TW201920414A - Resin composition - Google Patents

Abstract

This invention provides a resin composition capable of obtaining a cured product capable of maintaining well-balanced adhesion with a conductor layer after an environmental test performed under a high temperature and high humidity environment even if a large amount of inorganic filler is used. A resin composition comprises an epoxy resin (A), a benzoxazine compound (B), and an inorganic filler (C), wherein the (B) component is represented by the following general formula (B-1): the content of the component (C) is 67% by mass or more when the nonvolatile component in the resin composition is 100% by mass. In formula (B-1), R1 represents an n-valent group containing an oxygen atom, and R2 each independently represents a halogen atom, an alkyl group, or an aryl group. n represents an integer of 2 to 4, and m represents an integer of 0 to 4.

Description

Resin composition

The present invention relates to a resin composition. The present invention further relates to a resin sheet, a printed circuit board, and a semiconductor device obtained by using the resin composition.

As a manufacturing technique of a printed circuit board, a manufacturing method in which an accumulation method in which an insulating layer and a conductor layer are alternately overlapped is known. In the manufacturing method by the accumulation method, the insulating layer is generally formed by curing a resin composition.

For example, Patent Document 1 discloses a thermosetting resin composition containing 50 to 99% by mass of benzoxazine and 50 to 1% by mass of phenolox methane. In addition, Patent Document 2 discloses that the active ester compound (B) contains a polyfunctional epoxy compound (A), an active ester compound (B), a benzoxazine compound (C), and a filler (D). The ratio of the ester group to the phenolic hydroxyl group of the benzoxazine compound (C) is calculated as a curable resin composition having a phenolic hydroxyl group / active ester group equivalent ratio of 0.3 to 0.9.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] JP 2012-171968
[Patent Document 2] JP 2014-148562

[Problems Solved by the Invention]

Generally, it is known that the resin composition to which a large amount of an inorganic filler is added tends to reduce the adhesiveness of a conductive layer. The present inventors further conducted a review and found that the resin composition containing more inorganic fillers would reduce the density of the conductive layer even after an environmental test (HAST test) under a high temperature and high humidity environment. Adhesion is difficult to maintain over a long period of time. Especially for printed circuit boards, due to the elimination of the non-conformity between the thermal expansion coefficients of the conductor layer and the insulating layer, more inorganic fillers are sometimes added, which is important in maintaining the adhesion after environmental tests.

An object of the present invention is to provide a resin composition that can obtain a hardened product capable of maintaining a balance of adhesion with a conductor layer after an environmental test under a high temperature and high humidity environment, even if a large amount of inorganic filler is used; A resin sheet of a resin composition; a printed circuit board and a semiconductor device including an insulating layer formed using the resin composition.

[Means for solving problems]

In order to solve the problem of the present invention, the present inventors conducted a detailed review and found that even if a large amount of inorganic filler is used, the resin composition contains a specific benzoxazine compound, and the conductor layer and the conductive layer can be maintained even after an environmental test. Adhesion between insulation layers. In addition, they found that in addition to the above-mentioned adhesion, they also have excellent stain removal properties, and completed the present invention.

That is, the present invention includes the following.
[1] A resin composition, which is a resin composition containing (A) an epoxy resin, (B) a benzoxazine compound, and (C) an inorganic filler,
(B) The component is represented by the following general formula (B-1),
(C) The content of the component is 67% by mass or more when the nonvolatile content in the resin composition is 100% by mass;

In the formula (B-1), R ¹ represents an n-valent group containing an oxygen atom, and R ² each independently represents a halogen atom, an alkyl group, or an aryl group. n represents an integer from 2 to 4, and m represents an integer from 0 to 4.
[2] The resin composition according to [1], wherein when the content of the component (B) is 100% by mass of a nonvolatile component in the resin composition, the content is 0.1% by mass or more and 10% by mass or less.
[3] The resin composition according to [1] or [2], further comprising (D) an active ester compound.
[4] The resin composition according to [3], wherein the content of the component (D) is 5 mass% or more when the content of the non-volatile component in the resin composition is 100 mass%.
[5] The resin composition according to any one of [1] to [4], wherein the average particle diameter of the (C) inorganic filler is 0.5 μm or more.
[6] The resin composition according to any one of [1] to [5], wherein in the general formula (B-1), R ¹ is an n-valent group formed by a combination of an oxygen atom and an arylene group.
[7] The resin composition according to any one of [1] to [6], wherein m represents 0 in the general formula (B-1).
[8] The resin composition according to any one of [1] to [7], which is used for forming an insulating layer of a printed circuit board.
[9] The resin composition according to any one of [1] to [8], which is used for forming an interlayer insulating layer of a printed circuit board.
[10] A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of [1] to [9] provided on the support.
[11] The resin sheet according to [10], wherein the thickness of the resin composition layer is 25 μm or less.
[12] A printed circuit board comprising a first conductor layer, a second conductor layer, and an insulation layer formed between the first conductor layer and the second conductor layer, and the insulation layer is as described in [1] ~ [ 9] A cured product of the resin composition according to any one of the above.
[13] A semiconductor device comprising the printed circuit board according to [12].

[Effect of the invention]

According to the present invention, it is possible to provide a resin composition that is a hardened material that can achieve a balance of maintaining the adhesion with the conductor layer after an environmental test under a high temperature and high humidity environment even if a large amount of inorganic filler is used. A resin composition; a resin sheet containing the resin composition; a printed circuit board and a semiconductor device including an insulating layer formed using the resin composition;

[Form of Implementing Invention]

The resin composition, resin sheet, printed circuit board, and semiconductor device of the present invention will be described in detail below.

[Resin composition]
The resin composition of the present invention is a resin composition containing (A) an epoxy resin, (B) a benzoxazine compound, and (C) an inorganic filler, and the (B) component is represented by the following general formula (B-1) The content of the component (C) is 67% by mass or more when the nonvolatile component in the resin composition is 100% by mass.

In the formula (B-1), R ¹ represents an n-valent group containing an oxygen atom, and R ² each independently represents a halogen atom, an alkyl group, or an aryl group. n represents an integer from 2 to 4, and m represents an integer from 0 to 4.

In the present invention, when the non-volatile content in the resin composition is 100% by mass, even if a large amount of inorganic fillers of 67% by mass or more are used, the specific benzoxazine compound is contained, even in a high-temperature and high-humidity environment. After the environmental test, a hardened material with excellent adhesion to the conductor layer and excellent stain removal properties can be obtained. Normally, even after an environmental test under such a high temperature and high humidity environment, a hardened material that can maintain high adhesion can exhibit high adhesion over a long period of time.

It has been known from the past that (B) benzoxazine compounds can function as hardeners for epoxy resins. However, the present inventors have found that even if a large amount of inorganic filler is used, the adhesion between the conductor layer and the insulating layer can be maintained after an environmental test in a high temperature and high humidity environment by containing a specific benzoxazine compound. In addition, it was found that in addition to the above-mentioned adhesion, it has excellent stain removal properties. By containing a specific benzoxazine compound, even if a large number of inorganic fillers are used, high adhesion can be maintained after an environmental test under a high temperature and high humidity environment, and the technical concept of excellent stain removal properties is based on the inventors As we know, it has not been proposed at all in the past.

In addition to the components (A) to (C), the resin composition may contain (D) an active ester compound, (E) a hardener, (F) a hardening accelerator, (G) a thermoplastic resin, and (H) any additives as necessary. . Hereinafter, each component contained in the resin composition of this invention is demonstrated in detail.

＜ (A) Epoxy resin ＞
The resin composition contains (A) an epoxy resin. Examples of the (A) epoxy resin include a biscresol epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, and a bisphenol AF ring. Epoxy resin, dicyclopentadiene epoxy resin, phenol novolac epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin , Naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, cresol novolac epoxy resin, biphenyl Epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane ring Oxygen resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin and the like. The epoxy resin may be used singly or in combination of two or more kinds.

(A) Epoxy resins are based on the viewpoint that a hardened product that maintains high adhesion can be obtained even after an environmental test under a high temperature and high humidity environment. An aromatic epoxy resin is preferred. A bisphenol A type epoxy resin, Either a bisphenol F-type epoxy resin or a naphthol-type epoxy resin is preferred.

