JP2020132676A - Resin composition - Google Patents

Abstract

To provide a rein composition, etc., that can yield a cured product capable of suppressing the generation of voids at the bottom of the via when forming a conductor layer by sputtering, and that is excellent in film handleability.SOLUTION: A resin composition, which is a resin composition for forming an insulation layer for forming a conductor layer by sputtering, contains (A-1) a liquid or semi-solid thermosetting resin, and (B) a thermoplastic resin, containing or not containing (C) an inorganic filler, and the contained amount of (C) inorganic filler is, setting the non-volatile component in the resin composition as 100 mass%, 50 mass% or less, and the specific surface area of (C) inorganic filler is 40 m/g or more.SELECTED DRAWING: None

Description

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

In recent years, electronic devices have become smaller and more sophisticated, and in multilayer printed wiring boards, the build-up layer has been made into multiple layers, and the miniaturization and high density of wiring have also been further advanced. As a conductor forming method, for example, a semi-additive method in which a conductor layer is formed 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. Generally, in order to improve the adhesion, the roughness of the surface of the insulating layer should be increased. Can be considered.

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

In Patent Document 1, an adhesive film having a resin composition layer formed on a support film is laminated on a circuit board, the resin composition layer is heat-cured, the support film is peeled off, and a sputtering method is applied to the surface of the insulating layer. Disclosed is a method of manufacturing a multilayer printed wiring board in which the conductor layer exhibits high peeling strength even though the roughness is relatively small by forming the conductor layer. Further, in Patent Document 2, in order to eliminate the mismatch between the coefficient of thermal expansion of the insulating layer and the copper wiring, a high amount of an inorganic filler is blended in the resin composition, further increasing the density and reducing the size. It is described that high peel strength is obtained in spite of the relatively small roughness to correspond.

JP-A-2007-273615 Japanese Unexamined Patent Publication No. 2015-150885

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

On the other hand, if the content of the inorganic filler is low in order to facilitate the formation of fine wiring, the stability of thickness control is lacking when the 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 seep out, resulting in poor film handleability. Further, when the 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.

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

As a result of diligent studies on the above problems, the present inventors have found that the above problems can be solved, and have 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.
Includes (A-1) liquid or semi-solid thermosetting resin and (B) thermoplastic resin.
(C) Does not contain or contains an inorganic filler,
The content of the inorganic filler (C) is 50% by mass or less when the non-volatile component in the resin composition is 100% by mass.
(C) A resin composition having a specific surface area of an inorganic filler 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 100% by mass.
[3] The resin composition according to [1] or [2], wherein the component (A-1) is at least one selected from an epoxy resin, a (meth) acrylic resin, an amine resin, and an allyl resin.
[4] Any of [1] to [3], wherein the content of the 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 the component (B) is at least one selected from a polyimide resin, a polycarbonate resin, and a phenoxy resin.
[6] 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, according to any one of [1] to [5]. Resin composition.
[7] The resin composition according to any one of [1] to [6], wherein the component (C) is silica.
[8] The resin composition according to any one of [1] to [7], further comprising a solid thermosetting resin (A-2).
[9] The resin composition according to [8], wherein the 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.
A support and a resin composition layer containing the resin composition provided on the support are included.
The resin composition contains (A) a thermosetting resin and (B) a thermoplastic resin, and (C) does not contain or contains an inorganic filler, and (C) the content of the inorganic filler is the resin composition. When the non-volatile component in the resin is 100% by mass, it is 50% by mass or less, and (C) the specific surface area of the inorganic filler is 40 m ² / g or more.
A resin sheet having a minimum melt viscosity of the resin composition layer of 100 poise or more and 4000 poise or less.
[12] A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [10].
[13] The insulating layer formed by the cured product of the resin composition according to any one of [1] to [10] or the cured product of the resin composition layer of the resin sheet according to claim 11 or 12 is included. , Printed wiring board.
[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) A step of thermosetting the resin composition layer to form an insulating layer.
A method for manufacturing a printed wiring board, which comprises (3) a step of drilling holes in the insulating layer and (4) a step of 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, a cured product capable of suppressing the generation of via bottom voids in the formation of a conductor layer by sputtering can be obtained, and a resin composition having excellent film handleability; a resin composition is contained. A method for manufacturing a resin sheet, a printed wiring board, a semiconductor device, and a printed wiring board can be provided.

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

Hereinafter, the present invention will be described in detail according to the preferred embodiment thereof. However, the present invention is not limited to the following embodiments and examples, and may be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof.

[Resin composition]
The resin composition of the present invention contains (A-1) a liquid or semi-solid thermosetting resin, and (B) a thermoplastic resin, and (C) does not contain or contains an inorganic filler, and (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, and (C) the specific surface area of the inorganic filler is 40 m ² / g or more. Further, 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 having excellent film handleability. Will be able to. Furthermore, in the formation of the conductor layer by sputtering, uneven roughened surfaces such as irregularities due to the inorganic filler and distortion due to the mismatch of thermal expansion 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 further contain any component other than the (C) inorganic filler in combination with the components (A-1) and (B). Examples of the optional component include (A-2) a solid thermosetting resin, (D) a curing accelerator, and (E) other additives. Hereinafter, each component contained in the resin composition will be described in detail.

In the present specification, the component (A-1) and the component (A-2) may be collectively referred to as "(A) thermosetting resin". Further, in the present specification, the “resin component” refers to a component which excludes (C) an inorganic filler from the components constituting the resin composition.

<(A) Thermosetting resin>
As the thermosetting resin (A), a thermosetting resin 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, phenol resins, naphthol resins, benzoxazine resins, active ester resins, cyanate ester resins, and carbodiimide resins. , Amine-based resin, allyl-based resin, acid anhydride-based resin and the like. The term "(meth) acrylic resin" includes acrylic resin and methacrylic resin.

The thermosetting resin (A) may be used alone or in combination of two or more. Here, epoxy resins (meth) such as phenol-based resins, naphthol-based resins, benzoxazine-based resins, active ester-based resins, cyanate ester-based resins, carbodiimide-based resins, amine-based resins, and acid anhydride-based resins. The components that can cure the resin composition by reacting with the acrylic resin and the maleimide resin may be collectively referred to as a "hardener".

The term "(A) thermosetting resin" includes (A-1) liquid or semi-solid thermosetting resin, and (A-2) solid thermosetting resin. Here, the determination of liquid, semi-solid, and solid is performed in accordance with the attached second "Confirmation method of liquid" of the Ministerial Ordinance on Dangerous Goods Test and Properties (Ministerial Ordinance No. 1 of 1989). The specific determination method is as follows.

(1) Equipment constant temperature water tank:
Use a stirrer, heater, thermometer, and automatic temperature controller (those that can control the temperature at ± 0.1 ° C) with a depth of 150 mm or more.
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) manufactured by Yamato Scientific Co., Ltd. and a charging type constant temperature device Thermomate (model BF500) was used, and tap water was about. Put 22 liters in a low temperature constant temperature water tank (model BU300), turn on the power of the thermomate (model BF500) attached to it, set it to the set temperature (20 ° C or 60 ° C), and set the water temperature to the set temperature ± 0.1. The temperature was finely adjusted with a thermomate (model BF500), but any device capable of the same adjustment can be used.

