JP2022176199A - Resin sheet, and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that can give a cured body capable of suppressing generation of a via bottom void in conductor layer formation by sputtering and is excellent in film handling ability, and to provide a resin sheet or the like containing the resin composition.

SOLUTION: A resin sheet laminated on an inner layer substrate so as to bond to the inner layer substrate includes a support medium, and a resin composition layer that is set on the support medium and contains a resin composition. The resin composition contains a liquid or semisolid thermosetting resin (A-1) and a thermoplastic resin (B), and contains or does not contain an inorganic filler (C). The content of the inorganic filler (C) is 40 mass% or less relative to 100 mass% of nonvolatile components in the resin composition. The inorganic filler (C) has a specific surface area of 40 m²/g or more. The resin composition layer has a lowest melt viscosity of 100 poise or higher and 4,000 poise or lower.

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

The present invention relates to resin compositions. Furthermore, it relates to a resin sheet, a printed wiring board, a semiconductor device, and a method for producing a printed wiring board containing the resin composition.

2. Description of the Related Art In recent years, electronic devices have become more compact and have higher performance. In multilayer printed wiring boards, build-up layers have been multi-layered, and wiring has become finer and denser. As a conductor forming method, for example, a semi-additive method of forming a conductor layer by electroless plating and electrolytic plating is known. The adhesion between the insulating layer and the plated conductor layer is affected by the degree of unevenness formed by the roughening treatment of the insulating layer. can be considered.

However, when the roughness of the surface of the insulating layer is large, the limitation on the width between circuits formed on the surface is inevitably large, which is disadvantageous for high-density wiring. Therefore, in order to increase the wiring density, there is a demand for a method of forming a conductor layer on the surface of an insulating layer which is excellent in adhesion even if the roughness after the roughening treatment is small.

In Patent Document 1, an adhesive film in which a resin composition layer is formed on a support film is laminated on a circuit board, the support film is peeled off after the resin composition layer is thermally cured, and a sputtering method is applied to the surface of the insulating layer. Disclosed is a method for manufacturing a multilayer printed wiring board in which the conductor layer exhibits high peel strength in spite of the relatively low roughness by forming the conductor layer by the method. In addition, in Patent Document 2, in order to eliminate the mismatch between the thermal expansion coefficients of the insulating layer and the copper wiring, a high amount of inorganic filler is added to the resin composition. It is described to obtain high peel strength despite relatively low roughness to accommodate.

JP 2007-273615 A JP 2015-150885 A

As a result of further studies by the present inventors, when a dry roughening process is performed after forming a via hole in a conventional insulating layer containing an inorganic filler, it remains at the bottom of the via hole (via bottom) It has been found that the inorganic filler cannot be removed and remains as it is. After that, when an attempt is made to form a conductor layer by sputtering, voids are generated in places where the inorganic filler remains because the formation of the conductor layer is hindered, and fine wiring formability and conduction reliability deteriorate ( occurrence of via bottom voids).

On the other hand, if the amount of the inorganic filler is low in order to facilitate the formation of fine wiring, the stability of thickness control is lost when a resin sheet formed from the resin composition is laminated on a circuit board such as a printed wiring board. As a result, the resin composition tends to ooze out, resulting in inferior film handleability. In addition, when a resin sheet is laminated on the fine wiring and cured, the resin sheet becomes difficult to follow the fine wiring, and voids, which are appearance defects, may occur between the fine wiring and the resin sheet. , the film handleability may be inferior.

Accordingly, an object of the present invention is to provide a resin composition capable of obtaining a cured product capable of suppressing the generation of voids at the bottom of vias in the formation of a conductor layer by sputtering and having excellent film handleability; To provide a resin sheet, a printed wiring board, a semiconductor device, and a method for manufacturing a printed wiring board containing

As a result of intensive studies on the above problems, the inventors of the present invention have found that the above problems can be solved, and completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition for forming an insulating layer for forming a conductor layer by sputtering,
(A-1) a liquid or semi-solid thermosetting resin, and (B) a thermoplastic resin,
(C) does not contain or contains inorganic fillers;
(C) the content of the inorganic filler is 50% by mass or less when the non-volatile component in the resin composition is 100% by mass;
(C) A resin composition in which the inorganic filler has a specific surface area of 40 m ² /g or more.
[2] The resin composition according to [1], wherein the content of the resin component is 50% by mass or more when the non-volatile component in the resin composition is taken as 100% by mass.
[3] The resin composition according to [1] or [2], wherein component (A-1) is at least one selected from epoxy resins, (meth)acrylic resins, amine-based resins, and allyl-based resins.
[4] Any one of [1] to [3], wherein the content of component (A-1) is 5% by mass or more and 30% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to .
[5] The resin composition according to any one of [1] to [4], wherein component (B) is at least one selected from polyimide resins, polycarbonate resins and phenoxy resins.
[6] Any one of [1] to [5], wherein the content of the component (B) is 10% by mass or more and 50% by mass or less when the non-volatile component in the resin composition is 100% by mass. of the resin composition.
[7] The resin composition according to any one of [1] to [6], wherein component (C) is silica.
[8] (A-2) The resin composition according to any one of [1] to [7], further comprising a solid thermosetting resin.
[9] The resin composition according to [8], wherein component (A-2) is at least one of a cyanate ester resin, a carbodiimide resin, and a maleimide resin.
[10] The resin composition according to any one of [1] to [9], which is used for forming an insulating layer of a multilayer printed wiring board.
[11] A resin sheet for forming an insulating layer for forming a conductor layer by sputtering,
comprising a support and a resin composition layer containing a resin composition provided on the support;
The resin composition contains (A) a thermosetting resin and (B) a thermoplastic resin, does not contain or contains (C) an inorganic filler, and the content of the (C) inorganic filler is the resin composition When the nonvolatile component in the inside is 100% by mass, it is 50% by mass or less, and the specific surface area of (C) the inorganic filler is 40 m ² /g or more,
A resin sheet in which the resin composition layer has a minimum melt viscosity of 100 poise or more and 4000 poise or less.
[12] A resin sheet comprising a support and a resin composition layer containing the resin composition according to any one of [1] to [10] provided on the support.
[13] An insulating layer formed of a cured product of the resin composition according to any one of [1] to [10], or a cured product of the resin composition layer of the resin sheet according to [11] or [12]. printed wiring boards, including;
[14] (1) A step of laminating the resin composition layer of the resin sheet according to [11] or [12] on the inner layer substrate so as to be bonded to the inner layer substrate;
(2) thermosetting the resin composition layer to form an insulating layer;
(3) A method of manufacturing a printed wiring board, comprising the steps of: (3) forming holes in an insulating layer; and (4) forming a conductor layer on the insulating layer by sputtering.
[15] A semiconductor device including the printed wiring board according to [13].

According to the present invention, in the formation of a conductor layer by sputtering, it is possible to obtain a cured product capable of suppressing the generation of voids at the bottom of vias, and the resin composition is excellent in film handleability; It is possible to provide a resin sheet, a printed wiring board, a semiconductor device, and a method for manufacturing a printed wiring board.

FIG. 1 is a schematic side view showing an example of two test tubes used for determining whether a thermosetting resin is liquid, semi-solid, or solid.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

[Resin composition]
The resin composition of the present invention contains (A-1) a liquid or semi-solid thermosetting resin, and (B) a thermoplastic resin, (C) does not contain or contains an inorganic filler, and (C (C) The inorganic filler has a specific surface area of 40 m ² /g or more; Moreover, the resin composition of the present invention is suitable as a resin composition for forming an insulating layer for forming a conductor layer by sputtering. By using such a resin composition, it is possible to obtain a cured product capable of suppressing the generation of via bottom voids in the formation of a conductor layer by sputtering, and to obtain a resin sheet excellent in film handleability. will be available. Furthermore, in the formation of a conductor layer by sputtering, uneven roughened surfaces such as unevenness caused by inorganic fillers and distortion due to thermal expansion mismatch between the copper wiring and the insulating layer greatly affect the yield of fine wiring formation. However, by using such a resin composition, it is possible to obtain a cured product having a low arithmetic mean roughness Ra and a low coefficient of linear thermal expansion, which also contributes to the formation of fine wiring.

The resin composition may contain, in combination with the components (A-1) and (B), any component other than the inorganic filler (C). Examples of optional components include (A-2) a solid thermosetting resin, (D) a curing accelerator, and (E) other additives. Each component contained in the resin composition will be described in detail below.

In this specification, the components (A-1) and (A-2) are sometimes collectively referred to as "(A) thermosetting resin". Further, in this specification, the term “resin component” refers to components excluding (C) the inorganic filler among the components constituting the resin composition.

<(A) Thermosetting resin>
(A) As the thermosetting resin, a thermosetting resin that is used when forming an insulating layer of a wiring board can be used. Examples of such thermosetting resins include epoxy resins, (meth)acrylic resins, maleimide resins, phenolic resins, naphthol-based resins, benzoxazine-based resins, active ester-based resins, cyanate ester-based resins, and carbodiimide-based resins. , amine-based resins, allyl-based resins, acid anhydride-based resins, and the like. The term "(meth)acrylic resin" includes acrylic resins and methacrylic resins.

(A) The thermosetting resin may be used singly or in combination of two or more. Here, epoxy resins, (meth) A component that reacts with the acrylic resin and the maleimide resin to cure the resin composition may be collectively referred to as a "curing agent".

The term "(A) thermosetting resin" includes (A-1) liquid or semi-solid thermosetting resin and (A-2) solid thermosetting resin. Here, liquid, semi-solid, and solid state judgments are made according to Attachment No. 2 "Confirmation method of liquid state" of Ministerial Ordinance Concerning Testing and Properties of Hazardous Substances (Ministry of Home Affairs Ordinance No. 1 of 1989). A specific determination method is as follows.