(A) The epoxy resin is preferably one having two or more epoxy groups in one molecule. When the non-volatile content 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 is a combination of a liquid epoxy resin (hereinafter also referred to as a "liquid epoxy resin") at a temperature of 20 ° C and a solid epoxy resin (also referred to as a "solid state" at a temperature of 20 ° C). Epoxy resin ") is preferred. The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, and an aromatic liquid epoxy resin having two or more epoxy groups in one molecule. Which is better. The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule. Which is better. In the present invention, the term “aromatic epoxy resin” means an epoxy resin having an aromatic ring in the molecule.

As the liquid epoxy resin, there are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, and glycidyl group. Amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin A resin and an epoxy resin having a butadiene structure are preferable, and a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC, "828US", "jER828EL", " 825 "," EPICOAT828EL "(bisphenol A type epoxy resin)," jER807 "," 1750 "(bisphenol F type epoxy resin)," jER152 "(phenol novolac type epoxy resin)," 630 ", "630LSD" (glycidylamine type epoxy resin), "Nippon Steel & Sumitomo Chemical Co., Ltd." "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), Nagase Chemtex company "EX-721" (glycidyl ester type epoxy resin), "CELLOXIDE2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel Chemical Industries, Ltd., "PB-3600" (with succinic acid) Epoxy resin with olefin structure), "ZX1658", "ZX1658GS" (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and "630LSD" manufactured by Mitsubishi Chemical Corporation (Glycidylamine type epoxy resin) and the like are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

As the solid epoxy resin, bis-cresol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type 4-functional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, Ginseng type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type ring Oxygen resin and tetraphenylethane type epoxy resin are preferable, and naphthalene type epoxy resin is more preferable. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), and " "N-690" (cresol novolac epoxy resin), "N-695" (cresol novolac epoxy resin), "HP-7200" (dicyclopentadiene epoxy resin), "HP -7200HH "," HP-7200H "," EXA-7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(naphthylene ether ring Oxygen resin), "EPPN-502H" (ginsenophenol-type epoxy resin), "NC7000L" (naphthol novolac-type epoxy resin), "NC3000H", "NC3000", "NC3000L", `` NC3100 '' (biphenyl type epoxy resin), `` ESN475V '' (naphthalene type epoxy resin), `` ESN485 '' (naphthol novolac type epoxy resin) by Nippon Steel & Sumitomo Chemical Co., Ltd., and Mitsubishi Chemical Corporation "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bisxylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), Osaka Gas Chemical Company-based PG-100 "," CG-500 "," YL7760 "(bisphenol AF type epoxy resin)," YL7800 "(type epoxy resin) made by Mitsubishi Chemical Corporation," jER1010 "(solid made by Mitsubishi Chemical Corporation) Bisphenol A epoxy resin), "jER1031S" (tetraphenylethane epoxy resin), and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

When the liquid epoxy resin and the solid epoxy resin are used as the component (A), the quantity ratio (liquid epoxy resin: solid epoxy resin) is 1: 1 to 1:20 when calculated by mass ratio. The range is better. When the amount ratio of the liquid epoxy resin to the solid epoxy resin is within this range, i) can be obtained with moderate adhesion when used in the form of a resin sheet, and ii) when used in the form of a resin sheet. It is possible to obtain sufficient flexibility to improve handling properties, and iii) to obtain effects such as a hardened material having sufficient breaking strength. From the viewpoint of the effects of i) to iii) above, when the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is calculated as the mass ratio, the ratio is 1: A range of 1 to 1: 15 is preferable, and a range of 1: 1 to 1: 10 is more preferable.

The content of the component (A) in the resin composition is from the viewpoint that an insulating layer showing good mechanical strength and insulation reliability can be obtained. When the nonvolatile component in the resin composition is 100% by mass, the content is 5 It is preferably at least mass%, more preferably at least 10 mass%, and even more preferably at least 15 mass%. The upper limit of the content of the epoxy resin is not particularly limited as long as it can achieve the effects of the present invention, and is preferably 30% by mass or less, more preferably 25% by mass or less, and more preferably 20% by mass or less.
In addition, in the present invention, the content of each component in the resin composition is a value when the nonvolatile 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, more preferably 80 to 2000, and still more preferably 110 to 1,000. Within this range, the crosslinked density of the hardened material becomes sufficient, and an insulating layer with a small surface roughness can be obtained. The epoxy equivalent can be measured in accordance with JIS K7236, and is the mass of a resin containing 1 equivalent of an 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. The weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

＜ (B) benzoxazine compound ＞
The resin composition contains a benzoxazine compound (B) represented by the following general formula (B-1).

In the formula (B-1), R ¹ represents an n-valent group containing an oxygen atom, and R ² each independently represents a halogen atom, an alkyl group, or an aryl group. n represents an integer from 2 to 4, and m represents an integer from 0 to 4.

R ¹ represents an n-valent group containing an oxygen atom. Examples of such a base include an n-valent group composed of a combination of an oxygen atom and an alkylene group, an n-valent group composed of a combination of an oxygen atom and an alkylene group, and an n-valent group composed of an oxygen atom and an alkylene group and an alkylene group. From the viewpoint of improving the adhesion between the insulating layer and the conductor layer after the environmental test, and from the viewpoint of effectively improving the stain removal property, the n-valent group formed by the combination of A combination of n-valent bases is preferred.

As the arylene group, an arylene group having 6 to 20 carbon atoms is preferable, an arylene group having 6 to 15 carbon atoms is more preferable, and an arylene group having 6 to 12 carbon atoms is more preferable. Specific examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, and a bisphenylene group, and the phenylene group is preferred.
As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferred, an alkylene group having 1 to 6 carbon atoms is more preferred, and an alkylene group having 1 to 3 carbon atoms is more preferred. Specific examples of the alkylene group include a methyl group, an ethyl group, and a propyl group, and a methyl group is preferred.

Specific examples of the n-valent group containing an oxygen atom include the following groups. In the formula, "*" represents a bonding key.

The arylene group and the alkylene group may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, -OH, and -OC _1-6.
Alkyl, -N (C _1-6 alkyl) ₂ , C _1-6 alkyl, C _6-10 aryl, -NH ₂ , -CN,
-C (O) OC _1-6 alkyl, -COOH, -C (O) H, -NO ₂ and the like. The term “C _pq ” (p and q are positive integers and satisfy p <q) means that the number of carbon atoms of the organic group described in the term is p to q. For example, the expression "C _1-6 alkyl" means an alkyl group having 1 to 6 carbon atoms.

The said substituent may further have a substituent (henceforth a "secondary substituent"). As a secondary substituent, unless otherwise stated, the same thing as the said substituent can be used.

R ² each independently represents a halogen atom, an alkyl group, or an aryl group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms. The halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The alkyl group and the aryl group may have a substituent. The substituent is the same as the substituent which may have the above-mentioned arylene group.

n represents an integer of 2 to 4, an integer of 2 to 3 is preferred, and 2 is more preferred. m represents an integer from 0 to 4, an integer from 0 to 3 is preferred, and 0 is more preferred.

From the viewpoint that the desired effect of the present invention can be effectively obtained, the benzoxazine compound represented by the general formula (B-1) is preferably a benzoxazine compound represented by the following general formula (B-2).

The benzoxazine compound represented by the general formula (B-2) is preferably at least one of the benzoxazine compound represented by the general formula (B-3) and the general formula (B-4).

The benzoxazine compound represented by the general formula (B-1) may be used singly or in combination of two or more kinds. For example, when a benzoxazine compound represented by the general formula (B-3) and a benzoxazine compound represented by the general formula (B-4) are used as a mixture, the mass mixing ratio (general formula (B-3): general formula (B-4)) 1: 10 ~ 10: 1 is preferred, 1: 5 ~ 5: 1 is preferred, and 1: 3 ~ 3: 1 is more preferred. When the mass mixing ratio is within this range, the adhesion between the insulating layer and the conductor layer after the environmental test can be improved. Smear removal is often further effectively improved.