Test tube:
As shown in FIG. 1, the test tube is made of flat-bottomed cylindrical transparent glass having an inner diameter of 30 mm and a height of 120 mm, and marked lines 11A and 12B are attached at heights of 55 mm and 85 mm from the tube bottom, respectively. , A rubber stopper 13b having the same size as the liquid judgment test tube 10a in which the mouth of the test tube is sealed with a rubber stopper 13a, and having a hole in the center for inserting and supporting a thermometer. The test tube 10b for temperature measurement is used in which the mouth of the test tube is sealed and the thermometer 14 is inserted in the rubber stopper 13b. Hereinafter, the marked line having a height of 55 mm from the bottom of the pipe is referred to as "line A", and the marked line having a height of 85 mm from the bottom of the pipe is referred to as "line B".
As the thermometer 14, a thermometer for measuring the freezing point (SOP-58 scale range 0 to 100 ° C.) specified in JIS B7410 (1982) "Glass thermometer for petroleum test" is used, but the temperature is 0 to 100 ° C. Anything that can measure the range will do.

(2) Test implementation procedure Samples left for 24 hours or more under atmospheric pressure at a temperature of 60 ± 5 ° C. are subjected to a liquid determination test tube 10a shown in FIG. 1A and a temperature measurement test shown in FIG. 1B. Put up to 11A line in each tube 10b. The two test tubes 10a and 10b are placed upright in a low-temperature constant temperature water tank so that the 12B line is below the water surface. 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, keep it as it is for 10 minutes. After 10 minutes, take out the liquid judgment test tube 10a from the low-temperature constant temperature water tank, immediately lay it horizontally on a horizontal test table, and use a stopwatch to measure the time when the tip of the liquid level in the test tube moves from line 11A to line 12B. Measure and record.

Similarly, for a sample left at atmospheric pressure of 20 ± 5 ° C. for 24 hours or more, the test is carried out in the same manner as when it is left at atmospheric pressure of 60 ± 5 ° C. for 24 hours or more, and the liquid in the test tube is subjected to the same test. The time when the tip of the surface moves from the 11A line to the 12B line is measured and recorded with a stopwatch.

If the measured time is 90 seconds or less at 20 ° C., it is determined to be liquid.
Those having a measured time of more than 90 seconds at 20 ° C. and a measured time of 90 seconds or less at 60 ° C. are determined to be semi-solid.
If the measured time exceeds 90 seconds at 60 ° C., it is determined to be solid.
Hereinafter, the component (A-1) and the component (A-2) will be described.

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

The component (A-1) is preferably at least one selected from, for example, an epoxy resin, a (meth) acrylic resin, an amine resin, and an allyl resin, from the epoxy resin and the (meth) acrylic resin. It is more preferable that it is at least one selected.

The liquid or semi-solid epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. Further, the epoxy resin preferably has an aromatic structure, and when two or more kinds of epoxy resins are used, it is more preferable that at least one of them has an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles. 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 component of the epoxy resin. % Or more.

Examples of the liquid epoxy resin and semi-solid epoxy resin include glycyrrole type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, and glycidyl amine type epoxy. 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 preferable, and glycylol type epoxy resins, bisphenol A type epoxy resins, and bisphenol F type Epoxy resin is more preferred. Specific examples of the liquid epoxy resin and the semi-solid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US" and "jER828EL" manufactured by Mitsubishi Chemical Co., Ltd. ( Bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin); Mitsubishi Chemical Co., Ltd. "630", "630LSD" (glycidylamine type epoxy resin), ADEKA "ED-523T" (glycylol type epoxy resin (adecaglycyrole)), "EP-3980S" (glycidylamine type epoxy resin), "EP-4088S" (dicyclopentadiene type epoxy resin); Nittetsu Chemical Co., Ltd. & Materials "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., Ltd .; "Selokiside" manufactured by Daicel Co., Ltd. 2021P "(epoxy resin having an ester skeleton)," PB-3600 "(epoxy resin having a butadiene structure);" ZX1658 "," ZX1658GS "(liquid 1,4-glycidyl) manufactured by Nittetsu Chemical & Materials Co., Ltd. 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. ~ 5000 g / eq. , More preferably 50 g / eq. ~ 3000 g / eq. , More preferably 80 g / eq. ~ 2000g / eq. , Even more preferably 110 g / eq. ~ 1000 g / eq. Is. Within this range, the crosslink density of the cured product becomes sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.

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

The liquid or semi-solid (meth) acrylic resin preferably has two or more (meth) acryloyl groups per molecule from the viewpoint of remarkably obtaining the desired effect 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 remarkably obtaining the desired effect of the present invention. As the cyclic structure, a divalent cyclic group is preferable. The divalent cyclic group may be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Above all, a cyclic group containing an alicyclic structure is preferable from the viewpoint of remarkably 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, from the viewpoint of remarkably obtaining the desired effect of the present invention. Hereinafter, it is more preferably 15-membered ring or less, still more preferably 10-membered ring or less. Further, the divalent cyclic group may have a monocyclic structure or a polycyclic structure.

The ring skeleton of the divalent cyclic group may be composed of a hetero atom other than the carbon atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like, and an oxygen atom is preferable. The hetero atom may have one heteroatom in the ring, or may have two or more heteroatoms.

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

The divalent cyclic group may have a substituent. Examples of such a substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group and a hydroxy group. Examples thereof include a mercapto group and an oxo group, and an alkyl group is preferable.

The (meth) acryloyl group may be directly attached to a divalent cyclic group or may be attached via a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, -C (= O) O-, -O-, -NHC (= O)-, and -NC (= O). Examples thereof include N-, -NHC (= O) O-, -C (= O)-, -S-, -SO-, -NH-, and the like, and a group in which a plurality of these are combined may be used. 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 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms. Is even more preferable. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a 1,1-dimethylethylene group and the like, and a methylene group, an ethylene group and 1,1 -Dimethylethylene groups are preferred. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferable, an alkenylene group having 2 to 6 carbon atoms is more preferable, and an alkenylene group having 2 to 5 carbon atoms is further preferable. As the arylene group and the heteroarylene group, an arylene group or a heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or a 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 the formula (1), R ¹ and R ⁴ independently represent an acryloyl group or a methacryloyl group, and 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 independently represent an acryloyl group or a methacryloyl group, and an acryloyl group is preferable.

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 above divalent cyclic group.

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

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

As the liquid or semi-solid (meth) acrylic resin, a commercially available product may be used. For example, "A-DOG" ((meth) acryloyl group equivalent 163) manufactured by Shin-Nakamura Chemical Industry Co., Ltd., manufactured by Kyoeisha Chemical Co., Ltd. "DCP-A" ((meth) acryloyl group equivalent 152), "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 88) ) Acryloyl group equivalent 96) and the like.

The (meth) acryloyl group equivalent of the liquid or semi-solid (meth) acrylic resin is preferably 30 g / eq. From the viewpoint of significantly obtaining the desired effect of the present invention. ~ 400 g / eq. , More preferably 50 g / eq. ~ 300 g / eq. , More preferably 75 g / eq. ~ 200 g / eq. Is. The (meth) acryloyl group equivalent is the mass of the (meth) acrylic resin containing one equivalent of the (meth) acryloyl group.

