage build-up laminator manufactured by Nikko Materials Co., Ltd., CVP700). It was laminated on both sides of the inner layer circuit board so as to be in contact with the inner layer circuit board. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and crimping at 130 ° C. and a pressure of 0.74 MPa for 45 seconds. Then, 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 thermoset for 30 minutes after being placed in an oven at 100 ° C., and then transferred to an oven at 180 ° C. for 30 minutes to increase the thickness. An insulating layer of 5 μm was formed. This is referred to as substrate C.

(4) Step of Roughening Treatment The release PET of the substrate C was peeled off, and the insulating layer was subjected to desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was carried out.

Wet desmear treatment:
In a swollen solution (Atotech Japan's "Swelling Dip Securigant P", an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, then an oxidizing agent solution (Atotech Japan's "Concentrate Compact CP"" , Aqueous solution with potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80 ° C. for 20 minutes, and finally in a neutralizing solution (Atotech Japan's "Reduction Solution Securigant P", sulfuric acid aqueous solution). After soaking 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 a 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.) A conductor layer was formed by performing a copper plating step) using a chemical solution made in Japan.

1. 1. Alkaline cleaning (cleaning of the surface of the insulating layer with via holes and charge adjustment)
The surface of the roughened substrate D was washed with Cleaning Cleaner Security 902 (trade name) at 60 ° C. for 5 minutes.
2. Soft etching (cleaning inside the via hole)
The surface of the roughened substrate D was treated with an aqueous solution of sodium sulfate-acidic peroxodisulfate at 30 ° C. for 1 minute.
3. 3. Predip (Adjustment of charge on the surface of the insulating layer for Pd application)
The surface of the roughened substrate D was prepared by Pre. Treatment was performed at room temperature for 1 minute using Dip Neoganth B (trade name).
4. Applying an activator (adding Pd to the surface of the insulating layer)
The surface of the roughened substrate D was treated with Activator Neoganth 834 (trade name) at 35 ° C. for 5 minutes.
5. Reduction (Reduction of Pd applied to the insulating layer)
The surface of the roughened substrate D was subjected to Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. Using a mixed solution with (trade name), the treatment was carried out at 30 ° C. for 5 minutes.
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 mixed with 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 Step Next, an electrolytic copper plating step was carried out under the condition that the via hole was filled with copper using a chemical solution manufactured by Atotech Japan. After that, as a resist pattern for patterning by etching, a land pattern having a diameter of 1 mm conducted through the via hole and a circular conductor pattern having a diameter of 10 mm not connected to the lower layer conductor were used, and a thickness of 10 μm was used on the surface of the insulating layer. A conductor layer with lands and conductor patterns was formed. Next, the annealing treatment was performed at 200 ° C. for 90 minutes. This substrate was designated as "insulation evaluation substrate E".

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

(7) Measurement of Thickness of Insulating Layer Between Conductors The cross section of the insulating substrate E was observed using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology Co., Ltd.). Specifically, a cross section in a direction perpendicular to the surface of the conductor layer was cut out by a FIB (focused ion beam), and the thickness of the insulating layer between the conductor layers was measured from the cross section SEM image. For each sample, five randomly selected cross-sectional SEM images were observed, and the average value was taken as the thickness (μm) of the insulating layer between the conductor layers and is shown in the table below.

(8) Evaluation of Insulation Reliability (Insulation) of Insulation Layer An inner layer circuit board connected to a land having a diameter of 1 mm with the circular conductor side of the insulation evaluation substrate E obtained above having a diameter of 10 mm as a + electrode. Using a highly accelerated life test device (“PM422” manufactured by ETAC) with the lattice conductor (copper) side as a − electrode, 200 hours were allowed to elapse under the conditions of 130 ° C., 85% relative humidity, and 3.3 V DC voltage application. The insulation resistance value was measured with an electrochemical migration tester (“ECM-100” manufactured by J-RAS). This measurement is performed six times, the resistance value in all test pieces of 6 points to the case of more than 10 ⁷ Omega as "○", when less than even one 10 ⁷ Omega is a "×", the evaluation result and the insulation resistance The values are shown in the table below. The insulation resistance values shown in the table below are the minimum insulation resistance values of the six test pieces.

<Preparation of substrate for laser workability evaluation>
(1) Via hole formation A CO ₂ laser machine (YB-HCS03T04) manufactured by Matsushita Welding System Co., Ltd. is used to drill a hole in the insulating layer on the substrate C under the conditions of a pulse width of 8 μsec and a number of shots of 3 at a frequency of 2000 Hz. A via hole having a top diameter (diameter) of 25 μm on the surface of the insulating layer and a diameter of 20 μm at the bottom of the via hole on the bottom surface of the insulating layer was formed.

(2) Step of roughening treatment The release PET was peeled off, and the insulating layer was subjected to desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was carried out.

Wet desmear treatment:
In a swollen solution (Atotech Japan's "Swelling Dip Securigant P", an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, then an oxidizing agent solution (Atotech Japan's "Concentrate Compact CP"" , Aqueous solution with potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80 ° C. for 20 minutes, and finally in a neutralizing solution (Atotech Japan's "Reduction Solution Securigant P", sulfuric acid aqueous solution). After soaking at 40 ° C. for 5 minutes, it was dried at 80 ° C. for 15 minutes.

<Evaluation of laser workability>
The circumference of the bottom of the via hole was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface 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 evaluated as “◯”, and the case where the maximum smear length was 3 μm or more was evaluated as “x”.

In Examples 1 to 5, it has been confirmed that even when the components (D) to (G) are not contained, the same result as in the above-mentioned Examples is obtained, although the degree is different.

Claims (13)

A resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler.
The component (C) is a resin composition having a coefficient of variation of particle size distribution of 20 % 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 non-volatile component in the resin composition is 100% by mass. The resin composition according to claim 1 or 2, wherein the average particle size of the component (C) is 0.1 μm or more and 3 μm or less. The resin composition according to any one of claims 1 to 3, which is used for forming an insulating layer of a printed wiring board. In any one of claims 1 to 4, the ratio (L / S) of the circuit width (L (μm)) to the width between circuits (S (μm)) is 10 μm / 10 μm or less for forming a circuit. The resin composition 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 mean 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 vias by laser irradiation. Arbitrary 10 points on the surface of the cured product obtained by thermosetting the resin composition at 200 ° C. for 90 minutes were selected, and among the cross-sectional images perpendicular to the surface of the cured product at those points, the width was 100 μm and the depth was 5 μm. 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 according to any one of claims 1 to 7, which satisfies the relationship of R1 <1.4 × R2. Arbitrary 10 points on the surface of the cured product obtained by thermosetting the resin composition at 200 ° C. for 90 minutes were selected, and among the cross-sectional images perpendicular to the surface of the cured product at those points, the width was 100 μm and the depth was 5 μm. 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 × R2) μm or more is 4 or less. 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 claims 1 to 9. The resin sheet according to claim 10, wherein the thickness of the resin composition layer is 15 μm 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 insulating layer is a printed wiring board which is a cured product of the resin composition according to any one of claims 1 to 9. To claim 1 2 comprising a printed wiring board according semiconductor device.

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