Specific examples of the (B) benzoxazine compound include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd .; "Fa" manufactured by Shikoku Chemical Industry Co., Ltd .; and manufactured by Showa Polymer Co., Ltd. "HFB2006M", etc.

The molecular weight of the (B) benzoxazine compound is preferably 200 or more, more preferably 300 or more, more preferably 400 or more, more preferably 1,000 or less, and more preferably 800 from the viewpoint of improving adhesion. Below, more preferably 500 or less.

(B) When the content of the benzoxazine compound is 100% by mass of the nonvolatile matter in the resin composition, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 1% by mass. %the above. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, more preferably 5% by mass or less or 3% by mass. When the content of the component (B) is within this range, the adhesion between the insulating layer and the conductor layer after the environmental test can be improved. Smear removal is often effectively further improved.

＜ (C) Inorganic fillers ＞
The resin composition contains (C) an inorganic filler. (C) The content of the inorganic filler is from the viewpoint of reducing the thermal expansion rate. When the non-volatile content in the resin composition is 100% by mass, it is preferably 67% by mass or more, and preferably 68% by mass or more. It is 70 mass% or more. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less. In the present invention, by containing the (B) benzoxazine compound, the adhesiveness after the HAST test can be maintained even if the (C) inorganic filler is 67% by mass or more.

(C) The material of the inorganic filler is not particularly limited as long as it is an inorganic compound, and examples thereof include silicon dioxide, alumina, glass, cordierite, silicate, barium sulfate, barium carbonate, talc, clay, Mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, titanic acid Strontium, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconia, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silicon dioxide is particularly preferred. Examples of the silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. Further, as the silica, spherical silica is preferred. The inorganic filler may be used singly or in combination of two or more kinds.

Examples of commercially available products of (C) inorganic fillers include "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials; "YC100C", "YA050C", and "YA050C" manufactured by Admatechs -MJE "," YA010C ";" UFP-30 "by Denka;" SilfirNSS-3N "," SilfirNSS-4N "," SilfirNSS-5N "by Tokuyama;" SC2500SQ "," SO by Admatechs " -C4 "," SO-C2 "," SO-C1 ", etc.

The (C) inorganic filler is usually contained in the resin composition in a particulate state. (C) From the viewpoint that the average particle diameter of the inorganic filler can remarkably obtain the desired effect of the present invention, it is preferably 0.01 μm or more, more preferably 0.1 μm or more, particularly preferably 0.5 μm or more, and more preferably 5.0 μm or less. Is preferably 2.0 μm or less, and more preferably 1.0 μm or less. In addition, when the average particle diameter of the (C) inorganic filler is in the aforementioned range, the circuit embedding property of the resin composition layer can be generally improved, the surface roughness of the insulating layer can be reduced, or a large amount of (C) inorganic filler can be easily filled. .

(C) The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the (C) inorganic filler is prepared on a volume basis using a laser diffraction scattering particle size distribution measurement device, and the median diameter can be measured as the average particle size. The measurement sample is preferably one in which (C) an inorganic filler is dispersed in methyl ethyl ketone by ultrasound. As a laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba, Ltd., and "SALD-2200" manufactured by Shimadzu Corporation can be used.

(C) The specific surface area of the inorganic filler is preferably 1 m ² / g or more, more preferably 3 m ² / g or more, and more preferably 5 m ² / g or more, from the viewpoint that the desired effect of the present invention can be significantly obtained. Although the upper limit is not particularly limited, it is preferably 30 m ² / g or less, more preferably 20 m ² / g or less, and even more preferably 10 m ² / g or less.
The specific surface area was obtained by adsorbing nitrogen on the surface of the sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area by the BET multipoint method.

(C) From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler can be surface-treated with a surface-treating agent. Examples of the surface treatment agent include an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane, an organic silazane compound, and a titanate-based coupling agent. Mixture and so on. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "KBM803" (3-mercaptopropyl) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Trimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industries, "KBM573" (N-phenyl-3-aminopropyltrimethyl) manufactured by Shin-Etsu Chemical Industries, Ltd. Oxysilane), Shin-Etsu Chemical Industry Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Industry Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Industry Co., Ltd. "KBM- 4803 "(long-chain epoxy-type silane coupling agent)," KBM-7103 "(3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like. The surface treatment agent may be used singly or in combination of two or more kinds.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (C) inorganic filler. (C) The carbon content per unit surface area of the inorganic filler is preferably 0.02 mg / m ² or more, more preferably 0.1 mg / m ² or more, from the viewpoint of improving the dispersibility of the inorganic filler (C). It is more preferably 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 paint and the melt viscosity in the form of a sheet, it is preferably 1 mg / m ² or less, more preferably 0.8 mg / m ² or less, and 0.5 mg / m ² . It is more preferably m ² or less.

The carbon content per unit surface area of the (C) inorganic filler can be measured after the surface-treated (C) inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent was added to the (C) inorganic filler surface-treated with a surface-treating agent, and ultrasonic cleaning was performed at 25 ° C for 5 minutes. After removing the upper liquid and drying the solid content, the carbon content per unit surface area of the (C) inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

<(D) Active ester compound>
In one embodiment, the resin composition contains (D) an active ester compound. It is known that when an active ester compound is used, stain removability is generally deteriorated. However, since the cured product of the resin composition of the present invention has excellent stain removal properties, the stain removal properties are not deteriorated even when the active ester compound is used.

The active ester compound is not particularly limited. Generally, esters using phenolic esters, thiophenolic esters, N-hydroxyamine esters, and heterocyclic hydroxy compounds are equal to two or more highly reactive esters in one molecule. Compounds based on radicals are preferred. The active ester compound is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalazine, methylated bisphenol A, methylated bisphenol F, and methylformate. Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, resorcinol, benzenetriol, dicyclopentadiene type diphenol Compounds, phenol novolacs, etc. The so-called "dicyclopentadiene-type diphenol compound" is a diphenol compound obtained by condensing two molecules of phenol in one molecule of dicyclopentadiene.

Specifically, the active ester compound containing a dicyclopentadiene-type diphenol structure, the active ester compound containing a naphthalene structure, the active ester compound containing an acetic acid compound of a phenol novolac, and the activity of a benzamidine compound containing a phenol novolac An ester compound is preferable, and an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are also preferable. The "dicyclopentadiene-type diphenol structure" means a divalent structural unit formed of phenylene-bicyclopentyl-phenylene.

Examples of commercially available active ester compounds containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC- 8000H-65TM "," EXB8000L-65TM "," EXB8150-65T "(manufactured by DIC Corporation), as the active ester compound containing a naphthalene structure," EXB9416-70BK "(manufactured by DIC Corporation), and phenol novolac Examples of the active ester compound of acetamate include "DC808" (manufactured by Mitsubishi Chemical Corporation), and as the active ester compound of benzophenone containing phenol novolac, "YLH1026" (made by Mitsubishi Chemical Corporation) Examples of the active ester compound of the acetic acid compound of phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation), and the example of the active ester compound of the benzoic acid compound of phenol novolac includes "YLH1026" (Mitsubishi Chemical company), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc.

When the resin composition contains (D) an active ester compound, the ratio of the amount of the epoxy resin to the active ester compound is the ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the active ester compound]. In the following, a range of 1: 0.01 to 1: 5 is preferable, 1: 0.05 to 1: 3 is more preferable, and 1: 0.1 to 1: 1.5 is more preferable. Among them, the reactive group of the active ester compound is an active ester group. The total number of epoxy groups of the epoxy resin is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent. The total value is calculated for all epoxy resins. The total count is a value obtained by dividing the solid content mass of each active ester compound by the reactive group equivalent for all active ester compounds. When the amount ratio of the epoxy resin to the active ester compound is within this range, the heat resistance of the cured product of the resin composition can be further improved.

When the resin composition contains the (D) active ester compound, when the content of the (D) component is 100% by mass of the nonvolatile component in the resin composition, it is preferably 1% by mass or more, and more preferably 2% by mass. The above is more preferably 3% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. By setting the content of the (D) component within this range, the peel strength before and after the environmental test can be improved.