(1) Device constant temperature water bath:
A device equipped with a stirrer, a heater, a thermometer, and an automatic temperature controller (capable of temperature control at ±0.1° C.) and having a depth of 150 mm or more is used.
In addition, in the determination of the thermosetting resin used in the examples described later, a combination of a low temperature constant temperature water tank (model BU300) and an injection type constant temperature device Thermomate (model BF500) manufactured by Yamato Scientific Co., Ltd. was used. Put 22 liters in a low temperature constant temperature water tank (model BU300), turn on the power of Thermomate (model BF500) assembled in this, set the temperature to the set temperature (20 ° C. or 60 ° C.), and set the water temperature ± 0.1 The temperature was finely adjusted with Thermomate (Model BF500), but any device capable of similar adjustment can be used.

Test tube:
As shown in FIG. 1, the test tube was made of flat-bottomed transparent glass with an inner diameter of 30 mm and a height of 120 mm. A rubber stopper 13b having the same size, a similarly marked line, and a hole in the center for inserting and supporting a thermometer. The opening of the test tube is sealed with , and a temperature measuring test tube 10b having a thermometer 14 inserted into a rubber plug 13b is used. Hereinafter, a marked line at a height of 55 mm from the tube bottom is referred to as "A line", and a marked line at a height of 85 mm from the tube bottom is referred to as "B line".
As the thermometer 14, the one for measuring the freezing point (SOP-58 scale range 0 to 100 ° C.) specified in JIS B7410 (1982) "Petroleum test glass thermometer" is used, but the temperature of 0 to 100 ° C. It is sufficient if the range can be measured.

(2) Test procedure A sample left at a temperature of 60 ± 5 ° C. under atmospheric pressure for 24 hours or more is subjected to a liquid determination test tube 10a shown in FIG. 1(a) and a temperature measurement test shown in FIG. The tubes 10b are each fed up to line 11A. The two test tubes 10a and 10b are placed upright in a low temperature constant temperature water bath so that the line 12B is below the surface of the water. The lower end of the thermometer should be 30 mm below the 11A line.
After the sample temperature reaches the set temperature ±0.1°C, the state is kept as it is for 10 minutes. After 10 minutes, take out the test tube 10a for judging the liquid state from the low-temperature constant temperature water bath, immediately lay it horizontally on a horizontal test table, and use a stopwatch to measure the time when the tip of the liquid surface in the test tube moves from line 11A to line 12B. Measure and record.

Similarly, the sample left at a temperature of 20 ± 5°C under atmospheric pressure for 24 hours or more was also tested in the same manner as when left at a temperature of 60 ± 5°C under atmospheric pressure for 24 hours or more. The time taken by the tip of the surface to move from line 11A to line 12B is measured with a stopwatch and recorded.

If the measured time is within 90 seconds at 20° C., it is determined to be liquid.
A semi-solid state is determined when the measured time exceeds 90 seconds at 20°C and the measured time does not exceed 90 seconds at 60°C.
If the measured time exceeds 90 seconds at 60° C., it is determined to be solid.
The components (A-1) and (A-2) are described below.

-(A-1) Liquid or semi-solid thermosetting resin-
The resin composition contains a liquid or semi-solid thermosetting resin as component (A-1). By including the component (A-1) in the resin composition, the minimum melt viscosity can be lowered and the embedding properties can be improved, resulting in improved film handleability.

Component (A-1) is, for example, preferably at least one selected from epoxy resins, (meth)acrylic resins, amine-based resins, and allyl-based resins, and epoxy resins and (meth)acrylic resins. At least one selected is more preferable.

The liquid or semi-solid epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. Moreover, the epoxy resin preferably has an aromatic structure, and when two or more epoxy resins are used, at least one of them more preferably has an aromatic structure. Aromatic structures are chemical structures generally defined as aromatic and also include polycyclic aromatic and heteroaromatic rings. The ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass with respect to 100% by mass of the non-volatile components of the epoxy resin. % or more.

Liquid epoxy resins and semi-solid epoxy resins include glycylol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins. Resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexanedimethanol type epoxy resins, and epoxy resins having a butadiene structure are preferred, and glycyrrol type epoxy resins, bisphenol A type epoxy resins, and bisphenol F type epoxy resins. Epoxy resins are more preferred. Specific examples of liquid epoxy resins and semi-solid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US" and "jER828EL" manufactured by Mitsubishi Chemical Corporation ( bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin); "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, ADEKA "ED-523T" (glycirrol type epoxy resin (ADEKA GLYCIROL)), "EP-3980S" (glycidylamine type epoxy resin), "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd. & Materials Co., Ltd. "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX Co., Ltd. "EX-721" (glycidyl ester type epoxy resin); Daicel Co., Ltd. "Celoxide 2021P” (alicyclic epoxy resin having an ester skeleton), “PB-3600” (epoxy resin having a butadiene structure); “ZX1658” and “ZX1658GS” (liquid 1,4-glycidyl cyclohexane), "ELM-100" manufactured by Sumitomo Chemical Co., Ltd., and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The epoxy equivalent of the liquid or semi-solid epoxy resin is preferably 50 g/eq. ~5000g/eq. , more preferably 50 g/eq. ~3000g/eq. , more preferably 80 g/eq. ~2000 g/eq. , even more preferably 110 g/eq. ~1000g/eq. is. Within this range, the crosslink density of the cured product is sufficient, and an insulating layer with a small surface roughness can be obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing one equivalent of epoxy groups.

The liquid or semisolid epoxy resin preferably has a weight average molecular weight of 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. Here, the weight average molecular weight of the epoxy resin is the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

The liquid or semi-solid (meth)acrylic resin preferably has two or more (meth)acryloyl groups per molecule from the viewpoint of significantly obtaining the desired effects of the present invention. The term "(meth)acryloyl group" includes acryloyl groups and methacryloyl groups and combinations thereof.

The liquid or semi-solid (meth)acrylic resin preferably has a cyclic structure from the viewpoint of significantly obtaining the desired effects of the present invention. As the cyclic structure, a divalent cyclic group is preferred. The divalent cyclic group may be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Among them, a cyclic group containing an alicyclic structure is preferable from the viewpoint of significantly obtaining the desired effects of the present invention.

From the viewpoint of significantly obtaining the desired effect of the present invention, the divalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, still more preferably a 5-membered ring or more, and preferably a 20-membered ring. Below, it is more preferably a 15-membered ring or less, still more preferably a 10-membered ring or less. Moreover, the divalent cyclic group may have a monocyclic structure or a polycyclic structure.

The ring in the divalent cyclic group may have a ring skeleton composed of heteroatoms other than carbon atoms. The heteroatom includes, for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc., and an oxygen atom is preferred. The ring may have one heteroatom, or may have two or more.

Specific examples of divalent cyclic groups include the following divalent groups (i) to (xi). Among them, (x) or (xi) is preferable as the divalent cyclic group.

The bivalent cyclic group may have a substituent. Examples of such substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, arylalkyl groups, silyl groups, acyl groups, acyloxy groups, carboxy groups, sulfo groups, cyano groups, nitro groups, hydroxy groups, A mercapto group, an oxo group and the like can be mentioned, and an alkyl group is preferred.

The (meth)acryloyl group may be directly bonded to the divalent cyclic group, or may be bonded via a divalent linking group. Examples of divalent linking groups include alkylene groups, alkenylene groups, arylene groups, heteroarylene groups, -C(=O)O-, -O-, -NHC(=O)-, and -NC(=O). Examples include N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, and -NH-, and may be a group combining a plurality of these. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms. is more preferred. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, 1,1-dimethylethylene group and the like. - dimethylethylene group is preferred. The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and even more preferably an alkenylene group having 2 to 5 carbon atoms. As the arylene group and heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferable. As the divalent linking group, an alkylene group is preferable, and a methylene group and a 1,1-dimethylethylene group are particularly preferable.

（式（１）中、Ｒ^１及びＲ^４はそれぞれ独立にアクリロイル基又はメタクリロイル基を表し、Ｒ^２及びＲ^３はそれぞれ独立に２価の連結基を表す。環Ａは、２価の環状基を表す。） The liquid or semi-solid (meth)acrylic resin is preferably represented by the following formula (1).

(In formula (1), R ¹ and R ⁴ each independently represent an acryloyl group or a methacryloyl group, R ² and R ³ each independently represent a divalent linking group. Ring A is a divalent cyclic group. represents.)

R ¹ and R ⁴ each independently represent an acryloyl group or a methacryloyl group, preferably an acryloyl group.

R ² and R ³ each independently represent a divalent linking group. The divalent linking group is the same as the above divalent linking group.

Ring A represents a divalent cyclic group. Ring A is the same as the divalent cyclic group described above.

Ring A may have a substituent. The substituent is the same as the substituent that the divalent cyclic group may have.

Specific examples of the liquid or semi-solid (meth)acrylic resin include the following, but the present invention is not limited thereto.

Liquid or semi-solid (meth)acrylic resins may be commercially available products, for example, "A-DOG" ((meth)acryloyl group equivalent 163) manufactured by Shin-Nakamura Chemical Co., Ltd., manufactured by Kyoeisha Chemical Co., Ltd. "DCP-A" ((meth) acryloyl group equivalent 152), Nippon Kayaku "NPDGA" ((meth) acryloyl group equivalent 106), "FM-400" ((meth) acryloyl group equivalent 156), " R-687" ((meth) acryloyl group equivalent 187), "THE-330" ((meth) acryloyl group equivalent 143), "PET-30" ((meth) acryloyl group equivalent 88), "DPHA" ((meth) ) acryloyl group equivalent weight 96) and the like.

The (meth)acryloyl group equivalent of the liquid or semisolid (meth)acrylic resin is preferably 30 g/eq. from the viewpoint of significantly obtaining the desired effects of the present invention. ~400 g/eq. , more preferably 50 g/eq. ~300 g/eq. , more preferably 75 g/eq. ~200 g/eq. is. A (meth)acryloyl group equivalent is the mass of a (meth)acrylic resin containing one equivalent of a (meth)acryloyl group.