The allyl resin, which is liquid or semi-solid, is a compound having at least one allyl group in the molecule. The allyl resin preferably has one or more allyl groups per molecule, and more preferably has two or more allyl groups. Further, the allyl resin preferably has either an isocyanul ring structure or a benzoxazine ring structure in addition to the allyl group from the viewpoint of remarkably obtaining the desired effect of the present invention. The allyl resin having an isocyanul structure preferably has a nitrogen atom having an isocyanul structure and an allyl group directly bonded to each other. Further, the allyl resin having a benzoxazine ring is preferably bonded to either a nitrogen atom or a benzene ring of the benzoxazine ring, and more preferably bonded to a nitrogen atom. Examples of such a resin include allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate and the like.

As the liquid or semi-solid allyl resin, a commercially available product may be used, and examples thereof include "L-DAIC" manufactured by Shikoku Chemicals Corporation and "ALP-d" manufactured by JFE Chemicals Corporation.

The allyl group equivalent of the liquid or semi-solid allyl resin is preferably 20 g / eq. From the viewpoint of remarkably obtaining the desired effect 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 an allyl resin containing 1 equivalent of an allyl group.

As the liquid or semi-solid amine resin, a resin having one or more amino groups in one molecule can be used. Examples of the liquid or semi-solid amine-based resin include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like, among which the desired effects of the present invention are exhibited. From the viewpoint, aromatic amines are preferable. The amine-based resin is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of amine-based resins include 4,4'-methylenebis (2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, and m-phenylenediamine. , M-xylylene diamine, 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, etc. Commercially available products may be used as the amine resin, for example, "KAYABOND C-200S", "KAYABOND C-100", "Kayahard A-A", "Kayahard AB", "Kayahard" manufactured by Nippon Kayaku Corporation. Examples include "AS" and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

The amino group equivalent of the liquid or semi-solid amine resin is preferably 20 g / eq. From the viewpoint of remarkably obtaining the desired effect 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 amino group equivalent is the mass of an amine resin containing 1 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. As mentioned above, it is more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less, 25% by mass or less, 20% by mass. % Or less, 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 minimum melt viscosity of the epoxy resin and the (meth) acrylic resin as the component (A-1) is lowered. 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, still more preferably 5% by mass or more, from the viewpoint of improving the embedding property. Yes, preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or 15% by mass or less.

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

-(A-2) Solid thermosetting resin-
The resin composition may contain a solid thermosetting resin as an arbitrary component and further as a component (A-2). By including the component (A-2) in the resin composition, the film handleability can be further improved.

Examples of the component (A-2) include epoxy resin, maleimide resin, phenol resin, naphthol resin, active ester resin, cyanate ester resin, carbodiimide resin, benzoxazine resin, acid anhydride resin and the like. The epoxy resin, the cyanate ester resin, the carbodiimide resin, and the maleimide resin are preferable, and at least one of the cyanate ester resin, the carbodiimide resin, and the maleimide resin is more preferable.

The solid epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. Further, the epoxy resin preferably has an aromatic structure, and when two or more kinds of epoxy resins are used, it is more preferable that at least one of them 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 component of the epoxy resin. % Or more.

Examples of the solid epoxy resin 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, and naphthylene ether type epoxy resin. Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" manufactured by DIC. Cresol novolac 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) manufactured by Nippon Kayakusha. Phenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" manufactured by Nittetsu Chemical & Materials Co., Ltd. (Naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. ), "YX8800" (anthracene type epoxy resin); "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "YL7800" ( Fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin) and the like.

The epoxy equivalent and weight average molecular weight of the solid epoxy resin are the same as those of the liquid or semi-solid epoxy resin.

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

The number of maleimide groups per molecule of the maleimide resin is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 3 or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. Is 10 or less, more preferably 6 or less, and particularly preferably 3 or less.

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, from the viewpoint of remarkably obtaining the desired effect of the present invention. Is more preferable.

As the aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group is preferable, a divalent saturated aliphatic hydrocarbon group is more preferable, and an alkylene group is further preferable. 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 further preferable, and a methylene group is particularly preferable.

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

In the maleimide resin, the nitrogen atom of the maleimide group is preferably directly bonded to a monovalent or divalent aromatic hydrocarbon group from the viewpoint of remarkably obtaining the desired effect of the present invention. 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 by the following formula (3), for example.

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 a divalent aromatic group. m1 and m2 independently represent an integer of 1 to 10, and n represents an integer of 1 to 100.

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

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 further preferable. The alkyl group may be linear, branched or cyclic. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group and the like.

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 a monocyclic ring or a condensed ring. Examples of such an aryl group include a phenyl group, a naphthyl group, an anthracenyl group and the like.

The alkyl group and the aryl group may have a substituent. The substituent is not particularly limited, and is, for example, a halogen atom, -OH, -OC _1-6 alkyl group, -N (C _1-10 alkyl group) ₂ , C _1-10 alkyl group, C _6-. Examples thereof include a 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 " (p and q are positive integers and satisfy p <q) is described immediately after this term and the number of carbon atoms of the organic group is p to q. Indicates that there is. For example, the expression "C _1-10 alkyl group" indicates an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring.

The above-mentioned substituent may further have a substituent (hereinafter, may be referred to as a "secondary substituent"). Unless otherwise specified, the same as the above-mentioned substituent may be used as the secondary substituent.

D in the 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, a biphenylaralkyl group and the like. Among them, a biphenylene group and a biphenylaralkyl group are preferable, and a biphenylene group is more preferable. .. 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 the 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 1 is even more preferable.

n represents an integer of 1 to 100, preferably 1 to 50, more preferably 1 to 20, and even more preferably 1 to 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, the resin represented by the formula (4) is preferable.

In formula (4), R ²¹ and R ²² represent maleimide groups. n1 represents an integer of 1 to 100.

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

As the maleimide resin, a commercially available product can be used. Examples of commercially available products include "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.

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

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

As the solid active ester resin, a resin having one or more active ester groups in one molecule can be used. Among them, as the solid active ester resin, 2 ester groups having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are contained in one molecule. A resin having more than one is preferable. 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 resin obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable.

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

Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

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 product of phenol novolac, and phenol. Examples thereof include active ester-based resins containing novolak benzoylides. Of these, an active ester resin containing a naphthalene structure and an active ester resin containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Commercially available solid active ester-based resins include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC" as active ester-based resins containing a dicyclopentadiene-type diphenol structure. -8000H-65TM "," EXB-8000L-65TM "(manufactured by DIC);" EXB9416-70BK "," EXB-8150-65T "(manufactured by DIC) as active ester resins containing a naphthalene structure; "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester resin containing an acetylated product; "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester resin containing a benzoylated product of phenol novolac; an active ester which is an acetylated product of phenol novolac. "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as a system resin; "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.) as active ester-based resins that are benzoylated phenol novolac (Made by Chemical Co., Ltd.); etc.

Examples of the solid cyanate ester resin include bisphenol A cyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylencianate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4 , 4'-Etilidendiphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5) Bifunctional cyanates such as −dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether. Resins; polyfunctional cyanate resins derived from phenol novolac, cresol novolak, etc .; prepolymers in which these cyanate resins are partially triazined; and the like. Specific examples of the cyanate ester resin include "PT30", "PT30-80M" and "PT60" (phenol novolac type polyfunctional cyanate ester resin) and "ULL-950S" (polyfunctional cyanate ester resin) manufactured by Ronza Japan. ), "BA230", "BA230S75" (prepolymer in which a part or all of bisphenol A disyanate is triazined to form a trimer) and the like.

Specific examples of the solid carbodiimide-based resin include carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216, V-05 (carbodiimide group equivalent: 262)) and V-07 (carbodiimide group equivalent) manufactured by Nisshinbo Chemical Co., Ltd. : 200); V-09 (carbodiimide group equivalent: 200); Stavaxol® P (carbodiimide group equivalent: 302) manufactured by Rheinchemy.