＜ (E) Hardener ＞
In one embodiment, the resin composition contains a (E) hardener. However, (D) the active ester compound is not contained in (E) the hardener. The (E) curing agent is not particularly limited as long as it can have the component (A), and examples thereof include a phenol-based curing agent, a naphthol-based curing agent, a cyanate ester-based curing agent, and a carbodiimide. Amine-based hardeners, etc. Among them, from the viewpoint of improving insulation reliability, the (E) hardener is any one or more of a phenol-based hardener, a naphthol-based hardener, a cyanate-based hardener, and a carbodiimide-based hardener. Preferably, a phenolic hardener is included. The hardener may be used alone or in combination of two or more.

As the phenol-based hardener and naphthol-based hardener, from the viewpoints of heat resistance and water resistance, a phenol-based hardener having a novolac structure or a naphthol-based hardener having a novolac structure is preferred. From the viewpoint of adhesion with the conductor layer, a nitrogen-containing phenol-based hardener is preferred, and a triazine skeleton contains a phenol-based hardener.

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

Examples of the cyanate ester-based hardener include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylphenyl cyanate), 4,4 '-Methylenebis (2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2 -Bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1 , 3-bis (4-cyanatephenyl-1- (methylethylene)) benzene, bis (4-cyanatephenyl) thioether and bis (4-cyanatephenyl) ether Polyfunctional cyanate resins derived from bifunctional cyanate resins, phenol novolacs, cresol novolacs, etc., and triazinated prepolymers are part of these cyanate resins. Specific examples of the cyanate ester-based hardener include "PT30" and "PT60" (phenol novolac-type polyfunctional cyanate ester resin) and "ULL-950S" (polyfunctional cyanide resin) manufactured by Lonza Japan. Acid ester resin), "BA230", "BA230S75" (prepolymers in which a part or all of the bisphenol A dicyanate is triazinated to become a trimer).

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

When the resin composition contains (E) a hardener, the amount ratio of the epoxy resin to the hardener is at a ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of hardener], and The range of 1: 0.01 ~ 1: 2 is preferable, 1: 0.03 ~ 1: 3 is preferable, and 1: 0.05 ~ 1: 1.5 is more preferable. Among them, the reactive group of the hardener is an active hydroxyl group or the like, and it varies depending on the type of the hardener. In addition, the total number of epoxy groups of the epoxy resin means the value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent with respect to the total value of all epoxy resins. The value obtained by dividing the solid content mass of each hardener by the reactive group equivalent is the total value of the hardeners. By setting the amount ratio of the epoxy resin to the hardener within this range, the heat resistance of the hardened product of the resin composition can be further improved.

When the resin composition contains (D) an active ester compound and (E) a hardener, the amount ratio of the epoxy resin to the active ester compound is [total number of epoxy groups of the epoxy resin]: [(D) and (E ) The ratio of the total number of reaction groups of the components] is preferably in the range of 1: 0.01 to 1: 5, more preferably 1: 0.05 to 1: 3, and more preferably 1: 0.1 to 1: 1.5. When the amount ratio of the epoxy resin to the (D) component and the (E) component is set within this range, the heat resistance of the cured product of the resin composition can be further improved.

When the resin composition contains the (E) hardener, the content of the (E) hardener is preferably 0.1% by mass or more, and more preferably 0.3% by mass when the nonvolatile content in the resin composition is 100% by mass. The above is preferably 0.5% by mass or more. The upper limit is preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 1 mass% or less. When the content of the (E) hardener is within this range, the adhesion between the insulating layer and the conductor layer can be improved.

＜ (F) Hardening accelerator ＞
In one embodiment, the resin composition contains (F) a hardening accelerator. Examples of the hardening accelerator include phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, and metal-based hardening accelerators. Phosphorus-based hardening accelerators and amine-based hardening agents are mentioned. Accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferred, and amine-based hardening accelerators are more preferred. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine, osmium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, and tetrabutylphosphonium decanoate. (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., with triphenylphosphine, tetrabutyl Phenyl decanoate is preferred.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,- Ginseng (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) -undecene, etc., 4-dimethylaminopyridine, 1,8-diaza Heterobicyclic (5,4,0) -undecene is preferred.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2 -Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl 2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4' -Methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s- Triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] Imidazole compounds such as imidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and the addition of imidazole compounds and epoxy resins The product is preferably 2-ethyl-4-methylimidazole or 1-benzyl-2-phenylimidazole.

As the imidazole-based hardening accelerator, a commercially available product can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based hardening accelerator include dicyandiamine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, Dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl -1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl Alkyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1- (o-tolyl) biguanide Etc. Preferably, dicyandiamine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene is preferred.

Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetopyruvate and cobalt (III) acetopyruvate, and organic copper complexes such as copper (II) acetopyruvate Body, organic zinc complexes such as zinc (II) acetam pyruvate, organic iron complexes such as iron (III) acetam pyruvate, organic nickel complexes such as nickel (II) acetam pyruvate, and manganese (II ) Organomanganese complexes such as acetamidine pyruvate and the like. Examples of the organic metal salt include zinc octanoate, tin octanoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

When the resin composition contains (F) a hardening accelerator, the content of the hardening accelerator is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more, when the nonvolatile component in the resin composition is 100% by mass. And more preferably 0.1% by mass or more. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. When the content of the hardening accelerator is set within this range, a hardened product having particularly excellent adhesion after an environmental test under a high temperature and high humidity environment when a large amount of inorganic filler is used can be used.

＜ (G) Thermoplastic resin ＞
In one embodiment, the resin composition is a thermoplastic resin containing (G). Examples of (G) thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyimide resin, and polyetherimide. Amine resins, polyfluorene resins, polymethylene resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, polyester resins, and the like are preferably phenoxy resins. The thermoplastic resin may be used singly or in combination of two or more kinds.

(G) The polystyrene equivalent weight average molecular weight of the thermoplastic resin is preferably 38,000 or more, more preferably 40,000 or more, and even more preferably 42,000 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. (G) The polystyrene-equivalent weight average molecular weight of the thermoplastic resin can be measured by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight in terms of polystyrene in terms of (G) thermoplastic resin is that LC-9A / RID-6A manufactured by Shimadzu Corporation is used as a measuring device, and Shodex K-800P / K manufactured by Showa Denko Corporation is used as a column. -804L / K-804L, using chloroform or the like as a mobile phase, measuring the column temperature at 40 ° C, and calculating using a standard polystyrene calibration curve.

Examples of the phenoxy resin include those having a structure selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, and dicyclopentane. One or more types of phenoxy resins composed of a diene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene 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 singly or in combination of two or more kinds. Specific examples of the phenoxy resin include "1256" and "4250" (both are phenoxy resins containing a bisphenol A skeleton) and "YX8100" (benzenes containing a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation. Oxyresin) and "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton), and other examples include "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and "FX293" manufactured by Mitsubishi Chemical Corporation "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482", etc.

Examples of the polyvinyl acetal resin include polyvinyl formaldehyde resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include, for example, "Electrobutyral 4000-2", "Electrobutyral 5000-A", "Electrobutyral 6000-C", manufactured by Denki Kogyo Co., Ltd., "Electrochemical butyral 6000-EP", S-LECBH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series, etc. manufactured by Sekisui Chemical Industry Co., Ltd.

Specific examples of the polyimide resin include "RIKACOATSN20" and "RIKACOATPN20" manufactured by Shinnippon Chemical Co., Ltd. Specific examples of the polyfluorene imide resin include a linear polyfluorene imide obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetravalent acid anhydride (described in Japanese Patent Application Laid-Open No. 2006-37083). Polyimide), and a polysiloxane skeleton containing modified polyimide (polyimide described in JP 2002-12667 and JP 2000-319386, etc.).

Specific examples of the polyamidamine / imide resin include "VylomaxHR11NN" and "VylomaxHR16NN" manufactured by Toyobo Corporation. Specific examples of the polyimide resin include denatured polyimide resins such as "KS9100" and "KS9300" (polysiloxane imide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Industries, Ltd. amine.