A liquid or semi-solid allyl-based resin is a compound having at least one allyl group in the molecule. The allyl-based resin preferably has one or more allyl groups per molecule, more preferably two or more allyl groups. Moreover, the allyl-based resin preferably has either an isocyanuric ring structure or a benzoxazine ring structure in addition to the allyl group, from the viewpoint of significantly obtaining the desired effects of the present invention. In the allyl-based resin having an isocyanuric structure, the nitrogen atom of the isocyanuric structure and the allyl group are preferably directly bonded. Moreover, the allyl-based resin having a benzoxazine ring is preferably bonded to either the nitrogen atom of the benzoxazine ring or the benzene ring, and more preferably bonded to the nitrogen atom. Examples of such resins include allyl isocyanurate, diallyl isocyanurate, and triallyl isocyanurate.

Commercially available liquid or semi-solid allyl-based resins may be used, and examples thereof include "L-DAIC" manufactured by Shikoku Kasei Co., Ltd., and "ALP-d" manufactured by JFE Chemical.

The allyl group equivalent of the liquid or semi-solid allyl resin is preferably 20 g/eq. from the viewpoint of significantly obtaining the desired effects of the present invention. ~1000 g/eq. , more preferably 50 g/eq. ~500 g/eq. , more preferably 100 g/eq. ~300 g/eq. is. The allyl group equivalent is the mass of the allyl-based resin containing one equivalent of allyl groups.

As the liquid or semi-solid amine-based resin, a resin having one or more amino groups in one molecule can be used. Liquid or semi-solid amine resins include, for example, aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, the desired effects of the present invention are exhibited. From this point of view, aromatic amines are preferred. The amine-based resin is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of amine resins include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine. , m-xylylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3 ,3′-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4 -aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4′-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy) ) phenyl) sulfone, and the like. Commercially available amine-based resins may be used. AS", Mitsubishi Chemical's "Epicure W", and the like.

The amino group equivalent of the liquid or semi-solid amine resin is preferably 20 g/eq. from the viewpoint of significantly obtaining the desired effects of the present invention. ~1000g/eq. , more preferably 50 g/eq. ~500 g/eq. , more preferably 100 g/eq. ~300 g/eq. is. An amino group equivalent is the mass of an amine-based resin containing one equivalent of an amino group.

The content of the component (A-1) is preferably 1% by mass when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of being able to lower the minimum melt viscosity and improving the embedding property. Above, more preferably 3% by mass or more, still more preferably 5% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, 25% by mass or less, 20% by mass % or less and 15% by mass or less. In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass, unless otherwise specified.

When the component (A-1) contains either an epoxy resin or a (meth)acrylic resin, the content of the epoxy resin and the (meth)acrylic resin as the component (A-1) reduces the minimum melt viscosity. From the viewpoint of improving the embedding property, when the non-volatile component in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. Yes, preferably 30 mass % or less, more preferably 25 mass % or less, still more preferably 20 mass % or 15 mass % or less.

When the component (A-1) contains a curing agent, the content of the curing agent as the component (A-1) is determined from the viewpoint of reducing the minimum melt viscosity and improving the embedding property of the resin composition. When the non-volatile component in the medium is 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, preferably 40% by mass or less, more preferably 30% by mass. 25% by mass or less, more preferably 25% by mass or less.

-(A-2) Solid thermosetting resin-
The resin composition may further contain a solid thermosetting resin as an optional component (A-2). Inclusion of the component (A-2) in the resin composition can further improve film handleability.

Component (A-2) includes, for example, epoxy resins, maleimide resins, phenolic resins, naphthol-based resins, active ester-based resins, cyanate ester-based resins, carbodiimide-based resins, benzoxazine-based resins, acid anhydride-based resins, and the like. Epoxy resins, cyanate ester resins, carbodiimide resins and maleimide resins are preferred, and at least one of cyanate ester resins, carbodiimide resins and maleimide resins is more preferred.

The solid epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. Moreover, the epoxy resin preferably has an aromatic structure, and when two or more epoxy resins are used, at least one of them more preferably has an aromatic structure. The ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass with respect to 100% by mass of the non-volatile components of the epoxy resin. % or more.

Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin and tetraphenylethane type epoxy resin are preferred, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin and biphenyl type epoxy resin are more preferred. Specific examples of solid epoxy resins include DIC's "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" ( cresol novolak type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200" "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311" , "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (Tris phenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" manufactured by Nippon Steel Chemical & Materials Co., Ltd. (naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation ), “YX8800” (anthracene type epoxy resin); “PG-100” and “CG-500” manufactured by Osaka Gas Chemicals Co., Ltd., “YL7760” manufactured by Mitsubishi Chemical Corporation (bisphenol AF type epoxy resin), “YL7800” ( fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin) and the like.

The epoxy equivalent weight and weight average molecular weight of solid epoxy resins are similar to those of liquid or semi-solid epoxy resins.

A solid maleimide resin is a compound containing a maleimide group represented by the following formula (2) in the molecule.

From the viewpoint of significantly obtaining the desired effects of the present invention, the number of maleimide groups per molecule of the maleimide resin is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. is 10 or less, more preferably 6 or less, particularly preferably 3 or less.

From the viewpoint of significantly obtaining the desired effects of the present invention, the maleimide resin preferably has either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and has an aliphatic hydrocarbon group and an aromatic hydrocarbon group. is more preferable.

The aliphatic hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, more preferably a divalent saturated aliphatic hydrocarbon group, and still more preferably an alkylene group. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, an alkylene group having 1 to 3 carbon atoms is more preferable, and a methylene group is particularly preferable.

The aromatic hydrocarbon group is preferably a monovalent or divalent aromatic hydrocarbon group, more preferably an aryl group or an arylene group. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferable, an arylene group having 6 to 20 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is even more preferable. Examples of such an arylene group include a phenylene group, a naphthylene group, an anthracenylene group, an aralkyl group, a biphenylene group, and a biphenylaralkyl group. A phenylene group, an aralkyl group, and a biphenylene group are more preferred. The aryl group is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, even more preferably an aryl group having 6 to 10 carbon atoms, and particularly preferably a phenyl group.

In the maleimide resin, from the viewpoint of significantly obtaining the desired effects of the present invention, the nitrogen atom of the maleimide group is preferably directly bonded to a monovalent or divalent aromatic hydrocarbon group. Here, "directly" means that there is no other group between the nitrogen atom of the maleimide group and the aromatic hydrocarbon group.

式（３）中、Ｒ^１１及びＲ^１６はマレイミド基を表し、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５は、それぞれ独立に水素原子、アルキル基、又はアリール基を表し、Ｄはそれぞれ独立に２価の芳香族基を表す。ｍ１及びｍ２はそれぞれ独立に１～１０の整数を表し、ｎは１～１００の整数を表す。 The maleimide resin preferably has a structure represented, for example, by the following formula (3).

In formula (3), R ¹¹ and R ¹⁶ represent a maleimide group, R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and D each independently represents represents a divalent aromatic group. m1 and m2 each independently represent an integer of 1-10, and n represents an integer of 1-100.

R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ in formula (3) each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom.

As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms is even more preferable. Alkyl groups may be straight, branched or cyclic. Examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, and isopropyl groups.

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 aryl group may be monocyclic or condensed. Examples of such aryl groups include phenyl, naphthyl and anthracenyl groups.

Alkyl groups and aryl groups may have a substituent. The substituents are not particularly limited, and examples thereof include halogen atoms, —OH, —O—C _1-6 alkyl groups, —N(C _1-10 alkyl groups) ₂ , C _1-10 alkyl groups, C _{6- 10} aryl group, —NH ₂ , —CN, —C(O)O—C _1-10 alkyl group, —COOH, —C(O)H, —NO ₂ and the like. Here, the term “C _p−q ” (where p and q are positive integers and satisfies p<q) means that the organic group described immediately after this term has p to q carbon atoms. represents something. For example, the phrase “C _1-10 alkyl group” indicates an alkyl group having 1 to 10 carbon atoms. These substituents may combine with each other to form a ring, and the ring structure includes spiro rings and condensed rings.

The substituents described above may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). As secondary substituents, unless otherwise specified, the same substituents as described above may be used.

D in formula (3) represents a divalent aromatic group. Examples of the divalent aromatic group include a phenylene group, a naphthylene group, an anthracenylene group, an aralkyl group, a biphenylene group, and a biphenylaralkyl group. . The divalent aromatic group may have a substituent. The substituent is the same as the substituent that the alkyl group represented by R ¹² in formula (3) may have.

m1 and m2 each independently represent an integer of 1 to 10, preferably 1 to 6, more preferably 1 to 3, still more preferably 1 to 2, and even more preferably 1.

n represents an integer of 1-100, preferably 1-50, more preferably 1-20, still more preferably 1-5.

式（４）中、Ｒ^２１及びＲ^２２はマレイミド基を表す。ｎ１は１～１００の整数を表す。 As the maleimide resin, a resin represented by Formula (4) is preferable.

In formula ⁽ 4), R21 and ^R22 represent a maleimide group. n1 represents an integer from 1 to 100;

n1 is the same as n in formula (3), and the preferred range is also the same.

A commercial item can be used for the maleimide resin. Examples of commercially available products include "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. and the like.

As the solid phenol-based resin and the solid naphthol-based resin, those having a novolac structure are preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based resin is more preferable.

Specific examples of such phenolic resins and naphtholic resins include "MEH-7700", "MEH-7810" and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN" manufactured by Nippon Kayaku Co., Ltd. , "CBN", "GPH", Nippon Steel Chemical & Materials "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375" , "SN395", DIC's "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" and the like. .

As the solid active ester-based resin, a resin having one or more active ester groups in one molecule can be used. Among them, as solid active ester resins, phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. have two highly reactive ester groups in one molecule. A resin having at least one is preferred. The active ester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester-based resin obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred.

Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Preferred specific examples of the solid active ester resin include an active ester resin containing a dicyclopentadiene type diphenol structure, an active ester resin containing a naphthalene structure, an active ester resin containing an acetylated phenol novolac, and a phenol Active ester resins containing benzoylated novolacs are included. Among them, an active ester resin containing a naphthalene structure and an active ester resin containing a dicyclopentadiene type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available solid active ester resins include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC -8000H-65TM", "EXB-8000L-65TM" (manufactured by DIC); "EXB9416-70BK" and "EXB-8150-65T" (manufactured by DIC) as active ester resins containing a naphthalene structure; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester resin containing an acetylated product; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester resin containing a benzoylated phenol novolak; an active ester that is an acetylated product of phenol novolak. "DC808" (manufactured by Mitsubishi Chemical Corporation) as a base resin; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (Mitsubishi chemical company); and the like.

Examples of solid cyanate ester resins include bisphenol A dicyanate, polyphenolcyanate, oligo(3-methylene-1,5-phenylenecyanate), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4 ,4′-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5 -dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, and the like. resins; polyfunctional cyanate resins derived from phenol novolacs, cresol novolaks, etc.; prepolymers obtained by partially triazinizing these cyanate resins; and the like. Specific examples of cyanate ester resins include "PT30", "PT30-80M" and "PT60" (phenol novolac type polyfunctional cyanate ester resins) manufactured by Lonza Japan, and "ULL-950S" (polyfunctional cyanate ester resins ), “BA230”, and “BA230S75” (a prepolymer in which part or all of bisphenol A dicyanate is triazined to form a trimer).

Specific examples of solid carbodiimide resins include Carbodiimide (registered trademark) V-03 (carbodiimide group equivalent: 216, V-05 (carbodiimide group equivalent: 262), V-07 (carbodiimide group equivalent) manufactured by Nisshinbo Chemical Co., Ltd. : 200); V-09 (carbodiimide group equivalent: 200); Rhein Chemie Stabaxol (registered trademark) P (carbodiimide group equivalent: 302).

Specific examples of solid benzoxazine-based resins (excluding those corresponding to allyl-based resins) include "HFB2006M" manufactured by Showa Polymer Co., Ltd., "JBZ-OP100D" manufactured by JFE Chemical Co., Ltd., "ODA- BOZ"; "Fa" manufactured by Shikoku Kasei Kogyo Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.;

Examples of solid acid anhydride-based resins include resins having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride resins include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic anhydride. trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyl Sulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1, Polymer type acid anhydrides such as 3-dione, ethylene glycol bis(anhydrotrimellitate), styrene/maleic acid resin obtained by copolymerizing styrene and maleic acid, and the like can be mentioned.

The content of component (A-2) is preferably 10% by mass or more, more preferably 10% by mass or more, and more preferably 15% by mass or more, more preferably 20% by mass or more, 25% by mass or more, 30% by mass or more, 40% by mass or more, preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass % or less and 60% by mass or less.

When the resin composition contains component (A-2), it preferably contains an epoxy resin and a curing agent as component (A-2). In this case, the total content of the epoxy resin and the curing agent as the component (A-2) is, from the viewpoint of significantly obtaining the desired effect of the present invention, when the non-volatile component in the resin composition is 100% by mass, It is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, preferably 75% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.

When the resin composition contains component (A-2), it preferably contains a maleimide resin as component (A-2). In this case, the content of the maleimide resin as the component (A-2) is preferably 25% when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the desired effect of the present invention. % by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.

When component (A-1) contains a curing agent, component (A-2) preferably contains either an epoxy resin or a maleimide resin, more preferably a maleimide resin. In this case, the mass ratio of the curing agent as component (A-1) to the epoxy resin and maleimide resin as component (A-2) (% by mass of component (A-2)/of component (A-1) %) is preferably 1 or more, more preferably 1.5 or more, still more preferably 2 or more, preferably 15 or less, more preferably 10 or less, and still more preferably 8 or less. By setting the mass ratio within this range, the thermosetting of the resin composition can proceed more effectively, and the mechanical strength of the cured product can be further enhanced.

Further, when the component (A-1) contains either an epoxy resin or a (meth)acrylic resin, the component (A-2) preferably contains either an epoxy resin or a curing agent, and contains a curing agent. is more preferred. In this case, the mass ratio of the epoxy resin and (meth)acrylic resin as component (A-1) to the epoxy resin and curing agent as component (A-2) (mass% of component (A-2)/( A-1) mass % of component) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, preferably 2 or less, more preferably 1.5 or less, It is more preferably 1 or less. By setting the mass ratio within this range, the thermosetting of the resin composition can proceed more effectively, and the mechanical strength of the cured product can be further enhanced.

The content of the component (A) (the total content of the components (A-1) and (A-2)) is the non-volatile component in the resin composition from the viewpoint of significantly obtaining the desired effects of the present invention. is 100% by mass, preferably 11% by mass or more, more preferably 18% by mass or more, still more preferably 25% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and more preferably is 70% by mass or less and 60% by mass or less.

<(B) Thermoplastic resin>
The resin composition contains (B) a thermoplastic resin. The film handleability can be improved by including the thermoplastic resin as the component (B) in the resin composition. In addition, by including (B) the thermoplastic resin in the resin composition, it is also possible to reduce the coefficient of linear thermal expansion of the cured product.

(B) Thermoplastic resins include, for example, phenoxy resins, polycarbonate resins, polyvinyl acetal resins, polyolefin resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyether Ether ketone resins, polyester resins and the like can be mentioned. Among them, at least one selected from polyimide resins, polycarbonate resins and phenoxy resins is preferable from the viewpoint of significantly obtaining the desired effects of the present invention. Moreover, (B) thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more types.

A resin having an imide structure can be used as the polyimide resin. Polyimide resins generally include those obtained by the imidization reaction between a diamine compound and an acid anhydride.

The diamine compound for preparing the polyimide resin is not particularly limited, and examples thereof include aliphatic diamine compounds and aromatic diamine compounds.

Examples of aliphatic diamine compounds include 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, and 1,5-diaminopentane. , 1,10-diaminodecane and other linear aliphatic diamine compounds; 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane, and 2-methyl-1,5- Branched aliphatic diamine compounds such as diaminopentane; 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4′-methylenebis(cyclohexyl) alicyclic diamine compounds such as amines); dimer acid-type diamines (hereinafter also referred to as "dimer diamines"), and the like. A dimer acid-type diamine is a diamine compound obtained by substituting _two terminal carboxylic acid groups (--COOH) of a dimer _acid with an aminomethyl group (--CH.sub.2--NH.sub.2) or an amino group ( _--NH.sub.2 ). means. Dimer acid is a known compound obtained by dimerizing an unsaturated fatty acid (preferably having 11 to 22 carbon atoms, particularly preferably having 18 carbon atoms), and its industrial production process is almost Standardized.

Examples of aromatic diamine compounds include phenylenediamine compounds, naphthalenediamine compounds, and dianiline compounds.

A phenylenediamine compound means a compound consisting of a benzene ring having two amino groups, and the benzene ring may optionally have 1 to 3 substituents. The substituents here are not particularly limited. Specific examples of phenylenediamine compounds include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diamino biphenyl, 2,4,5,6-tetrafluoro-1,3-phenylenediamine and the like.

A naphthalenediamine compound means a compound consisting of a naphthalene ring having two amino groups, and the naphthalene ring herein may optionally have 1 to 3 substituents. The substituents here are not particularly limited. Specific examples of naphthalenediamine compounds include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,3-diaminonaphthalene.

A dianiline compound means a compound containing two aniline structures in the molecule, and two benzene rings in the two aniline structures each further optionally have 1 to 3 substituents. can. The substituents here are not particularly limited. Two aniline structures in a dianiline compound are directly bonded and/or bonded via 1 or 2 linker structures having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. can. Dianiline compounds also include those in which two aniline structures are bound by two bonds.

Specific examples of the "linker structure" in the dianiline compound include -NHCO-, -CONH-, -OCO-, -COO-, -CH ₂ -, -CH ₂ CH ₂ -, and -CH ₂ CH ₂ CH ₂ -. , -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - , -CH=CH-, -O-, -S-, -CO-, -SO ₂ -, -NH-, -Ph-, -Ph-Ph-, -C(CH ₃ ) ₂ -Ph-C( CH ₃ ) ₂ -, -O-Ph-O-, -O-Ph-Ph-O-, -O-Ph-SO ₂ -Ph-O-, -O-Ph-C(CH ₃ ) ₂ -Ph —O—, —C(CH ₃ ) ₂ —Ph—C(CH ₃ ) ₂ —,

etc. As used herein, "Ph" represents a 1,4-phenylene group, a 1,3-phenylene group or a 1,2-phenylene group.

In one embodiment, the dianiline compound specifically includes 4,4′-diamino-2,2′-ditrifluoromethyl-1,1′-biphenyl, 3,4′-diaminodiphenyl ether, 4,4′- Diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1,3-bis(3-aminophenoxy) Benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropyl lidene)dianiline, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, α,α-bis[4- (4-aminophenoxy)phenyl]-1,3-diisopropylbenzene, α,α-bis[4-(4-aminophenoxy)phenyl]-1,4-diisopropylbenzene, 4,4′-(9-fluorenylidene) Dianiline, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl- 1,1′-biphenyl, 4,4′-diamino-2,2′-dimethyl-1,1′-biphenyl, 9,9′-bis(3-methyl-4-aminophenyl)fluorene, 5-(4 -aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane and the like.

A commercially available diamine compound may be used, or one synthesized by a known method may be used. A diamine compound may be used individually by 1 type, and may be used in combination of 2 or more type.

The acid anhydride for preparing the polyimide resin is not particularly limited, but in a preferred embodiment, it is an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic dianhydride include benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, anthracenetetracarboxylic dianhydride, diphthalic dianhydride and the like, preferably It is diphthalic dianhydride.

Benzenetetracarboxylic dianhydride means the dianhydride of benzene having 4 carboxy groups, and further, the benzene ring herein may optionally have 1-3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and —X ³³ —R ³³ (as defined in formula (1B) below). Specific examples of benzenetetracarboxylic dianhydride include pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride.

Naphthalenetetracarboxylic dianhydride means a dianhydride of naphthalene having 4 carboxy groups, and furthermore, the naphthalene ring herein may optionally have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and —X ³³ —R ³³ (as defined in formula (1B) below). Specific examples of the naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride and 2,3,6,7-naphthalenetetracarboxylic dianhydride.