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., and "ODA-". "BOZ"; "FA" manufactured by Shikoku Kasei Kogyo Co., Ltd .; "HFB2006M" manufactured by Showa Polymer Co., Ltd. and the like can be mentioned.

Examples of the solid acid anhydride-based resin include resins having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride-based resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, and methylnadic hydride anhydride. Trialkyltetrahydrophthalic anhydride, succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimerit anhydride Acid, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenyl Sulphontetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1, Examples thereof include 3-dione, ethylene glycol bis (anhydrotrimeritate), and polymer-type acid anhydrides such as styrene / maleic acid resin in which styrene and maleic acid are copolymerized.

The content of the component (A-2) is preferably 10% by mass or more, more preferably 10% by mass or more, when the non-volatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. 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, 60% by mass or less.

When the resin composition contains the component (A-2), it is preferable to include an epoxy resin and a curing agent as the component (A-2). In this case, the total content of the epoxy resin and the curing agent as the component (A-2) is determined 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. 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, still more preferably 60% by mass or less.

When the resin composition contains the component (A-2), it is preferable to contain the maleimide resin as the 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 remarkably obtaining the desired effect of the present invention. It is mass% or more, more preferably 30% by mass or more, further preferably 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.

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

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 preferably contains a curing agent. Is more preferable. In this case, the mass ratio of the epoxy resin and (meth) acrylic resin as the component (A-1) to the epoxy resin and the curing agent as the component (A-2) (mass% of the component (A-2) / ( A-1) The mass% of the 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. More preferably, it is 1 or less. By setting the mass ratio within such a range, the thermosetting of the resin composition can be more effectively promoted, and the mechanical strength of the cured product can be further increased.

The content of the component (A) (the total content of the component (A-1) and the component (A-2)) is a non-volatile component in the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. Is 100% by mass or more, 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, still 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. When the resin composition contains the thermoplastic resin as the component (B), the film handleability can be improved. Further, by incorporating (B) a thermoplastic resin in the resin composition, it is possible to reduce the coefficient of linear thermal expansion of the cured product.

Examples of the thermoplastic resin include phenoxy resin, polycarbonate resin, polyvinyl acetal resin, polyolefin resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, and polyether. Examples thereof include ether ketone resin and polyester resin. Among them, at least one selected from a polyimide resin, a polycarbonate resin and a phenoxy resin is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. Further, (B) the thermoplastic resin may be used alone by one type, or may be used in combination of two or more types.

As the polyimide resin, a resin having an imide structure can be used. The polyimide resin generally includes those obtained by an imidization reaction of a diamine compound and an acid anhydride.

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

Examples of the aliphatic diamine compound 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 chain aliphatic diamine compounds such as diaminopentane; 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexyl) An alicyclic diamine compound such as amine); a dimer acid type diamine (hereinafter, also referred to as “dimer diamine”) and the like can be mentioned. The diamine acid type diamine is a diamine compound obtained by substituting two terminal carboxylic acid groups (-COOH) of dimer acid with an aminomethyl group (-CH _2- NH ₂ ) or an amino group (-NH ₂ ). means. Dimeric acid is a known compound obtained by dimerizing unsaturated fatty acids (preferably those having 11 to 22 carbon atoms, particularly preferably those having 18 carbon atoms), and its industrial production process is almost the same in the industry. It is standardized.

Examples of the aromatic diamine compound include a phenylenediamine compound, a naphthalene diamine compound, a dianiline compound and the like.

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

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

The dianiline compound means a compound containing two aniline structures in the molecule, and each of the two benzene rings in the two aniline structures further optionally has 1 to 3 substituents. Can be. The substituent here is not particularly limited. The two aniline structures in the dianiline compound are directly bonded and / or bonded via one or two linker structures having 1 to 100 skeleton atoms selected from carbon, oxygen, sulfur and nitrogen atoms. Can be done. 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- , -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- ,

And so on. In the present specification, "Ph" indicates 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'-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfide, 4-aminophenyl4-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'-(hexafluoroisopropi) Liden) 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-trimethylindan and the like.

As the diamine compound, a commercially available one may be used, or a compound synthesized by a known method may be used. The diamine compound may be used alone or in combination of two or more.

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 acid dianhydride and the like, and preferred examples thereof. It is a diphthalic dianhydride.

The benzenetetracarboxylic dianhydride means a benzene dianhydride having 4 carboxy groups, and the benzene ring here may optionally have 1 to 3 substituents. Here, as the substituent, those selected from a halogen atom, a cyano group, and -X ^33- R ³³ (same as the definition of the following formula (1B)) are preferable. Specific examples of the benzenetetracarboxylic dianhydride include pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride and the like.

The naphthalenetetracarboxylic dianhydride means a naphthalene dianhydride having 4 carboxy groups, and the naphthalene ring here may optionally have 1 to 3 substituents. Here, as the substituent, those selected from a halogen atom, a cyano group, and -X ^33- R ³³ (same as the definition of the following formula (1B)) are preferable. Specific examples of the naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride and the like.

The anthracene tetracarboxylic dianhydride means an anthracene dianhydride having 4 carboxy groups, and the anthracene ring here may optionally have 1 to 3 substituents. Here, as the substituent, those selected from a halogen atom, a cyano group, and -X ^33- R ³³ (same as the definition of the following formula (1B)) are preferable. Specific examples of the anthracene tetracarboxylic dianhydride include 2,3,6,7-anthracene tetracarboxylic dianhydride.

The diphthalic anhydride means a compound containing two phthalic anhydrides in the molecule, and the two benzene rings in the two phthalic anhydrides are optionally 1 to 3 rings, respectively. It may have a substituent. Here, as the substituent, those selected from a halogen atom, a cyano group, and -X ^33- R ³³ (same as the definition of the following formula (1B)) are preferable. The two phthalic anhydrides in diphthalic acid dianhydride can be bonded directly or via a linker structure having 1 to 100 skeleton atoms selected from carbon, oxygen, sulfur and nitrogen atoms.

As the diphthalic acid dianhydride, for example, the formula (1B):

[During the ceremony,
R ³¹ and R ³² independently represent a halogen atom, a cyano group, a nitro group, or -X ^33- R ³³ , respectively.
X ³³ are each independently a single ^{bond, -NR 33 '-, - O} -, - S -, - CO -, - SO 2 -, - NR 33' CO -, - CONR 33 '-, - OCO -Or -COO-, indicating
R ³³ independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group.
R ^{33'independently} represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group.
Y represents a single bond or a linker structure having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms.
n10 and m10 each independently represent an integer of 0 to 3. ]
Examples thereof include compounds represented by.

Y is preferably a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. n and m are preferably 0.

The "linker structure" in 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 − [in the formula, A is an independently single-bonded, − (substituted or unsubstituted alkylene group”. ) -, - O -, - S -, - CO -, - SO 2 -, - CONH -, - NHCO -, - COO-, or -OCO- indicates, a and b are each independently 0 Indicates an integer of ~ 2 (preferably 0 or 1). ] Is a divalent group represented by.

"Linker structure" in Y, _{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-,- Examples thereof include O-Ph-SO ₂ -Ph-O-, -O-Ph-C (CH ₃ ) ₂ -Ph-O-. In the present specification, "Ph" indicates a 1,4-phenylene group, a 1,3-phenylene group or a 1,2-phenylene group.