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

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

Among them, as the (G) thermoplastic resin, a phenoxy resin and a polyvinyl acetal resin are preferred. Therefore, in a preferred embodiment, the thermoplastic resin contains one or more members selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin. Among them, as the thermoplastic resin, a phenoxy resin is preferable, and a phenoxy resin having a weight average molecular weight of 40,000 or more is particularly preferable.

When the resin composition contains a (G) thermoplastic resin, the content of the (G) thermoplastic resin is preferably 0.1% by mass or more, and more preferably 0.2% by mass or more, when the nonvolatile content of the resin composition is 100% by mass. And more preferably 0.3% by mass or more. The upper limit is preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 1 mass% or less. When the content of the (G) thermoplastic resin is set within this range, a cured product having particularly excellent adhesion after an environmental test under a high temperature and high humidity environment when a large amount of inorganic filler is used can be obtained.

＜ (H) Any additive ＞
In one embodiment, the resin composition may contain other additives for further blending. Examples of the other additives include organic metals such as flame retardants, organic fillers, organic copper compounds, organic zinc compounds, and organic cobalt compounds. Compounds, and resin additives such as tackifiers, defoamers, leveling agents, adhesion imparting agents, and coloring agents.

Examples of the flame retardant include a phosphazene compound, an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polysiloxane flame retardant, and a metal hydroxide. Specific examples of the phosphazene compound include "SPH-100", "SPS-100", "SPB-100", "SPE-100" manufactured by Otsuka Chemical Corporation, and "FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd. "", "FP-110", "FP-300", "FP-400", etc., as flame retardants other than phosphazene compounds, commercially available products can be used, for example, "HCA-HQ" manufactured by Sanko Corporation , "PX-200" manufactured by Big Eight Chemical Industries, etc.

As the organic filler, any organic filler used when forming an insulating layer of a printed circuit board can be used, and examples thereof include rubber particles, polyamide fine particles, and polysiloxane particles. As the rubber particles, commercially available products can be used, and examples thereof include "EXL2655" manufactured by Dow Chemical Japan, "AC3401N" and "AC3816N" manufactured by Aika Industries.

<Physical properties and uses of resin composition>
The resin composition was cured at 100 ° C. for 30 minutes, at 170 ° C. for 30 minutes, and then at 200 ° C. for 90 minutes. The cured product usually showed the copper foil peel strength (peeling) before the environmental test (HAST test). Strength) Excellent characteristics. That is, an insulating layer having excellent adhesion before the environmental test was obtained. The peel strength before the environmental test is preferably 0.5 kgf / cm or more, more preferably 0.55 kgf / cm or more, and still more preferably 0.6 kgf / cm or more. Although the upper limit is not particularly limited, 10 kgf / cm or less can be obtained. The copper foil peeling strength before the environmental test can be measured by the method described in Examples described later.

The resin composition is cured at 100 ° C. for 30 minutes, at 170 ° C. for 30 minutes, and then at 200 ° C. for 90 minutes. The cured product usually exhibits excellent copper foil tensile strength (peel strength) after environmental testing. . That is, an insulating layer having excellent adhesion after an environmental test and exhibiting high adhesion over a long period of time can be obtained. The peel strength after the environmental test is preferably 0.15 kgf / cm or more, more preferably 0.2 kgf / cm or more, and even more preferably 0.25 kgf / cm or more. Although the upper limit is not particularly limited, 10 kgf / cm or less can be obtained. The peel strength after the environmental test can be measured by a method described in Examples described later.

The hardened | cured material which heat-cured the resin composition at 100 degreeC for 30 minutes, and 170 degreeC for 30 minutes after that normally shows the characteristic of the outstanding stain | stain removal property. That is, even if a through-hole is formed in the hardened material, an insulating layer having a maximum stain length of 5 μm or less at the bottom of the through-hole is obtained. The stain removal property was measured by the method described in Examples described later.

The resin composition of the present invention has excellent thin-film insulation properties, and after an environmental test under a high-temperature and high-humidity environment, an insulation layer capable of maintaining adhesion with the conductor layer can be obtained. Therefore, the resin composition of the present invention is suitable for use as a resin composition for insulation applications. Specifically, it is a resin composition (a resin composition for forming an insulating layer used to form a conductor layer) used when the insulating layer to be formed on the conductive layer (including a redistribution layer) to be formed is suitable for use as an insulating layer. A resin composition (resin composition for an insulating layer of a printed circuit board) to be used for forming an insulating layer of a printed circuit board, and is suitable as a resin composition (interlayer insulation layer of a printed circuit board) to be used for forming an interlayer insulation layer of a printed circuit board. Use resin composition). In addition, the resin composition of the present invention can be suitably used when the printed circuit board is a circuit board with built-in parts because it can achieve an insulating layer with good part embedding properties.
In addition, for example, when manufacturing a semiconductor wafer package through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition (rewiring formation) for a rewiring formation layer in which an insulating layer of the rewiring layer is to be formed. A resin composition for forming a layer), and a resin composition for sealing a semiconductor wafer (resin composition for sealing a semiconductor wafer). When manufacturing a semiconductor chip package, a redistribution layer may be further formed on the sealing layer.
(1) the step of laminating a temporary fixing film on a substrate,
(2) a step of temporarily fixing a semiconductor wafer to a temporary fixing film,
(3) a step of forming a sealing layer on a semiconductor wafer,
(4) a step of peeling the substrate and the temporary fixing film from the semiconductor wafer,
(5) a step of forming a rewiring forming layer as an insulating layer on the substrate of the semiconductor wafer and the surface on which the temporary fixing film is peeled, and
(6) A step of forming a redistribution layer as a conductor layer on the redistribution forming layer.

[Resin sheet]
The resin sheet of the present invention includes a support and a resin composition layer formed on the support and formed from the resin composition of the present invention.

The thickness of the resin composition layer is preferably 15 μm or less, more preferably 13 μm or less, and more preferably 10 μm or less from the viewpoint of reducing the thickness of the printed circuit board and a cured material that can improve the insulation even with a thin film. 8 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it is usually 1 μm or more, 1.5 μm or more, 2 μm or more, and the like.

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

When a film made of a plastic material is used as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate Polyesters such as esters (hereinafter sometimes referred to simply as "PEN"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, and triethylpyrene Cellulose (TAC), polyether sulfide (PES), polyetherketone, polyimide and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and cheap polyethylene terephthalate is particularly preferred.

When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferred. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

The support is such that a matting treatment, a corona treatment, or a charge prevention treatment can be applied to the surface bonded to the resin composition layer.

As the support, a support having a release layer and a release layer having a release layer can be used on the surface bonded to the resin composition layer. Examples of the release agent used in the release layer of a support provided with a release layer include 1 selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. More than one release agent. A commercially available product can be used as the support with a release layer, and examples thereof include "SK-1" and "AL" made by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based release agent as a main component. -5 "," AL-7 "," Lumirror T60 "manufactured by Toray Corporation," Purex "manufactured by Teijin Corporation," Unipiel "manufactured by Unitika Corporation, etc.

The thickness of the support is not particularly limited, but is preferably in the range of 5 to 75 μm, and more preferably in the range of 10 to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably set to the above range.

In one embodiment, the resin sheet may further include other layers as necessary. Examples of the other layer include a protective film based on a support provided on a surface that is not bonded to the support of the resin composition layer (that is, a surface on the opposite side to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion or scratches on the surface of the resin composition layer can be suppressed.

The resin sheet can be produced by, for example, dissolving a resin composition with an organic solvent to prepare a resin varnish, applying the resin varnish to a support using a mold coating, and then drying the resin composition to form a resin composition layer.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and Carbitol acetate and other acetates; Cellulosics and carbitol such as butyl carbitol; Aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethylacetamide (DMAc) and ammonium solvents such as N-methylpyrrolidone and the like. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

Drying can be performed by a known method such as heating and blowing hot air. Although the drying conditions are not particularly limited, the content of the organic solvent in the resin composition layer is preferably 10% by mass or less, and it is preferable that the content is dried to 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin coating, for example, when using a resin coating containing 30% to 60% by mass of an organic solvent, drying is performed at 50 ° C to 150 ° C for 3 minutes to 10 minutes. , Can form a resin composition layer.