Anthracenetetracarboxylic dianhydride means an anthracene dianhydride having four carboxy groups, and the anthracene ring herein may optionally have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and —X ³³ —R ³³ (as defined in formula (1B) below). Specific examples of anthracenetetracarboxylic dianhydride include 2,3,6,7-anthracenetetracarboxylic dianhydride and the like.

Diphthalic dianhydride means a compound containing two phthalic anhydrides in the molecule, and two benzene rings in each of the two phthalic anhydrides are optionally 1 to 3 It can have substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and —X ³³ —R ³³ (as defined in formula (1B) below). Two phthalic anhydrides in diphthalic dianhydride can be linked directly or via a linker structure having 1 to 100 backbone atoms selected from carbon, oxygen, sulfur and nitrogen atoms.

Examples of diphthalic dianhydride include formula (1B):

[In the formula,
R ³¹ and R ³² each independently represent a halogen atom, a cyano group, a nitro group, or -X ³³ -R ³³ ,
X ³³ is each independently a single bond, -NR ^33' -, -O-, -S-, -CO-, -SO ₂ -, -NR ^33' CO-, -CONR ^33' -, -OCO -, or -COO-,
R ³³ each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group,
R ^33′ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group,
Y is a single bond or a linker structure having 1 to 100 skeleton atoms selected from carbon, oxygen, sulfur and nitrogen atoms;
n10 and m10 each independently represent an integer of 0 to 3; ]
The compound represented by is mentioned.

Y is preferably a linker structure having 1-100 backbone atoms selected from carbon, oxygen, sulfur and nitrogen atoms. n and m are preferably zero.

The “linker structure” for Y has 1 to 100 skeletal atoms selected from carbon, oxygen, sulfur and nitrogen atoms. The "linker structure" is preferably -[A-Ph] _a -A-[Ph-A] _b - [wherein each A is independently a single bond, - (substituted or unsubstituted alkylene group )-, -O-, -S-, -CO-, -SO ₂ -, -CONH-, -NHCO-, -COO-, or -OCO-, a and b are each independently 0 An integer from 1 to 2 (preferably 0 or 1). ] is a divalent group represented by

The "linker structure" for Y is specifically -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -O-, -CO-, -SO ₂ -, -Ph-, -O-Ph-O-, - O-Ph-SO ₂ -Ph-O-, -O-Ph-C(CH ₃ ) ₂ -Ph-O- and the like can be mentioned. As used herein, "Ph" represents a 1,4-phenylene group, a 1,3-phenylene group or a 1,2-phenylene group.

Specific examples of diphthalic dianhydride include 4,4′-oxydiphthalic anhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′- diphenyl ether tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 2 ,3,3′,4′-diphenyl ether tetracarboxylic dianhydride, 2,3,3′,4′-diphenylsulfone tetracarboxylic dianhydride 2,2′-bis(3,4-dicarboxyphenoxyphenyl ) sulfone dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethynylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride anhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic acid dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,4-bis(3, 4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 2 ,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4′-(4,4′-isopropyl dendiphenoxy)bisphthalic dianhydride and the like.

A commercially available acid anhydride may be used, or an acid anhydride synthesized by a known method or a method analogous thereto may be used. An acid anhydride may be used individually by 1 type, and may be used in combination of 2 or more type.

A commercially available polyimide resin can be used. Commercially available products include "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin Nippon Rika.

A resin having a carbonate structure can be used as the polycarbonate resin. Examples of such resins include carbonate resins having no reactive groups, hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxy group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, urethane group-containing carbonate resins, Containing carbonate resin etc. are mentioned. Here, the reactive group means a functional group capable of reacting with other components such as a hydroxyl group, a phenolic hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group, a urethane group and an epoxy group.

A commercially available product can be used as the carbonate resin. Commercial products include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, "C-1090", "C-2090", "C -3090" (polycarbonate diol).

Examples of phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, and terpene. Examples include phenoxy resins having one or more skeletons selected from the group consisting of skeletons and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

Specific examples of the phenoxy resin include Mitsubishi Chemical's "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins); Mitsubishi Chemical's "YX8100" (bisphenol S skeleton-containing phenoxy resin); Mitsubishi Chemical "YX6954" (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel Chemical &Materials; "FX280" and "FX293" manufactured by Nippon Steel Chemical &Materials; ", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482";

Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include S-lec BH series, BX series (eg BX-5Z), KS series (eg KS-1), BL series and BM series manufactured by Sekisui Chemical Co., Ltd.

Specific examples of polyamide-imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamideimide resins include modified polyamideimides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimides) manufactured by Hitachi Chemical Co., Ltd.

Specific examples of the polyethersulfone 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, Inc., and the like.

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

(B) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, and particularly preferably 20,000 or more, from the viewpoint of significantly obtaining the desired effects of the present invention. is preferably 70,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less.

(B) The content of the thermoplastic resin is preferably 1% by mass or more, more preferably 5% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of improving film handling properties. It is more preferably 10% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 25% by mass or less and 20% by mass or less.

The content of the resin component is preferably 70% by mass or more when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of suppressing the generation of via bottom voids and improving the film handleability. More preferably 73% by mass or more, still more preferably 75% by mass or more and 80% by mass or more. The upper limit is not particularly limited, but is preferably 100% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less.

<(C) Inorganic filler>
The resin composition may or may not contain (C) an inorganic filler. However, the content of (C) the inorganic filler is 50% by mass or less when the non-volatile component in the resin composition is 100% by mass. When containing an inorganic filler as component (C), the specific surface area of the inorganic filler (C) is 40 m ² /g or more. (C) The specific surface area of the inorganic filler represents the specific surface area of the entire inorganic filler contained in the resin composition.

In the resin composition containing the (A-1) component and the (B) component described above, when the (C) component satisfies the above requirements, it is possible to suppress the generation of voids at the bottom of vias, and the film handleability is improved. can be improved.

(C) The content of the inorganic filler is 50% by mass or less when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of suppressing the generation of via bottom voids and improving the film handleability. , preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. The lower limit is 0% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more.

The specific surface area of the inorganic filler (C) is 40 m ² /g or more, preferably 50 m ² /g or more, more preferably 60 m ² /g or more, from the viewpoint of suppressing the generation of via bottom voids. Although there is no particular upper limit, it is preferably 300 m ² /g or less, more preferably 200 m ² /g or less, and still more preferably 100 m ² /g or less from the viewpoint of further improving film handling properties. The specific surface area is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method and calculating the specific surface area using the BET multipoint method. .

An inorganic compound is used as the material of the inorganic filler. Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, 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, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide , barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as silica, spherical silica is preferable. (C) Inorganic fillers may be used singly or in combination of two or more.

(C) Commercially available inorganic fillers include, for example, "YA050C-MJE", "50nmSV-AM1" and "50nmSZ-AM1" manufactured by Admatechs; "NSS-4N" and "NSS- 5N”; “UFP-60” and “UFP-80” manufactured by Denka.

The average particle size of the inorganic filler (C) is preferably 100 nm or less, preferably 90 nm or less, more preferably 80 nm or less, from the viewpoint of suppressing the generation of via bottom voids. The lower limit of the average particle diameter is not particularly limited, but from the viewpoint of further improving the film handleability, it is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more.

(C) The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. A measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes. The measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, and the volume-based particle size distribution of the inorganic filler (C) is measured by the flow cell method. The average particle size can be calculated as the median size from the size distribution. Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.

(C) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate compounds. Coupling agents, (meth)acrylsilanes, and the like can be mentioned. Moreover, one type of surface treatment agent may be used alone, or two or more types may be used in combination.

Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industry Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" ( Hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent), Shin-Etsu Chemical Co., Ltd. "KBM- 7103” (3,3,3-trifluoropropyltrimethoxysilane).

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2-5 parts by mass of a surface treatment agent, and is surface-treated with 0.2-3 parts by mass. preferably 0.3 parts by mass to 2 parts by mass of the surface treatment.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon 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, and more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of suppressing the melt viscosity of the resin varnish and the melt viscosity in the sheet form, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and further preferably 0.5 mg/m ² or less. preferable.

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

<(D) Curing accelerator>
The resin composition may further contain (D) a curing accelerator as an optional component.

Examples of curing accelerators include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and peroxide-based curing accelerators. Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and peroxide-based curing accelerators are preferable. A physical curing accelerator is more preferred. The curing accelerator may be used singly or in combination of two or more.

Phosphorus curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

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

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(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, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and the like, and adducts of imidazole compounds and epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. organic zinc complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate; Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Examples of peroxide curing accelerators include t-butyl cumyl peroxide, t-butyl peroxyacetate, α,α'-di(t-butylperoxy)diisopropylbenzene, t-butyl peroxylaurate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, t-butylperoxybenzoate and the like.

Examples of commercially available peroxide curing accelerators include NOF Corporation's "PERBUTYL C", "PERBUTYL A", "PERBUTYL P", "PERBUTYL L", "PERBUTYL O", "PERBUTYL ND", "PERBUTYL Z", "PERCYL P", "PERCYL D" and the like.

(D) The content of the curing accelerator is preferably 0.001% by mass or more, more preferably 0.001% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the desired effects of the present invention. is 0.005% by mass or more, more preferably 0.01% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.3% by mass or less.

<(E) Other Additives>
The resin composition may further contain other additives as optional components in addition to the components described above. Examples of such additives include resin additives such as thickeners, antifoaming agents, leveling agents and adhesiveness imparting agents; polymerization initiators and the like. These additives may be used singly or in combination of two or more. Each content can be appropriately set by those skilled in the art.

The method of preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method of adding a solvent or the like to the compounding ingredients as necessary, and mixing and dispersing using a rotary mixer or the like.