Specific examples of the diphthalic dianhydride include 4,4'-oxydiphthalic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-. Diphenylethertetracarboxylic 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'-diphenylsulfonetetracarboxylic dianhydride 2,2'-bis (3,4-dicarboxyphenoxyphenyl) ) Spherone dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethinilidene-4,4'-diphthalic acid dianhydride, 2,2-propylidene-4,4'-diphthalic acid dianhydride Anhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthal 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 can be mentioned.

As the acid anhydride, a commercially available one may be used, or one synthesized by a known method or a method similar thereto may be used. The acid anhydride may be used alone or in combination of two or more.

A commercially available product can be used as the polyimide resin. Examples of commercially available products include "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd.

As the polycarbonate resin, a resin having a carbonate structure can be used. Examples of such resins include carbonate resins having no reactive group, hydroxy 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, and urethane groups. Examples include the contained carbonate resin. Here, the reactive group refers to a functional group capable of reacting with other components such as a hydroxy group, a phenolic hydroxyl group, a carboxy 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. Commercially available products include "FPC0220" manufactured by Mitsubishi Gas Chemical Company, "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and "C-1090", "C-2090" and "C" manufactured by Kuraray. -3090 ”(polycarbonate diol) and the like.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetphenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantan skeleton, and terpen Examples thereof include 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 "1256" and "4250" manufactured by Mitsubishi Chemical Co., Ltd. (both are bisphenol A skeleton-containing phenoxy resins); "YX8100" manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol S skeleton-containing phenoxy resin); "YX6954" (bisphenol acetophenone skeleton-containing phenoxy resin); "FX280" and "FX293" manufactured by Nittetsu Chemical &Materials; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd. , "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482"; and the like.

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include Eslek BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

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

Specific examples of the polyether sulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

Specific examples of the polyphenylene ether resin include oligophenylene ether / styrene resin “OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Company, Ltd.

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

(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 remarkably obtaining the desired effect of the present invention. It is preferably 70,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less.

The content of the thermoplastic resin (B) 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 the film handleability. 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. It is 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 further preferably 90% by mass or less.

<(C) Inorganic filler>
The resin composition contains or does not contain (C) an inorganic filler. However, the content of the inorganic filler (C) is 50% by mass or less when the non-volatile component in the resin composition is 100% by mass. When the component (C) is contained with the inorganic filler, the specific surface area of the (C) inorganic filler 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 above-mentioned components (A-1) and (B), when the component (C) satisfies the above requirements, it is possible to suppress the generation of via bottom voids, and the film handleability is improved. It becomes possible to improve.

The content of the inorganic filler (C) 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. It is preferably 40% by mass or less, more preferably 30% by mass or less, and further 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 further 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, and more preferably 60 m ² / g or more, from the viewpoint of suppressing the generation of via bottom voids. Although there is no particular limitation on the upper limit, it is preferably 300 m ² / g or less, more preferably 200 m ² / g or less, and further preferably 100 m ² / g or less from the viewpoint of further improving the film handleability. 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 materials for inorganic fillers 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, zirconate titanate , Barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconate titanate, zirconate tungsten phosphate and the like. Of these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. (C) The inorganic filler may be used alone or in combination of two or more.

(C) Commercially available inorganic fillers include, for example, "YA050C-MJE", "50 nmSV-AM1" and "50 nmSZ-AM1" manufactured by Admatex; "NSS-4N" and "NSS-" manufactured by Tokuyama Corporation. "5N"; "UFP-60" and "UFP-80" manufactured by Denka Corporation can be mentioned.

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

(C) The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, 100 mg of an inorganic filler and 10 g of methyl ethyl ketone can be weighed in a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device, the wavelengths of the light sources used were blue and red, and the volume-based particle size distribution of (C) the inorganic filler was measured by the flow cell method. The average particle size can be calculated as the median diameter from the diameter distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by HORIBA, Ltd.

The inorganic filler (C) is preferably treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilanes, organosilazane compounds, and titanates. Coupling agents, (meth) acrylic silane and the like can be mentioned. In addition, one type of surface treatment agent may be used alone, or two or more types may be used in any 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., and Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-" manufactured by Shin-Etsu Chemical Co., Ltd. 7103 ”(3,3,3-trifluoropropyltrimethoxysilane) and the like.

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

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is further preferable. 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 (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. or the like can be used.

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

Examples of the curing accelerator 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. Of these, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and peroxide-based curing accelerators are preferable, and imidazole-based curing accelerators, metal-based curing accelerators, and peroxides are preferred. A physical curing accelerator is more preferable. The curing accelerator may be used alone or in combination of two or more.

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

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 1,2-dimethyl imidazole, and the like. 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 trimerite, 1-cyanoethyl- 2-Phenylimidazolium trimerite, 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 isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-Phenylimidazoline and other imidazole compounds and adducts of the imidazole compound and an epoxy resin are mentioned, 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, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, and trimethylguanidine. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadesylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 Examples thereof include −allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biganide, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferable.

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

Examples of the peroxide-based curing accelerator include t-butylcumylperoxide, t-butylperoxyacetate, α, α'-di (t-butylperoxy) diisopropylbenzene, and t-butylperoxylaurate. Examples thereof include t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, and t-butylperoxybenzoate.

Examples of commercially available peroxide-based curing accelerators include "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", "Perbutyl O", and "Perbutyl ND" manufactured by NOF CORPORATION. Examples thereof include "perbutyl Z", "park mill P", and "park mill D".

The content of the curing accelerator (D) 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 remarkably obtaining the desired effect 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, still more preferably 0.3% by mass or less.

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

The method for 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 components as necessary and mixing and dispersing them using a rotary mixer or the like.

<Physical properties and uses of resin composition>
The resin composition of the present invention exhibits a property of being excellent in embedding property. Therefore, a resin sheet having excellent film handleability is provided. Specific examples of the measurement of embedding property include using a resin sheet as a glass cloth base material epoxy resin double-sided copper-clad laminate (copper foil thickness 3 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemicals Co., Ltd. “HL832NSF LCA”, 255 × (340 mm size) is laminated, 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, observe three arbitrarily set 1 cm squares on the wiring pattern of the evaluation substrate, and measure voids, which are appearance defects with a diameter of 10 μm or more. At this time, the number of voids is usually 0. The details of the evaluation of the implantability can be measured according to the method described in Examples described later.

The resin composition of the present invention exhibits a property of being excellent in exudability. Therefore, a resin sheet having excellent film handleability is provided. The exudation amount represents the ease of control at the time of manufacturing the inner layer substrate, and when the exudation amount is within the following range, the control at the time of manufacturing the inner layer substrate becomes easy. As a specific example of the exudability measuring method, the resin sheet is laminated on the inner layer circuit board, and the length of the resin exuded from the outer peripheral portion of the resin sheet is defined as the exuding amount. The amount of exudation at any 10 points is measured, and the average thereof is 0.5 mm or more and 5 mm or less. The details of the evaluation of the exudability can be measured according to the method described in Examples described later.

The surface of the 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 has a characteristic that the roughened surface has a low arithmetic mean roughness (Ra). Shown. Therefore, the cured product provides an insulating layer having 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 evaluation of the arithmetic mean roughness (Ra) can be measured according to the method described in Examples described later.