The resin sheet can be rolled into a roll and stored. When the resin sheet has a protective film, it can be used after peeling off the protective film.

The resin sheet of the present invention is an insulating layer (hardened product of a resin composition layer) capable of maintaining adhesion to a conductor layer after an environmental test under a thin film insulation property and a high temperature and high humidity environment. Therefore, the resin sheet of the present invention can be suitably used as a resin sheet for forming an insulating layer of a printed circuit board (for forming an insulating layer of a printed circuit board), and can be more suitably used as a resin sheet for forming an interlayer insulating layer of a printed circuit board ( A resin sheet for an interlayer insulating layer of a printed circuit board). In addition, for 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, an insulating layer is formed by the resin sheet of the present invention, The distance from the first and second conductor layers (the thickness of the insulating layer between the first and second conductor layers) is set to 6 μm or less (preferably 5.5 μm or less, and preferably 5 μm or less), but it has excellent film insulation By.

[A printed circuit board]
The printed circuit board of the present invention includes an insulating layer, a first conductor layer, and a second conductor layer formed of 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 the first conductor layer and the second conductor layer are provided as insulation (the conductor layer is sometimes referred to as a wiring layer).

Since the insulating layer can be formed from the cured product of the resin composition of the present invention, it has excellent thin film insulation properties. Therefore, the thickness of the insulating layer between the first and second conductor layers is preferably 6 μm or less, more preferably 5.5 μm or less, and even more preferably 5 μm or less. Although the lower limit is not particularly limited, it may be set to 0.1 μm or more. The distance between the first conductor layer and the second conductor layer (the thickness of the insulating layer between the first and second conductor layers) is an example shown in FIG. 1, which is the main surface 11 of the first conductor layer 1 and the second conductor layer. In terms of the thickness t1 of the insulating layer 3 between the main surfaces 21 of 2. The first and second conductor layers are conductor layers adjacent to each other 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 even more preferably 10 μm or less. Although the lower limit is not particularly limited, it is usually 1 μm or more, 1.5 μm or more, 2 μm or more, and the like.

The printed circuit board uses the resin sheet described above, and can be produced by a method including the following steps (I) and (II).
(I) a step of laminating the resin composition layer of the resin sheet and the inner substrate on the inner substrate
(II) A step of forming an insulating layer by thermally curing the resin composition layer

The "inner substrate" used in step (I) is a member that becomes a substrate of a printed circuit board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, Thermosetting polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one or both sides, and the conductor layer may also be subjected to pattern processing. The inner layer substrate of the conductor layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit substrate". Moreover, in the manufacture of a printed wiring board, an intermediate product which further forms an insulating layer and / or a conductor layer is also included in the so-called "inner layer substrate" in the present invention. When the printed circuit board is a component-embedded circuit board, an internal substrate with built-in components is used.

The lamination of the inner substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet on the inner substrate from the support side. The resin sheet is used as a member which is heat-pressed on the inner substrate (hereinafter also referred to as “heat-pressed member”), and examples thereof include a heated metal plate (SUS mirror plate, etc.), a metal roller (SUS roller), and the like. In addition, instead of directly pressing the heating and pressing member on the resin sheet, it is preferable that the resin sheet can sufficiently follow the unevenness on the surface of the inner substrate, and it is preferable to press through an elastic material such as a heat-resistant rubber.

The lamination of the inner substrate and the resin sheet can be performed by vacuum lamination. For the vacuum layer method, the heating and pressing temperature is preferably 60 ° C to 160 ° C, preferably in the range of 80 ° C to 140 ° C, and the heating and pressing pressure is preferably 0.098MPa to 1.77MPa, and preferably 0.29MPa to 1.47MPa. The range of the heating and pressing time is preferably 20 seconds to 400 seconds, and more preferably 30 seconds to 300 seconds. Lamination is carried out under reduced pressure at a pressure of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminate. Examples of commercially available vacuum laminates include vacuum pressurized laminates made by Meiki Seisakusho, vacuum applicators made by Nikko Materials Corporation, and batch vacuum pressurized laminates.

After lamination, under normal pressure (atmospheric pressure), for example, by pressing the heating and pressing member from the support side, the laminated resin sheet may be smoothed. The pressing conditions for the smoothing treatment can be set to the same conditions as the heating and pressing conditions for the lamination described above. The smoothing treatment can be performed by a commercially available laminate. The lamination and smoothing treatment can be performed in a continuous manner using the commercially available vacuum laminate.

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

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

The conditions for the thermosetting of the resin composition layer are not particularly limited, and when forming an insulating layer of a printed circuit board, generally used conditions can be used.

For example, the thermal curing conditions of the resin composition layer are different depending on the type of the resin composition, but the curing temperature is preferably 120 ° C to 240 ° C, preferably 150 ° C to 220 ° C, and more preferably 170 ° C to 200 ° C. . The hardening time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 90 minutes.

Before the thermosetting resin composition layer, the resin composition layer may be pre-heated at a lower temperature than the curing temperature. For example, the resin composition layer is first thermally cured at a temperature of 50 ° C to 120 ° C (preferably 60 ° C to 115 ° C, preferably 70 ° C to 110 ° C). 5 minutes or more (preferably 5 minutes to 150 minutes, preferably 15 minutes to 120 minutes, and more preferably 15 minutes to 100 minutes) preheating.

When manufacturing a printed circuit board, (III) a step of punching an insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductive layer may be further performed. These steps (III) to (V) can be carried out by various methods known to those skilled in the art of manufacturing printed circuit boards. Moreover, when the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and Implemented between steps (V). In addition, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) can be repeatedly performed, and a multilayer wiring board can also be formed. At this time, the thickness of the insulating layer (t1 in FIG. 1) between the conductor layers is preferably within the above range.

Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as through holes and through holes in the insulating layer. Step (III) is a combination of the composition of the resin composition used for the formation of the insulating layer, and can be carried out using, for example, a drill, a laser, or a plasma. The size or shape of the hole can be appropriately determined according to the design of the printed circuit board.

Step (IV) is a step of roughening the insulating layer. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions generally used when forming an insulating layer of a printed circuit board can be adopted. For example, the insulating layer may be roughened by a swelling treatment of a swelling liquid, a roughening treatment by an oxidizing agent, and a neutralization treatment by a neutralizing solution. The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkali solution and a surfactant solution. An alkali solution is preferred, and a sodium hydroxide solution and a potassium hydroxide solution are more preferred as the alkali solution. Examples of the sold swelling liquid include "Swelling Dip security Gans P" and "Swelling Dip security Gans SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, and it can be performed, for example, by impregnating the insulating layer with the swelling liquid at 30 ° C. to 90 ° C. for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable that the insulating layer is immersed in a swelling liquid at 40 ° C to 80 ° C for 5 to 15 minutes. The oxidizing agent used for the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment of an oxidant such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in the oxidant solution heated at 60 ° C to 80 ° C for 10 to 30 minutes. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5 mass% to 10 mass%. Examples of the oxidant to be sold include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing solution security Gans P" manufactured by Atotech Japan. The neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution. As a commercially available product, for example, "Reduction solutions security GansP" manufactured by Atotech Japan is mentioned. The treatment with the neutralizing solution can be performed by immersing the treated surface roughened with an oxidizing agent in a neutralizing solution at 30 ° C to 80 ° C for 5 to 30 minutes. From the viewpoints of workability and the like, a method of immersing an object subjected to a roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C to 70 ° C for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. Although the lower limit is not particularly limited, it is preferably 0.5 nm or more, and more preferably 1 nm or more. In addition, the doubled average square root roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited, but is preferably 0.5 nm or more, and more preferably 1 nm or more. The arithmetic average roughness (Ra) and square root mean square root roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

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

The conductive material used for the conductive layer is not particularly limited. In a preferred embodiment, the conductive layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include an alloy of two or more metals selected from the group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). ). Among them, from the viewpoints of versatility, cost, and ease of drawing made of a conductor layer, a separate metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or a nickel-chromium alloy The alloy layers of copper, nickel-copper alloy and copper-titanium alloy are preferred. Separate metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or alloy layers of nickel-chromium alloy are preferred. A separate metal layer of copper is more preferred.