<Physical properties and applications of the resin composition>
The resin composition of the present invention exhibits excellent embeddability. Therefore, a resin sheet having excellent film handleability is obtained. A specific example of the measurement of embeddability is to prepare a resin sheet as a glass cloth-based epoxy resin double-sided copper-clad laminate (thickness of copper foil: 3 μm, substrate thickness: 0.15 mm, “HL832NSF LCA” manufactured by Mitsubishi Gas Chemical Co., Ltd., 255× 340 mm size), and the resin composition layer is heat-cured at 100° C. for 20 minutes and then at 180° C. for 30 minutes to form an insulating layer to prepare an evaluation substrate. Using a digital microscope, arbitrarily set 1 cm squares on the wiring pattern of the evaluation substrate are observed at three points, and voids, which are appearance defects having a diameter of 10 μm or more, are measured. At this time, the number of voids is usually zero. The details of the evaluation of the embeddability can be measured according to the method described in Examples below.

The resin composition of the present invention exhibits a property of excellent exudation. Therefore, a resin sheet having excellent film handleability is obtained. The oozing amount indicates the ease of control during the production of the inner layer substrate, and when the oozing amount is within the following range, the control during the production of the inner layer substrate is facilitated. As a specific example of the method for measuring the seepage property, a resin sheet is laminated on an inner layer circuit board, and the length of the resin that seeps out from the outer peripheral portion of the resin sheet is defined as the amount of seepage. The amount of seepage at arbitrary 10 points is measured, and the average is 0.5 mm or more and 5 mm or less. The details of the evaluation of the exudation property can be measured according to the method described in Examples described later.

The resin composition of the present invention is heat-cured at 100° C. for 20 minutes and then at 180° C. for 30 minutes. show. Thus, said cured product provides an insulating layer with a low arithmetic mean roughness. The arithmetic mean roughness is preferably less than 100 nm, more preferably 90 nm or less, still more preferably 80 nm or less. On the other hand, the lower limit of the arithmetic mean roughness can be 1 nm or more. The arithmetic mean roughness (Ra) can be evaluated according to the method described in Examples below.

The resin composition of the present invention is heat-cured at 100° C. for 20 minutes and then at 180° C. for 30 minutes to form a via hole. . Therefore, the cured product provides an insulating layer in which via bottom voids are suppressed. A specific example of the measurement of voids at the bottom of vias is to prepare a resin sheet as a glass cloth-based epoxy resin double-sided copper-clad laminate (thickness of copper foil: 3 μm, substrate thickness: 0.15 mm, manufactured by Mitsubishi Gas Chemical Co., Ltd. “HL832NSF LCA”, 255 ×340 mm size), and the resin composition layer is heat-cured at 100° C. for 20 minutes and then at 180° C. for 30 minutes to form an insulating layer. A via hole is formed in the insulating layer by a UV-YAG laser, and after desmearing, a conductor layer is formed by sputtering. After forming the conductor layer, the cross section of the substrate is observed using SEM images of randomly selected 10 via holes. At this time, no via-bottom voids are normally generated in ten via holes. The details of the evaluation of via bottom voids can be measured according to the method described in Examples below.

A cured product obtained by thermally curing the resin composition of the present invention at 100° C. for 20 minutes and then at 180° C. for 30 minutes usually exhibits a low coefficient of linear thermal expansion. Thus, the cured product provides an insulating layer with a low coefficient of linear thermal expansion. The coefficient of linear thermal expansion is preferably less than 70 ppm, more preferably 65 ppm or less, still more preferably 60 ppm or less. On the other hand, the lower limit of the coefficient of linear thermal expansion can be set to 1 ppm or more. The linear thermal expansion coefficient can be measured according to the method described in Examples below.

The minimum melt viscosity of the resin composition of the present invention is 100 poise or more, preferably 200 poise or more, more preferably 300 poise or more, still more preferably 400 poise or more, and 4000 poise or less, preferably 3000 poise or less, more preferably 3000 poise or less. It is 2800 poise or less, more preferably 2500 poise or less, and particularly preferably 2000 poise or less. Here, the term "minimum melt viscosity" refers to the minimum melt viscosity between 60°C and 200°C. The minimum melt viscosity can be measured using a dynamic viscoelasticity measuring device. The minimum melt viscosity can be measured according to the method described in Examples below. When the minimum melt viscosity of the resin composition is within such a range, the film becomes excellent in handleability.

INDUSTRIAL APPLICABILITY The resin composition of the present invention can reduce the minimum melt viscosity and improve embedding properties, and as a result, can improve film handleability. Moreover, it is possible to obtain a cured product capable of suppressing the generation of via bottom voids. Therefore, the resin composition of the present invention is a resin composition for forming a conductor layer (including a rewiring layer) on an insulating layer by sputtering (a conductor layer is formed by sputtering). It can be suitably used as a resin composition for forming an insulating layer to be coated). In addition, in the multilayer printed wiring board described later, a resin composition for forming an insulating layer of the multilayer printed wiring board (a resin composition for forming an insulating layer of the multilayer printed wiring board), an interlayer insulating layer of the printed wiring board can be suitably used as a resin composition for forming a (resin composition for forming an interlayer insulating layer of a printed wiring board).

[Resin sheet]
The resin sheet of the present invention includes a support and a resin composition layer containing a resin composition provided on the support, wherein the resin composition comprises (A) a thermosetting resin and (B) It contains a thermoplastic resin, does not contain or contains (C) an inorganic filler, and the content of the (C) inorganic filler is 50% by mass or less when the non-volatile component in the resin composition is 100% by mass. (C) The inorganic filler has a specific surface area of 40 m ² /g or more, and the minimum melt viscosity of the resin composition layer is 100 poise or more and 4000 poise or less.

The resin composition contains (A) a thermosetting resin. Component (A) may contain at least one of component (A-1) and component (A-2), and preferably contains component (A-1). The components (A-1) and (A-2) are as explained above.

Components other than component (A) in the resin composition are as described above.

The minimum melt viscosity of the resin composition layer is preferably 100 poise or more, preferably 200 poise or more, more preferably 300 poise or more, still more preferably 400 poise or more and 4000 poise or less, from the viewpoint of improving film handling properties. is 3000 poise or less, more preferably 2800 poise or less, still more preferably 2500 poise or less, and particularly preferably 2000 poise or less.

The thickness of the resin composition layer is preferably 15 μm or less, more It is preferably 12 μm or less, more preferably 10 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 1 μm or more, 5 μm or more, or the like.

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

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, polyimides, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

The support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface to be bonded to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1" manufactured by Lintec Co., Ltd., "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

In one embodiment, the resin sheet may further contain other layers as necessary. Such other layers include, for example, a protective film conforming to the support provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). be done. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, the surface of the resin composition layer can be prevented from being dusted or scratched.

For the resin sheet, for example, a resin varnish is prepared by dissolving a resin composition in an organic solvent, the resin varnish is applied onto a support using a die coater or the like, and dried to form a resin composition layer. It can be manufactured by

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol; carbitols; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

[Printed wiring board and its manufacturing method]
The printed wiring board of the present invention includes an insulating layer formed from a cured product of the resin composition of the present invention. The resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer for forming a conductor layer by sputtering. Therefore, it is preferable to form the conductor layer by sputtering.

A printed wiring board can be produced, for example, using the resin sheet described above by a method including the following steps (1) to (4).
(1) A step of laminating the resin composition layer of the resin sheet on the inner layer substrate so as to be bonded to the inner layer substrate (2) A step of thermally curing the resin composition layer to form an insulating layer (3) On the insulating layer (4) forming a conductive layer on the insulating layer by sputtering;

The "inner layer substrate" used in step (1) is a member that serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. The substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Further, an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" as used in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components can be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). Instead of directly pressing the thermocompression member onto the resin sheet, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the unevenness of the surface of the inner layer substrate.

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

Lamination can be done with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch vacuum pressurized laminator, and the like.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned commercially available vacuum laminator.

The support may be removed between steps (1) and (2) or after step (2).

In step (2), the resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions for the resin composition layer are not particularly limited, and conditions that are commonly used for forming insulating layers of printed wiring boards may be used.

For example, although the thermosetting conditions for the resin composition layer vary depending on the type of resin composition, etc., the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and still more preferably 170°C to 210°C. °C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, even more preferably 15 minutes to 100 minutes.

Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is cured at a temperature of 50° C. or higher and less than 120° C. (preferably 60° C. or higher and 115° C. or lower, more preferably 70° C. or higher and 110° C. or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes).

The thickness of the insulating layer is preferably 30 μm or less, more preferably 20 μm or less, still more preferably 15 μm or less, and 10 μm or less. Although the lower limit is not particularly limited, it can usually be 1 μm or more, 5 μm or more, or the like.

In step (3), the insulating layer is perforated. Through the step (3), holes such as via holes and through holes can be formed in the insulating layer. Step (3) may be carried out using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

Since the insulating layer is formed of the cured resin composition of the present invention, it is possible to reduce the top diameter. The top diameter of the hole is preferably 45 μm or less, more preferably 40 μm or less, and more preferably 35 μm or less. The lower limit can be, for example, 1 μm or more.

When manufacturing a printed wiring board, after the step (3) and before the step (4), the step of (A) roughening the insulating layer may be further carried out. Step (A) may be carried out according to various methods known to those skilled in the art for use in manufacturing printed wiring boards. When the support is removed after step (2), the support may be removed between step (2) and step (3), between step (3) and step (A), or step ( It may be carried out between A) and step (4). If necessary, the steps (2), (3), (A), and (4) of forming an insulating layer and a conductor layer may be repeated to form a multilayer wiring board. .

Step (A) is a step of roughening the insulating layer. Smear is usually also removed in this step (A). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used in forming insulating layers of printed wiring boards can be employed. Moreover, either a dry method or a wet method may be used.

Step (4) is a step of forming a conductor layer on the insulating layer by sputtering. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloys, copper- Nickel alloys and copper-titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel-chromium alloy alloy layers are more preferred.