After forming via holes in the cured product obtained by thermosetting the resin composition of the present invention at 100 ° C. for 20 minutes and then at 180 ° C. for 30 minutes, the residue of the inorganic filler is suppressed on the bottom of the via. .. Therefore, the cured product provides an insulating layer in which via bottom voids are suppressed. A specific example of the measurement of the via bottom void is that the resin sheet is made of a glass cloth base material epoxy resin double-sided copper-clad laminate (copper foil thickness 3 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemicals Co., Ltd. “HL832NSF LCA”, 255. (× 340 mm size) is laminated, 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. Via holes are formed in the insulating layer by a UV-YAG laser, desmear treatment is performed, and then a conductor layer is formed by sputtering. The cross section of the substrate after forming the conductor layer is observed in cross section of 10 randomly selected via holes using an SEM image. At this time, normally, no via bottom void is generated in 10 via holes. The details of the evaluation of the via bottom void can be measured according to the method described in Examples described later.

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 characteristic of having a low coefficient of linear thermal expansion. Therefore, the cured product provides an insulating layer having 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 1 ppm or more. The linear thermal expansion coefficient can be measured according to the method described in Examples described later.

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, 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 at 60 ° C to 200 ° C. The minimum melt viscosity can be measured using a dynamic viscoelasticity measuring device. The measurement of the minimum melt viscosity can be carried out according to the method described in Examples described later. When the minimum melt viscosity of the resin composition is within such a range, the film handleability becomes excellent.

The resin composition of the present invention can reduce the minimum melt viscosity and improve the embedding property, and as a result, the film handleability can be improved. Further, a cured product capable of suppressing the generation of via bottom voids can be obtained. Therefore, the resin composition of the present invention is a resin composition for forming the insulating layer (including a rewiring layer) for forming a conductor layer by sputtering on the insulating layer (forming a conductor layer by sputtering). It can be suitably used as a resin composition for forming an insulating layer to be formed). Further, in the multilayer printed wiring board described later, a resin composition for forming an insulating layer of the multilayer printed wiring board (resin composition for forming an insulating layer of the multilayer printed wiring board) and an interlayer insulating layer of the printed wiring board. Can be suitably used as a resin composition for forming the above (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 the resin composition provided on the support, and the resin composition is (A) a thermosetting resin and (B). When the thermoplastic resin is contained and (C) the inorganic filler is not included or is contained, and the content of the (C) inorganic filler is 100% by mass of the non-volatile component in the resin composition, it is 50% by mass or less. Yes, (C) the specific surface area of the inorganic filler is 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. The component (A) may contain at least one of the component (A-1) and the component (A-2), and preferably contains the component (A-1). The components (A-1) and (A-2) are as described above.

Each component other than the component (A) in the resin composition is as described above.

The minimum melt viscosity of the resin composition layer 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 from the viewpoint of improving the film handleability. 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 from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product having excellent insulating properties even if the cured product of the resin composition is a thin film. It is preferably 12 μm or less, more preferably 10 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 μm or more, 5 μm or more, or the like.

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

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). ) Etc., polyester, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethylmethacrylate (PMMA), cyclic polyolefin, triacetylcellulose (TAC), polyethersulfide (PES), polyether. Examples thereof include ketones and polyimides. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

The surface of the support to be joined to the resin composition layer may be matted, corona-treated, or antistatic-treated.

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

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

In one embodiment, the resin sheet may further contain other layers, if desired. Examples of such other layers include a protective film similar to the support provided on a surface of the resin composition layer that is not bonded to the support (that is, a surface opposite to the support). Be done. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of dust and the like to the surface of the resin composition layer and scratches.

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

Examples of the organic solvent 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 and the like. Carbitols; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

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 depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition is obtained by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes. A material layer can be formed.

The resin sheet can be rolled up 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 of 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, the conductor layer is preferably formed by sputtering.

The printed wiring board can be manufactured, for example, by using the above-mentioned resin sheet 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) In the insulating layer Step of drilling (4) Step of forming a conductor layer on the insulating layer by sputtering

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

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

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

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

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

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

In step (2), the resin composition layer is thermoset to form an insulating layer. The thermosetting conditions of the resin composition layer are not particularly limited, and the conditions usually adopted when forming the insulating layer of the printed wiring board may be used.

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

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

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. The lower limit is not particularly limited, but may be usually 1 μm or more, 5 μm or more, or the like.

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

Since the insulating layer is formed of a cured product of the resin composition of the present invention, the top diameter can be reduced. 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 may be 1 μm or more.

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

The step (A) is a step of roughening the insulating layer. Usually, in this step (A), smear is also removed. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of the printed wiring board can be adopted. Moreover, either dry type or wet type may be used.

The 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 is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, etc.). A layer formed from a nickel alloy and a copper / titanium alloy) can be mentioned. Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper, etc. An alloy layer of a nickel alloy or a copper-titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable.

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

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

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. The surface of the insulating layer may be cleaned by reverse sputtering before forming the conductor seed layer by sputtering. As the gas used for the reverse sputtering, various gases can be used, and among them, Ar, O ₂ and N ₂ are preferable. Ar or O ₂ or Ar, O ₂ mixed gas when the seed layer is Cu and Cu alloy, Ar or N ₂ or Ar, N ₂ mixed gas when the seed layer is Ti, Cr and Cr alloy (Nichrome) In the case of), Ar or O ₂ or Ar, O ₂ mixed gas is preferable. Sputtering can be performed using various sputtering devices such as magnetron sputtering and mirrortron sputtering. Examples of the metal forming the conductor seed layer include Cr, Ni, Ti, nichrome and the like. Especially Cr and Ti are preferable. The thickness of the conductor seed layer is usually preferably 5 nm or more, more preferably 10 nm or more, preferably 1000 nm or less, and more preferably 500 nm or less. Examples of the metal forming the conductor sputter layer include Cu, Pt, Au, Pd and the like. Cu is particularly preferable. The thickness of the conductor sputtered layer is usually preferably 50 nm or more, more preferably 100 nm or more, preferably 3000 nm or less, and more preferably 1000 nm or less.

The surface roughness (Ra value) formed on the surface of the insulating layer at the time of forming the conductor seed layer is preferably 150 nm or less as a measured value after removing the conductor seed layer by etching, and further ranges from 10 to 150 nm. It is preferable, and more preferably 10 to 120 nm or less.

After forming the conductor layer by the sputtering method, 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, preferably 75 μm or less, and more preferably 35 μm or less. A known method such as a subtractive method or a semi-additive method can be used for circuit formation.