The conductor layer may be a single-layer structure, or may be a single metal layer made of dissimilar metals or alloys, or may be a multi-layer structure in which an alloy layer is laminated in two or more layers. When the conductor layer has a multiple-layer structure, the layer connected to the insulating layer is preferably a separate metal layer of chromium, zinc, or titanium or an alloy layer of a nickel-chromium alloy.

The thickness of the conductor layer is generally from 3 μm to 35 μm, and preferably from 5 μm to 30 μm, depending on the design of the desired printed circuit board.

In one embodiment, the conductive layer can be formed by plating. For example, a conventionally known technique such as semi-additive method and full-additive method can be used to plate the surface of an insulating layer to form a conductor layer having a desired wiring pattern. The former is better. An example in which a conductive layer is formed by a semi-additive method is shown below.

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

Since the resin sheet of the present invention can obtain an insulating layer with good part embedding, the printed circuit board can also be suitably used when a circuit board is built in the part. The component-embedded circuit board can be manufactured by a known manufacturing method.

The printed wiring board manufactured using the resin sheet of the present invention may also be in the form of an insulating layer including a cured product of a resin composition layer of the resin sheet, and an embedded wiring layer embedded in the insulating layer.

[Semiconductor device]
The semiconductor device of the present invention is a printed circuit board containing the present invention. The semiconductor device of the present invention can be manufactured using the printed circuit board of the present invention.

Examples of the semiconductor device include various semiconductor devices such as electric appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trams, ships, and aircraft).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor wafer) at a conductive position of a printed circuit board. The so-called "conducting position" is "a position for transmitting an electric signal in a printed circuit board", and its place may be a surface or an embedded position. The semiconductor wafer is not particularly limited as long as it is only an electric circuit element using a semiconductor as a material.

The method for mounting a semiconductor wafer when manufacturing a semiconductor device is not particularly limited as long as it enables the semiconductor wafer to effectively perform its functions. Specific examples include a wire bond mounting method, a flip chip mounting method, and no bumps. Installation method of cumulative lamination (BBUL), installation method by anisotropic conductive film (ACF), installation method by non-conductive film (NCF), and the like. The so-called "mounting method by bumpless accumulation lamination (BBUL)" means "mounting method of directly embedding a semiconductor wafer into a recessed portion of a printed circuit board and connecting the semiconductor wafer and the wiring on the printed circuit board".

[Example]

The present invention will be specifically described below through examples. The present invention is not limited to these examples. In addition, as shown below, the "parts" and "%" indicating the amount unless otherwise indicated, each indicates "mass part" and "mass%".

[Example 1]
10 parts of a bisphenol type epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., a 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169) and naphthol type epoxy resin ( 50 parts of "ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. (equivalent to about 330) and 40 parts of solvent naphtha are stirred and heated to dissolve. This was cooled to room temperature to prepare a dissolved composition of the epoxy resin (A). In addition, 5 parts of a benzoxazine compound ("JBZ-OP100D" manufactured by JFE Chemical Co., Ltd.) was heated and dissolved while stirring in 5 parts of MEK, and this was further cooled to room temperature to prepare (B) benzoxazine Compound solution.

5 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was mixed with the dissolved composition of this (A) epoxy resin, and triazine 5 parts of phenolic hardener ("LA-3018-50P" manufactured by DIC Corporation, approximately 151 active group equivalent, 2-methoxypropanol solution with 50% solids content), active ester compound (DIC "HPC-8000-65T" manufactured by the company, active ingredient equivalent of about 223, solid content 65% by weight toluene solution) 50 parts, hardening accelerator (1-benzyl-2-phenylimidazole (1B2PZ), solid content 10 5 parts by mass of MEK solution), spherical silica (average particle size 0.77 μm, specific surface area 5.9 m ² / g, surface-treated silica) with amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 250 parts of "SO-C2" (manufactured by Admatechs) and 10 parts of (B) benzoxazine compound solution were uniformly dispersed by a high-speed rotating mixer to produce a resin paint.

As a support, a polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness: 38 µm) was prepared with a release layer. The thickness of the resin composition layer after the aforementioned resin coating was uniformly applied to the release layer of the support was 25 μm. Thereafter, the resin paint was dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 4 minutes to obtain a resin sheet containing a support and a resin composition layer.

<Measurement of average particle diameter of inorganic filler>
100 mg of the inorganic filler, 0.1 g of a dispersant ("SN9228" manufactured by Sannopco), and 10 g of methyl ethyl ketone were weighed out and placed in a sample bottle, and dispersed for 20 minutes by ultrasonic waves. Using a laser diffraction particle size distribution measuring device ("SALD-2200" manufactured by Shimadzu Corporation), the particle size distribution was measured in a batch unit method, and the average particle size as a median diameter was calculated.

[Example 2]
In Example 1, 50 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, an active group equivalent of about 223, and a 65% by mass solid solution in toluene) was changed to an active ester compound ("EXB8000L- manufactured by DIC Corporation"). "65TM", active group equivalent 220, solid solution 65% toluene ･ MEK mixed solution) 50 parts. Except for the above matters, a resin paint and a resin sheet were produced in the same manner as in Example 1.

[Example 3]
In Example 1, 50 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, an active group equivalent of about 223, and a 65% by mass solid content toluene solution) were changed to an active ester compound ("EXB8150- manufactured by DIC Corporation" 60T ", active group equivalent 230, solid solution 60% toluene solution) 55 parts. Except for the above matters, a resin paint and a resin sheet were produced in the same manner as in Example 1.

[Comparative Example 1]
In Example 1, the amount of spherical silica (average particle size 0.77 μm, "SO-C2" manufactured by Admatechs) was surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.). From 250 parts to 240 parts, benzoxazine compounds ("JBZ-OP100D" manufactured by JFE Chemical Co., Ltd.) were not used. Except for the above matters, a resin paint and a resin sheet were produced in the same manner as in Example 1.

[Comparative Example 2]
In Example 2, the amount of spherical silica (average particle diameter 0.77 μm, "SO-C2" manufactured by Admatechs) was surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.). 250 parts were changed to 240 parts, and the benzoxazine compound ("JBZ-OP100D" by JFE Chemical Co., Ltd.) was not used. Except for the above matters, a resin paint and a resin sheet were produced in the same manner as in Example 1.

[Comparative Example 3]
In Example 3, the amount of spherical silica (average particle diameter 0.77 μm, "SO-C2" manufactured by Admatechs) was subjected to surface treatment with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 250 parts were changed to 240 parts, and the benzoxazine compound ("JBZ-OP100D" by JFE Chemical Co., Ltd.) was not used. Except for the above matters, a resin paint and a resin sheet were produced in the same manner as in Example 1.

[assessment method]
The resin sheets obtained in the above examples and comparative examples were evaluated by the following methods.

＜ Measurement of peeling strength ＞
(Fabrication of Evaluation Board)
(1) Basic processing of built-in substrate:
As the inner substrate, a double-sided copper-clad laminate with epoxy resin on a glass cloth substrate having a copper foil on the surface (copper foil thickness of 18 μm, substrate thickness of 0.8 mm, and “R1515A” manufactured by Panasonic Corporation) was prepared. All the copper foils on the surface of the inner substrate were removed by etching. Then, it dried at 190 degreeC for 30 minutes.

(2) Lamination of resin sheet:
The resin sheets obtained in the above examples and comparative examples were batch-type vacuum-pressed laminates (two-stage cumulative laminates "CVP700" manufactured by Nikko Materials Co., Ltd.), and the resin composition layer was to be connected to the aforementioned inner substrate. The lower layer is laminated on both sides of the inner substrate. This lamination was carried out by setting the pressure of the depressurization for 30 seconds to 13 hPa or less, and then performing the pressing for 30 seconds at a temperature of 100 ° C and a pressure of 0.74 MPa.
Next, the laminated resin sheet was smoothed by hot pressing at 100 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure. Thereafter, the support was peeled off to obtain "intermediate laminate I" contained in the order of the resin composition layer, the inner substrate, and the resin composition layer.