The conductor layer may have a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

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

When forming a conductor layer by sputtering, usually, a conductor seed layer is first formed on the surface of an insulating layer by sputtering, and then a conductor sputter layer is formed on the conductor seed layer by sputtering. Before forming the conductive seed layer by sputtering, the surface of the insulating layer may be cleaned by reverse sputtering. As the gas used for the reverse sputtering, various gases can be used, among which Ar, O ₂ and N ₂ are preferable. Ar or _O2 or Ar, _O2 mixed gas when the seed layer is Cu and Cu alloy, Ar or _N2 or Ar, _N2 mixed gas when the seed layer is Ti, Cr and Cr alloy (nichrome etc.), Ar or O ₂ or a mixed gas of Ar and O ₂ is preferable. Sputtering can be performed using various sputtering devices such as magnetron sputtering and mirrortron sputtering. Cr, Ni, Ti, nichrome, and the like are examples of metals that form the conductive seed layer. Cr and Ti are particularly preferred. The thickness of the conductor seed layer is usually preferably 5 nm or more, more preferably 10 nm or more, and preferably 1000 nm or less, more preferably 500 nm or less. Cu, Pt, Au, Pd, etc., can be used as the metal forming the conductor sputter layer. Cu is particularly preferred. The thickness of the conductor sputtered layer is usually preferably 50 nm or more, more preferably 100 nm or more, and preferably 3000 nm or less, more preferably 1000 nm or less.

When the conductor seed layer is formed, the surface roughness (Ra value) formed on the surface of the insulating layer is preferably 150 nm or less, more preferably 10 to 150 nm, as measured after the conductor seed layer is removed by etching. It is preferably 10 to 120 nm or less, and more preferably 10 to 120 nm or less.

After the conductor layer is formed by sputtering, a copper plating layer may be further formed on the conductor layer by electrolytic copper plating. The thickness of the copper plating layer is usually preferably 5 μm or more, more preferably 8 μm or more, and preferably 75 μm or less, more preferably 35 μm or less. Well-known methods, such as a subtractive method and a semi-additive method, can be used for circuit formation.

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

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

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. A "conducting part" is a "part where an electric signal is transmitted on a printed wiring board", and the place may be a surface or an embedded part. Also, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method, and the like. Here, "a mounting method using a build-up layer without bumps (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected." is.

EXAMPLES The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the description below, unless otherwise specified, "parts" and "%" mean "mass parts" and "mass%", respectively.

<(A) Liquid, semi-solid, and solid determination of thermosetting resin>
(A) Judgment of liquid, semi-solid, and solid state of thermosetting resin shall be made according to Attachment No. 2 “Confirmation method of liquid state” of Ministerial Ordinance Concerning Testing and Properties of Hazardous Materials (Ministry of Home Affairs Ordinance No. 1 of 1989). I went according to "Confirmation method of liquid state" was carried out as described above. The results are shown below.
"630" manufactured by Mitsubishi Chemical; liquid "ELM-100" manufactured by Sumitomo Chemical; liquid "A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.; liquid "AA" manufactured by Nippon Kayaku; liquid "L-DAIC" Shikoku Kasei Co., Ltd.; liquid "ALP-d" JFE Chemical Co.; liquid "YX4000" Mitsubishi Chemical Co.; solid "BA230S75" Lonza Japan Co.; solid "V-03" Nisshinbo Chemical Co.; MIR-3000-70MT” Nippon Kayaku Co., Ltd.; solid

<Measurement of specific surface area of inorganic filler>
Using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech), nitrogen gas is adsorbed on the surface of the inorganic filler, and the specific surface area is calculated using the BET multipoint method. Specific surface area was measured.
The inorganic filler dispersed in the organic solvent was dried in a drying oven at 60° C. for 12 hours to volatilize the organic solvent, and the specific surface area was measured. The results are shown below.
“YA050C-MJE” manufactured by Admatechs, surface treatment with methacrylsilane; 61.8 m ² /g
“UFP-30” manufactured by Denka; 30.7 m ² /g

<Synthesis Example 1: Synthesis of polyimide resin>
A 500 mL separable flask equipped with a water content receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer was prepared. The flask was charged with 20.3 g 4,4′-oxydiphthalic anhydride (ODPA), 200 g γ-butyrolactone, 20 g toluene, and 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy). Phenyl]-1,1,3-trimethylindane (29.6 g) was added, and the mixture was stirred at 45° C. for 2 hours under a nitrogen stream to carry out a reaction. Then, the temperature of this reaction solution was raised, and the condensed water was azeotropically removed together with toluene under a nitrogen stream while maintaining the temperature at about 160°C. It was confirmed that a predetermined amount of water was accumulated in the water content receiver, and that water was no longer seen to flow out. After confirmation, the reaction solution was further heated and stirred at 200° C. for 1 hour. Thereafter, the mixture was cooled to obtain a polyimide solution (non-volatile content: 20% by mass) containing a polyimide resin having a 1,1,3-trimethylindane skeleton. The obtained polyimide resin had a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). Moreover, the weight average molecular weight of the polyimide resin was 12,000.

<Example 1>
Glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 95 g / eq.) 3 parts, 30 parts of the polyimide resin prepared in Synthesis Example 1, inorganic filler (manufactured by Admatex Co., Ltd. "YA050C-MJE", ratio surface area 61.8 m ² /g, average particle diameter 50 nm, non-volatile content 50 mass% MEK solution) 20 parts, biphenyl type epoxy resin (Mitsubishi Chemical Corporation "YX4000", epoxy equivalent about 190 g / eq.) 5 parts, bisphenol A dicyanate prepolymer ("BA230S75" manufactured by Lonza Japan Co., Ltd., cyanate equivalent of about 232 g / eq., MEK solution with a nonvolatile content of 75% by mass) 20 parts, curing accelerator (cobalt (III) acetylacetone "(Co (acac) ₃ -1M", MEK solution with a non-volatile content of 1% by mass) was uniformly dispersed using a mixer to obtain a resin varnish.

As a support, a polyethylene terephthalate film (“AL5” manufactured by Lintec, thickness 38 μm, PET film) provided with a release layer was prepared. The above resin varnish was uniformly coated on the release layer of this support so that the thickness of the resin composition layer after drying was 15 μm. The resin varnish was then dried at 80° C.-100° C. (average 90° C.) for 3 minutes. Next, on the surface of the resin composition layer that is not bonded to the support, a rough surface of a polypropylene film (manufactured by Oji F-Tex Co., Ltd. "Alphan MA-411", thickness 15 μm) as a protective film is bonded to the resin composition layer. It was laminated so as to In this way, a resin sheet consisting of the support, the resin composition layer, and the protective film in this order was produced.

<Examples 2 to 14, Comparative Examples 1 to 5>
A resin composition and a resin sheet were obtained by uniform dispersion using a mixer in the same manner as in Example 1, except that each component was blended at the blending ratio shown in the table below.

<Measurement of coefficient of linear thermal expansion (CTE)>
(1) Preparation of Samples for Evaluating Cured Physical Properties Preliminarily prepared resin sheets of Examples and Comparative Examples were thermally cured at 200° C. for 90 minutes, and then the support was peeled off to prepare samples for evaluating cured physical properties. .

(2) Measurement of linear thermal expansion coefficient A sample for evaluating cured physical properties was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and a thermomechanical analyzer (Thermo Plus TMA8310, manufactured by Rigaku) was used to perform tensile Thermomechanical analysis was performed by weighted method. After mounting the test piece on the apparatus, the measurement was performed twice continuously under the measurement conditions of a load of 1 g and a temperature increase rate of 5° C./min. A coefficient of linear thermal expansion (ppm) from 30° C. to 150° C. in the second measurement was calculated.

<Measurement of minimum melt viscosity>
The melt viscosities of the resin composition layers of the previously prepared resin sheets of Examples and Comparative Examples were measured using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM Co., Ltd.). For 1 g of the sample resin composition, using a parallel plate with a diameter of 18 mm, the temperature was raised from the starting temperature of 60 ° C. to 200 ° C. at a heating rate of 5 ° C./min, and the measurement temperature interval was 2.5 ° C., vibration 1 Hz, strain The dynamic viscoelastic modulus was measured under 5 deg measurement conditions, and the lowest melt viscosity (minimum melt viscosity) was taken as an evaluation value.

<Evaluation of Film Handleability and Arithmetic Surface Roughness (Ra) after Roughening Treatment>
(1) Surface treatment of inner layer circuit board As an inner layer circuit board, a glass cloth-based epoxy resin double-sided copper-clad laminate (copper) having circuit conductors (copper) formed with a wiring pattern of L/S = 15 µm/15 µm on both sides ( A copper foil with a thickness of 18 μm, a substrate with a thickness of 0.15 mm, “HL832NSF LCA” manufactured by Mitsubishi Gas Chemical Co., Ltd., size of 255×340 mm was prepared.

(2) Lamination of resin sheet The protective film was peeled off from the prefabricated resin sheet of each example and each comparative example, and a batch-type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., two-stage build-up laminator, CVP700) was used. Then, it was laminated on both sides of the inner layer circuit board so that the resin composition layer was in contact with the inner layer circuit board. Lamination was carried out by pressure bonding for 45 seconds at 100° C. and a pressure of 0.74 MPa after reducing the pressure for 30 seconds to an air pressure of 13 hPa or less. Then, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Thermosetting of resin composition layer The inner layer circuit board laminated with the resin composition layer is placed in an oven at 100°C for 30 minutes, then transferred to an oven at 180°C and then heat-cured for 30 minutes to insulate. A substrate for evaluation was produced by forming a layer and peeling off the support.

(4) Evaluation of embeddability Using a digital microscope (“DIGITAL MICROSCOPE KH-8700” manufactured by Hilox), arbitrarily set 1 cm squares on the wiring pattern of the evaluation substrate were observed at three points. A case where there was one or more voids, which are appearance defects having a diameter of 10 μm or more, was evaluated as “×”, and a case where there were no voids was evaluated as “◯”. The absence of voids indicates excellent embeddability.

(5) Evaluation of seepage property In (2), when the resin sheet is laminated on the inner layer circuit board, the length of the resin that seeps out from the outer peripheral portion of the resin sheet is defined as the "bleed amount". The amount of seepage was measured at arbitrary 10 points, and the case where the average was 0.5 mm or more and 5 mm or less was evaluated as "O", and the case where the average was less than 0.5 mm or greater than 5 mm was evaluated as "X". The easiness of control at the time of substrate production is indicated when the amount of seepage is within the range.