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

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

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

The mounting method of the semiconductor chip in manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and a bumpless build-up layer. Examples thereof include a mounting method using (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, the "mounting method using the bumpless build-up layer (BBUL)" means "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board". Is.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the following description, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<(A) Judgment of liquid, semi-solid, and solid state of thermosetting resin>
(A) Judgment of liquid, semi-solid, and solid state of thermosetting resin is the second "confirmation method of liquid" of the Ministerial Ordinance on Dangerous Goods Test and Properties (Ministerial Ordinance No. 1 of 1989). It was done according to. The "liquid confirmation method" was carried out as described above. The results are shown below.
"630" manufactured by Mitsubishi Chemical Co., Ltd .; liquid "ELM-100" manufactured by Sumitomo Chemical Co., Ltd .; liquid "A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd .; liquid "AA" manufactured by Nippon Kayaku Co., Ltd .; liquid "L-DAIC" Shikoku Kasei Co., Ltd .; Liquid "ALP-d" manufactured by JFE Chemical Co., Ltd .; Liquid "YX4000" manufactured by Mitsubishi Chemical Co., Ltd .; Solid "BA230S75" manufactured by Lonza Japan Co., Ltd .; Solid "V-03" manufactured by Nisshinbo Chemical Co., Ltd .; Solid " MIR-3000-70MT "manufactured by 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 to calculate the specific surface area of the inorganic filler. The specific surface area was measured.
The inorganic filler dispersed in the organic solvent was dried in a drying furnace at 60 ° C. for 12 hours, and the specific surface area was measured by volatilizing the organic solvent. The results are shown below.
"YA050C-MJE" manufactured by Admatex, surface treatment with methacrylic silane; 61.8 m ² / g
"UFP-30" manufactured by Denka Co., Ltd .; 30.7m ² / g

<Synthesis Example 1: Synthesis of Polyimide Resin>
A 500 mL separable flask equipped with a moisture metering receiver connected to a reflux condenser, a nitrogen introduction pipe, and a stirrer was prepared. In this flask, 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) Phenyl] -1,1,3-trimethylindan 29.6 g was added, and the reaction was carried out by stirring at 45 ° C. for 2 hours under a nitrogen stream. The reaction solution was then heated to about 160 ° C. and the condensed water was azeotropically removed with toluene under a nitrogen stream. It was confirmed that a predetermined amount of water had accumulated in the moisture metering receiver and that no outflow of water was observed. After confirmation, the reaction solution was further heated and stirred at 200 ° C. for 1 hour. Then, it was cooled to obtain a polyimide solution (nonvolatile 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). The weight average molecular weight of the polyimide resin was 12,000.

<Example 1>
3 parts of glycidylamine type epoxy resin (Mitsubishi Chemical "630", epoxy equivalent 95 g / eq.), 30 parts of the polyimide resin prepared in Synthesis Example 1, inorganic filler ("YA050C-MJE" manufactured by Admatex), ratio 20 parts of MEK solution with a surface area of 61.8 m ² / g, an average particle size of 50 nm, and a non-volatile content of 50% by mass, 5 parts of biphenyl type epoxy resin (Mitsubishi Chemical Corporation "YX4000", epoxy equivalent about 190 g / eq.), Bisphenol 20 parts of A dicyanate prepolymer (“BA230S75” manufactured by Ronza Japan Co., Ltd., cyanate equivalent of about 232 g / eq., MEK solution having a non-volatile content of 75% by mass), curing accelerator (cobalt (III) acetylacetone “(Co (acac) ₃ ) 0.5 part of "-1M" (MEK solution having 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 Corporation, thickness 38 μm, PET film) having a release layer was prepared. The resin varnish was uniformly applied onto the release layer of the support so that the thickness of the resin composition layer after drying was 15 μm. Then, the resin varnish was dried at 80 ° C. to 100 ° C. (average 90 ° C.) for 3 minutes. Next, a rough surface of a polypropylene film (“Alfan MA-411” manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) as a protective film is bonded to the resin composition layer on the surface that is not bonded to the support of the resin composition layer. Laminated so as to. As a result, a resin sheet composed of a support, a resin composition layer, and a protective film was produced.

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

<Measurement of coefficient of linear thermal expansion (CTE)>
(1) Preparation of sample for evaluation of cured physical properties The resin sheets of each Example and each Comparative Example prepared in advance were heat-cured at 200 ° C. for 90 minutes, and then the support was peeled off to prepare a sample for evaluation of cured physical properties. ..

(2) Measurement of coefficient of linear thermal expansion A sample for evaluation of cured physical properties is cut into test pieces having a width of about 5 mm and a length of about 15 mm, and is tensioned using a thermomechanical analyzer (Thermo Plus TMA8310, manufactured by Rigaku). Thermomechanical analysis was performed by the weighting method. After the test piece was attached to the apparatus, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. The 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 viscosity of the resin composition layer of the resin sheet of each Example and each Comparative Example prepared in advance was measured using a dynamic viscoelasticity measuring device (“Rheosol-G3000” manufactured by UBM). Using a parallel plate with a diameter of 18 mm, 1 g of the sample resin composition was heated from a starting temperature of 60 ° C. to 200 ° C. at a heating rate of 5 ° C./min, with a measurement temperature interval of 2.5 ° C., vibration of 1 Hz, and strain. The dynamic viscoelasticity was measured under the measurement condition of 5 deg, and the lowest melt viscosity (minimum melt viscosity) was used as the evaluation value.

<Evaluation of film handleability and arithmetic surface roughness (Ra) after roughening treatment>
(1) Base treatment of inner layer circuit board A glass cloth base material epoxy resin double-sided copper-clad laminate having circuit conductors (copper) formed with a wiring pattern of L / S = 15 μm / 15 μm on both sides as an inner layer circuit board ( A copper foil thickness of 18 μm, a substrate thickness of 0.15 mm, and “HL832NSF LCA” manufactured by Mitsubishi Gas Chemicals Co., Ltd. (255 × 340 mm size) were prepared.

(2) Lamination of Resin Sheets The protective film is peeled off from the resin sheets of each example and each comparative example prepared in advance, and a batch type vacuum pressure laminator (2-stage build-up laminator manufactured by Nikko Materials Co., Ltd., CVP700) is used. The resin composition layer was laminated on both sides of the inner layer circuit board so as to be in contact with the inner layer circuit board. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and crimping at 100 ° C. and a pressure of 0.74 MPa for 45 seconds. Then, heat 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 on which the resin composition layer is laminated 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 for insulation. An evaluation substrate was prepared by forming a layer and peeling off the support.

(4) Evaluation of embedding property Using a digital microscope (“DIGITAL MICROSCOPE KH-8700” manufactured by Hirox Co., Ltd.), observe three arbitrarily set 1 cm squares on the wiring pattern of the evaluation board, and observe them in it. The case where there was one or more voids having an appearance defect of 10 μm or more in diameter was evaluated as “x”, and the case where there were no voids was evaluated as “◯”. The absence of voids indicates excellent embedding.

(5) Evaluation of exudability In (2), the length of the resin exuded from the outer peripheral portion of the resin sheet when the resin sheet is laminated on the inner layer circuit board is defined as the “exud amount”. The amount of exudation at any 10 points was measured, and the case where the average was 0.5 mm or more and 5 mm or less was evaluated as “◯”, and the case where the average was less than 0.5 mm or exceeded 5 mm was evaluated as “x”. The fact that the amount of exudation is within the range indicates the ease of control during substrate production.

(6) Step of roughening treatment The insulating layer of the evaluation substrate was subjected to desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was carried out.

Wet desmear treatment:
In a swollen solution (Atotech Japan's "Swelling Dip Securigant P", an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, then an oxidizing agent solution (Atotech Japan's "Concentrate Compact CP" , Aqueous solution of potassium permanganate concentration of about 6%, sodium hydroxide concentration of about 4%) at 80 ° C. for 20 minutes, and finally in a neutralizing solution (Atotech Japan's "Reduction Solution Securigant P", aqueous sulfuric acid solution) After soaking 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 Becoin Sturments), the measurement range is 121 μm × 92 μm with a VSI contact mode and a 50x lens. The value (nm) of the arithmetic surface roughness (Ra) of the roughened substrate was determined from the numerical value obtained as. Further, it was measured by obtaining the average value of 10 points.