In addition, a copper foil having a glossy surface (35 μm in thickness, “3EC-III” manufactured by Mitsui Metals Co., Ltd.) was prepared. The glossy surface of this copper foil was etched using a micro-etching agent ("CZ8101" manufactured by MEC Corporation) at a copper etching amount of 1 m, and roughened. The copper foil thus obtained is called "roughened copper foil".

The roughened copper foil is laminated on both sides of the intermediate multilayer body I, and is connected to the resin composition layer of the intermediate multilayer body I to which the roughened copper foil is subjected to a roughening treatment. This lamination is performed under the same conditions as the aforementioned lamination of the resin sheet for the inner substrate. Thereby, the "intermediate multilayer body II" contained in the order of roughened copper foil, a resin composition layer, an inner-layer substrate, a resin composition layer, and a roughened copper foil was obtained.

This intermediate multilayer body I was put into an oven at 100 ° C for 30 minutes for heating, and then transferred to an oven at 170 ° C for 30 minutes for heating. Next, the intermediate multilayer body II was taken out of the oven to make it a room temperature environment, and then put into a 200 ° C oven for additional heating for 90 minutes. Thereby, the resin composition layer is thermally cured to obtain a roughened copper foil, an insulation layer as a hardened material of the resin composition layer, an inner substrate, an insulation layer as a hardened material of the resin composition layer, and roughened copper. "Evaluation substrate A" contained in the order of the foil. In this evaluation substrate A, the roughened copper foil corresponds to a conductor layer.

(Measurement of peel strength before environmental test (HAST test))
Using the aforementioned evaluation substrate A, the peel strength of the roughened copper foil and the insulating layer was measured. The measurement of the peeling strength is performed in accordance with JIS C6481. Specifically, the peeling strength was measured by the following operation.

For the roughened copper foil of the evaluation substrate A, a rectangular portion with a width of 10 mm and a length of 100 mm was cut out. One end of the rectangular portion was peeled off, and it was caught with a jig (Autocom type testing machine "AC-50C-SL" manufactured by TSEE). The rectangular portion having a length of 35 mm was peeled in a vertical direction, and the load (kgf / cm) during the peeling was measured as the peel strength before the HAST test. The aforementioned peeling is performed at a speed of 50 mm / min at room temperature.

(Measurement of peel strength after environmental test (HAST test))
Thereafter, the evaluation substrate A was left for 100 hours under an environment of a temperature of 130 ° C. and a humidity of 85% RH to perform a HAST test. After the HAST test was performed, the evaluation of the peel strength of the roughened copper foil and the insulating layer of the substrate A was measured by the same method as before the HAST test.

<Evaluation of Smudge Removability>
(1) Basic processing of built-in substrate:
As the inner substrate, a double-sided copper-clad laminate with epoxy resin on a glass cloth substrate having a copper foil on the surface was prepared (the thickness of the copper foil was 18 μm, the thickness of the substrate was 0.8 mm, and “R1515A” manufactured by Panasonic Corporation) was prepared. The copper foil on the surface of this inner layer substrate was etched with a micro-etching agent ("CZ8101" manufactured by MEC Corporation) at a copper etching amount of 1 m, and roughened. Thereafter, it was dried at 190 ° C for 30 minutes.

(2) Lamination and hardening of resin sheet:
The resin sheets obtained in the above examples and comparative examples were laminated on both sides of an inner layer substrate using a batch type vacuum pressurized laminate (a two-stage cumulative laminate "CVP700" manufactured by Nikko Materials Corporation). The physical layer is bonded to the aforementioned inner substrate. This lamination was decompressed for 30 seconds, and the air pressure was set to 13 hPa or less. The lamination was carried out by pressing for 30 seconds at a temperature of 100 ° C and a pressure of 0.74 MPa.

Next, the laminated resin sheet was hot-pressed at a pressure of 0.5 MPa for 60 seconds at 100 ° C. under atmospheric pressure to smooth it. This was further put into an oven at 100 ° C for 30 minutes, and then transferred to an oven at 170 ° C for 30 minutes.

(3) Formation of through holes:
A CO ₂ laser processing machine (LK-2K212 / 2C) manufactured by Viamechanics was used to process the insulating layer at a frequency of 2000 Hz with a pulse width of 3 μs, input of 0.95 W, and a strike number of 3 to form an insulating layer on the surface of the insulating layer. A through hole having a top diameter (diameter) of 50 μm and a diameter of 40 μm in the bottom surface of the insulating layer. Thereafter, the support was further peeled to obtain a circuit board.

(4) Roughening:
The surface of the insulation layer of the circuit board was immersed in a swelling solution of Swelling Dip security GansP manufactured by Atotech Japan at 60 ° C for 10 minutes. Next, the surface of the insulation layer of the circuit board was immersed in a roughened solution of Concentrate · CompactP (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) manufactured by Atotech Japan Co., Ltd. at 80 ° C. for 25 minutes. Finally, the surface of the insulation layer of the circuit substrate was immersed in a neutralization solution of Reduction solutions Security GansP manufactured by Atotech Japan for 5 minutes at 40 ° C.

(5) Evaluation of the residue at the bottom of the through hole:
The periphery of the bottom of the through-hole was observed with a scanning electron microscope (SEM), and the maximum stain length from the wall surface of the bottom of the through-hole was measured from the obtained image, and evaluated based on the following criteria.
○: The maximum stain length is less than 5 μm
×: The maximum smear length is 5 μm or more

[result]
The results of the above examples and comparative examples are shown in the following table. In the following table, the amount of each component is expressed as a non-volatile component conversion amount.

In Examples 1 to 3, even if the components (D) to (F) were not contained, there was a certain degree of difference, but it was confirmed that the results were the same as those in the above examples.

1‧‧‧ the first conductor layer

11‧‧‧ Main surface of the first conductor layer

2‧‧‧ 2nd conductor layer

21‧‧‧ The main surface of the second conductor layer

3‧‧‧ Insulation

t1‧‧‧The distance between the first conductor layer and the second conductor layer (the thickness of the insulation layer between the first and second conductor layers)

t2‧‧‧All thickness of insulation layer

[FIG. 1] FIG. 1 is a partial cross-sectional view showing an example of a printed circuit board as a pattern.

Claims (13)

A resin composition is a resin composition containing (A) an epoxy resin, (B) a benzoxazine compound, and (C) an inorganic filler, wherein the (B) component is represented by the following general formula (B-1) ) Indicates that the content of the component (C) is 67% by mass or more when the nonvolatile component in the resin composition is 100% by mass; In the formula (B-1), R ¹ represents an n-valent group containing an oxygen atom, R ² each independently represents a halogen atom, an alkyl group, or an aryl group; n represents an integer of 2 to 4; and m represents an integer of 0 to 4. For example, if the content of the component (B) in the resin composition of claim 1 is set to 100% by mass of the nonvolatile component in the resin composition, it is 0.1% by mass to 10% by mass. The resin composition according to claim 1, further comprising (D) an active ester compound. For example, in the resin composition of claim 3, when the content of the (D) component is 100% by mass of the nonvolatile component in the resin composition, it is 5% by mass or more. The resin composition according to claim 1, wherein the average particle diameter of the (C) inorganic filler is 0.5 μm or more. For example, the resin composition of claim 1, wherein in the general formula (B-1), R ¹ is an n-valent group formed by a combination of an oxygen atom and an arylene group. The resin composition according to claim 1, wherein m represents 0 in the general formula (B-1). The resin composition according to claim 1, which is used for forming an insulating layer of a printed circuit board. The resin composition according to claim 1, which is used for forming an interlayer insulation layer of a printed circuit board. A resin sheet comprising a support and a resin composition layer formed on the support with a resin composition as claimed in claim 1. The resin sheet according to claim 10, wherein the thickness of the resin composition layer is 25 μm or less. A printed circuit board comprising a first conductor layer, a second conductor layer, and an insulation layer formed between the first conductor layer and the second conductor layer, characterized in that the insulation layer is as described in claims 1 to 9 A cured product of any one of the resin compositions. A semiconductor device comprising a printed circuit board as claimed in claim 12.