(6) Roughening Process The insulating layer of the substrate for evaluation was subjected to a desmearing process as a roughening process. As the desmear treatment, the following wet desmear treatment was performed.

Wet desmear treatment:
Swelling liquid ("Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, then an oxidizing agent solution ("Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd.) , an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80 ° C. for 20 minutes, and finally a neutralizing solution ("Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd., an aqueous sulfuric acid solution). After being immersed at 40°C for 5 minutes, it was dried at 80°C for 15 minutes. This is used as a roughened substrate.

(7) Evaluation of arithmetic surface roughness (Ra) after roughening treatment Using a non-contact surface roughness meter (WYKO NT3300 manufactured by Bcoinstruments), VSI contact mode, 50x lens, measuring range 121 μm × 92 μm The value (nm) of the arithmetic surface roughness (Ra) of the roughened substrate was obtained from the numerical value obtained as . Moreover, it measured by calculating|requiring the average value of 10 points|pieces.

<Evaluation of Voids at Bottom of Via>
(1) Surface treatment of inner layer circuit board As an inner layer circuit board, a glass cloth-based epoxy resin double-sided copper-clad laminate (copper) having circuit conductors (copper) formed with a wiring pattern of L/S = 2 µm/2 µm on both sides ( A copper foil with a thickness of 3 μm, a substrate with a thickness of 0.15 mm, “HL832NSF LCA” manufactured by Mitsubishi Gas Chemical Co., Ltd., size of 255×340 mm was prepared.

(2) Lamination of resin sheet The protective film was peeled off from the prefabricated resin sheet of each example and each comparative example, and a batch-type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., two-stage build-up laminator, CVP700) was used. Then, it was laminated on both sides of the inner layer circuit board so that the resin composition layer was in contact with the inner layer circuit board. Lamination was carried out by pressure bonding for 45 seconds at 100° C. and a pressure of 0.74 MPa after reducing the pressure for 30 seconds to an air pressure of 13 hPa or less. Then, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Thermosetting of resin composition layer The inner layer circuit board laminated with the resin composition layer is placed in an oven at 100°C for 30 minutes, then transferred to an oven at 180°C and then heat-cured for 30 minutes to insulate. A void evaluation substrate was produced by forming a layer and peeling off the support.

(4) Via hole formation by UV-YAG laser Peel off the support to expose the surface of the insulating layer, and use a UV-YAG laser processing machine (“LU-2L212/M50L” manufactured by Via Mechanics Co., Ltd.) to insulate. Via holes were formed in the layer under the following conditions.
Conditions: power 0.25 W, number of shots 20, target top diameter 20 μm

(5) Roughening Process A desmearing process was performed as a roughening process on the insulating layer of the void evaluation substrate. As the desmear treatment, the following wet desmear treatment was performed.

Wet desmear treatment:
Swelling liquid ("Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, then an oxidizing agent solution ("Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd.) , an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80 ° C. for 20 minutes, and finally a neutralizing solution ("Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd., an aqueous sulfuric acid solution). After being immersed at 40°C for 5 minutes, it was dried at 80°C for 15 minutes. This is used as a roughened substrate.

(6) Formation of conductor layer by dry method A titanium layer (thickness 30 nm) and then a copper layer (thickness 300 nm) were formed using a sputtering apparatus ("E-400S" manufactured by Canon Anelva). After annealing the obtained substrate by heating it at 150° C. for 30 minutes, an etching resist is formed according to the semi-additive method. A conductor layer was formed with a thickness of After forming the conductor pattern, annealing was performed by heating at 200° C. for 60 minutes. The printed wiring board thus obtained is called "evaluation board A".

(7) Evaluation of Residue by Cross-Sectional Observation A cross-sectional observation of the via hole of the evaluation substrate A was performed using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology). Specifically, a cross-section that allows observation of the via vertically was cut out by FIB (focused ion beam), and a cross-sectional SEM image (observation width of 40 μm) near the interface at the bottom of the via was confirmed. For each evaluation substrate A, the cross section of 10 vias selected at random was observed, and those with no voids at the bottom of all 10 vias were evaluated as "○", and those with at least one void were evaluated as "X". did.

Abbreviations and the like in the table below are as follows.
630: Glycidylamine type epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 95 g/eq., liquid thermosetting resin)
ELM-100: Glycidylamine type epoxy resin (manufactured by Sumitomo Chemical Co., Ltd., liquid thermosetting resin)
A-DOG: dioxane acrylic monomer (manufactured by Shin-Nakamura Chemical Co., Ltd., (meth) acryloyl group equivalent 163 g / eq., liquid thermosetting resin)
AA: amine resin (manufactured by Nippon Kayaku Co., Ltd., "Kayahard AA", liquid thermosetting resin)
L-DAIC: allyl resin (manufactured by Shikoku Kasei Co., Ltd., liquid thermosetting resin)
ALP-d: allyl resin (manufactured by JFE Chemical Co., liquid thermosetting resin)
Synthesis Example 1: Polyimide resin YL7553BH30 produced in Synthesis Example 1: Phenoxy resin (manufactured by Mitsubishi Chemical Corporation, 1:1 solution of MEK (methyl ethyl ketone) with a solid content of 30% by mass and cyclohexanone)
FPC0220: Carbonate resin (Mitsubishi Gas Chemical Co., Ltd.)
YA050C-MJE: Silica (manufactured by Admatechs, MEK solution with a solid content of 50% by mass, specific surface area of 61.8 m ² /g, average particle size of 50 nm)
UFP-30: Silica (manufactured by Denka, specific surface area 30.7 m ² /g)
YX4000: Biphenyl-type epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 190 g/eq., solid thermosetting resin)
BA230S75: Prepolymer of bisphenol A dicyanate (manufactured by Lonza Japan, cyanate equivalent of about 232 g/eq., MEK solution with nonvolatile content of 75% by mass, solid thermosetting resin)
V-03: Carbodiimide-based curing agent (manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent weight: about 216 g/eq., nonvolatile content: 50% by mass, toluene solution, solid thermosetting resin)
MIR-3000-70MT: Maleimide resin (manufactured by Nippon Kayaku Co., Ltd., MEK/toluene mixture with nonvolatile content of 70% by mass, solid thermosetting resin)
Co(acac) ₃ -1M: curing accelerator (cobalt (III) acetylacetone, MEK solution with nonvolatile content of 1% by mass)
1B2PZ-10M: 1-benzyl-2-phenylimidazole (MEK solution with a solid content of 10% by mass)
Perbutyl C: Peroxide curing accelerator (manufactured by NOF Corporation)

In Examples 1 to 14, even if the components (A-2) and (D) are not contained, although there is a difference in degree, it has been confirmed that results similar to those of the above Examples are obtained. .

Claims (16)

A resin sheet laminated on the inner layer substrate so as to be bonded to the inner layer substrate,
comprising a support and a resin composition layer containing a resin composition provided on the support;
The resin composition contains (A-1) a liquid or semi-solid thermosetting resin, and (B) a thermoplastic resin, (C) does not contain or contains an inorganic filler, and (C) an inorganic filler. is 40% by mass or less when the non-volatile component in the resin composition is 100% by mass, and (C) the inorganic filler has a specific surface area of 40 m ² /g or more,
A resin sheet in which the resin composition layer has a minimum melt viscosity of 100 poise or more and 4000 poise or less. The resin sheet according to claim 1, wherein the content of the resin component is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass. 3. The resin sheet according to claim 1, wherein component (A-1) is at least one selected from epoxy resins, (meth)acrylic resins, amine-based resins, and allyl-based resins. The content of component (A-1) is 1% by mass or more and 40% by mass or less when the non-volatile component in the resin composition is 100% by mass, according to any one of claims 1 to 3. resin sheet. The resin sheet according to any one of claims 1 to 4, wherein component (B) is at least one selected from polyimide resins, polycarbonate resins and phenoxy resins. The resin sheet according to any one of claims 1 to 5, wherein the content of component (B) is 10% by mass or more and 50% by mass or less when the non-volatile component in the resin composition is 100% by mass. . The resin sheet according to any one of claims 1 to 6, wherein component (C) is silica. (A-2) The resin sheet according to any one of claims 1 to 7, further comprising a solid thermosetting resin. 9. The resin sheet according to claim 8, wherein the component (A-2) is at least one of a cyanate ester resin, a carbodiimide resin, and a maleimide resin. The resin sheet according to any one of claims 1 to 9, which is used for forming an insulating layer of a multilayer printed wiring board. A resin composition for forming an insulating layer laminated on an inner layer substrate so as to be bonded to the inner layer substrate,
(A-1) a liquid or semi-solid thermosetting resin, and (B) a thermoplastic resin,
(C) does not contain or contains inorganic fillers;
(C) the content of the inorganic filler is 40% by mass or less when the non-volatile component in the resin composition is 100% by mass;
(C) A resin composition in which the inorganic filler has a specific surface area of 40 m ² /g or more. The resin composition according to claim 11, wherein the content of component (A-1) is 1% by mass or more and 40% by mass or less when the non-volatile component in the resin composition is 100% by mass. A resin sheet comprising a support and a resin composition layer containing the resin composition according to claim 11 or 12 provided on the support. A cured product of the resin composition according to claim 11 or 12, or an insulating layer formed from a cured product of the resin composition layer of the resin sheet according to any one of claims 1 to 10 and 13, printed wiring board. (1) A step of laminating the resin composition layer of the resin sheet according to any one of claims 1 to 10 and 13 on the inner layer substrate so as to be bonded to the inner layer substrate;
(2) thermosetting the resin composition layer to form an insulating layer;
(3) A method of manufacturing a printed wiring board, comprising the steps of: (3) forming holes in an insulating layer; and (4) forming a conductor layer on the insulating layer by sputtering. A semiconductor device comprising the printed wiring board according to claim 14 .

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