<Evaluation of voids at the bottom of the via>
(1) Base treatment of inner layer circuit board Glass cloth base material epoxy resin double-sided copper-clad laminate having circuit conductors (copper) formed with a wiring pattern of L / S = 2 μm / 2 μm on both sides as an inner layer circuit board ( A copper foil thickness of 3 μm, a substrate thickness of 0.15 mm, and “HL832NSF LCA” manufactured by Mitsubishi Gas Chemicals Co., Ltd. (255 × 340 mm size) were prepared.

(2) Lamination of Resin Sheets The protective film is peeled off from the resin sheets of each example and each comparative example prepared in advance, and a batch type vacuum pressure laminator (2-stage build-up laminator manufactured by Nikko Materials Co., Ltd., CVP700) is used. The resin composition layer was laminated on both sides of the inner layer circuit board so as to be in contact with the inner layer circuit board. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and crimping at 100 ° C. and a pressure of 0.74 MPa for 45 seconds. Then, heat 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 on which the resin composition layer is laminated 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 for insulation. A substrate for void evaluation was produced by forming a layer and peeling off the support.

(4) Formation of via holes with UV-YAG laser The support is peeled off to expose the surface of the insulating layer, and insulation is performed using a UV-YAG laser processing machine (“LU-2L212 / M50L” manufactured by Via Mechanics). Via holes were formed in the layer under the following conditions.
Conditions: Power 0.25W, number of shots 20, target top diameter 20μm

(5) Step of roughening treatment The insulating layer of the void evaluation substrate was subjected to desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was carried out.

Wet desmear treatment:
In a swollen solution (Atotech Japan's "Swelling Dip Securigant P", an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, then an oxidizing agent solution (Atotech Japan's "Concentrate Compact CP" , Aqueous solution of potassium permanganate concentration of about 6%, sodium hydroxide concentration of about 4%) at 80 ° C. for 20 minutes, and finally in a neutralizing solution (Atotech Japan's "Reduction Solution Securigant P", aqueous sulfuric acid solution) After soaking 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 Cannon Anerva). The obtained substrate was heated at 150 ° C. for 30 minutes for annealing, and then an etching resist was formed according to a semi-additive method. After pattern formation by exposure and development, copper sulfate electrolytic plating was performed to obtain 25 μm. A conductor layer was formed with the thickness of. After forming the conductor pattern, it was heated at 200 ° C. for 60 minutes to perform annealing treatment. The obtained printed wiring board is referred to as "evaluation board A".

(7) Evaluation of Residue by Cross-Section Observation A cross-section observation of the via hole of the evaluation substrate A was performed using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology Co., Ltd.). Specifically, a cross section in which the via can be observed vertically was cut out by a FIB (focused ion beam), and a cross-section SEM image (observation width 40 μm) near the interface of the via bottom was confirmed. For each evaluation board A, cross-section observation of 10 randomly selected vias was performed, and those with no voids at the bottoms of all 10 vias were marked with "○", and those with at least one were marked with "x". did.

The abbreviations in the table below are as follows.
630: Glycidylamine type epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 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 Industry Co., Ltd., (meth) acryloyl group equivalent 163 g / eq., Liquid thermosetting resin)
AA: Amine-based resin (Nippon Kayaku Co., Ltd., "Kayahard AA", liquid thermosetting resin)
L-DAIC: Allyl resin (manufactured by Shikoku Chemicals Corporation, liquid thermosetting resin)
ALP-d: Allyl resin (manufactured by JFE Chemical Co., Ltd., liquid thermosetting resin)
Synthesis Example 1: Polyimide resin YL7553BH30 produced in Synthesis Example 1: Phenoxy resin (manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK (methyl ethyl ketone) having a solid content of 30% by mass and cyclohexanone)
FPC0220: Carbonate resin (manufactured by Mitsubishi Gas Chemical Company)
YA050C-MJE: Silica (manufactured by Admatex, MEK solution with a solid content of 50% by mass, specific surface area 61.8 m ² / g, average particle size 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 about 190 g / eq., Solid thermosetting resin)
BA230S75: Prepolymer of bisphenol A disicanate (manufactured by Lonza Japan, cyanate equivalent of about 232 g / eq., MEK solution with 75% by mass of non-volatile content, solid thermosetting resin)
V-03: Carbodiimide-based curing agent (manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent of about 216 g / eq., Toluene solution having a non-volatile content of 50% by mass, solid thermosetting resin)
MIR-3000-70MT: Maleimide resin (manufactured by Nippon Kayaku Co., Ltd., MEK / toluene mixture with 70% by mass of non-volatile content, solid thermosetting resin)
Co _(acac) 3 -1M: curing accelerator (cobalt (III) acetylacetonate, nonvolatile content 1 wt% solution in MEK)
1B2PZ-10M: 1-benzyl-2-phenylimidazole (MEK solution with a solid content of 10% by mass)
Perbutyl C: Peroxide-based hardening accelerator (manufactured by NOF CORPORATION)

In Examples 1 to 14, it has been confirmed that even when the components (A-2) and (D) are not contained, the same results as those in the above-mentioned Examples are obtained, although the degree is different. ..

Claims (15)

A resin composition for forming an insulating layer for forming a conductor layer by sputtering.
Includes (A-1) liquid or semi-solid thermosetting resin and (B) thermoplastic resin.
(C) Does not contain or contains an inorganic filler,
The content of the inorganic filler (C) is 50% by mass or less when the non-volatile component in the resin composition is 100% by mass.
(C) A resin composition having a specific surface area of an inorganic filler of 40 m ² / g or more. The resin composition 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. The resin composition according to claim 1 or 2, wherein the component (A-1) is at least one selected from an epoxy resin, a (meth) acrylic resin, an amine resin, and an allyl resin. The item according to any one of claims 1 to 3, wherein the content of the 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. Resin composition. The resin composition according to any one of claims 1 to 4, wherein the component (B) is at least one selected from a polyimide resin, a polycarbonate resin, and a phenoxy resin. The resin composition according to any one of claims 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. object. The resin composition according to any one of claims 1 to 6, wherein the component (C) is silica. (A-2) The resin composition according to any one of claims 1 to 7, further comprising a solid thermosetting resin. The resin composition 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 composition 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 sheet for forming an insulating layer for forming a conductor layer by sputtering.
A support and a resin composition layer containing the resin composition provided on the support are included.
The resin composition contains (A) a thermosetting resin and (B) a thermoplastic resin, and (C) does not contain or contains an inorganic filler, and (C) the content of the inorganic filler is the resin composition. When the non-volatile component in the resin is 100% by mass, it is 50% by mass or less, and (C) the specific surface area of the inorganic filler is 40 m ² / g or more.
A resin sheet having a minimum melt viscosity of the resin composition layer of 100 poise or more and 4000 poise or less. A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition according to any one of claims 1 to 10. Printed wiring including an insulating layer formed by a cured product of the resin composition according to any one of claims 1 to 10 or a cured product of the resin composition layer of the resin sheet according to claim 11 or 12. Board. (1) A step of laminating the resin composition layer of the resin sheet according to claim 11 or 12 on the inner layer substrate so as to be bonded to the inner layer substrate.
(2) A step of thermosetting the resin composition layer to form an insulating layer.
A method for manufacturing a printed wiring board, which comprises (3) a step of drilling holes in the insulating layer and (4) a step of forming a conductor layer on the insulating layer by sputtering. A semiconductor device including the printed wiring board according to claim 13.

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